TW200911928A - Azo compound or salts thereof - Google Patents

Abstract

The present invention provides a novel azocompound which represents high color concentration and is represented by a formula (I) or a salt thereof. In the formula (I), Z represents O or S. A represents a phenyl group which is provided with at least one group selected from carboxy group, sulfo group, sulfamoyl and N-substituted sulfamoyl, or a naphthyl group which is provided with at least one group selected from sulfo group, sulfamoyl and N-substituted sulfamoyl. R<1> and R<2> are independent respectively, and represent hydrogen atom, aliphatic saturated group, alkoxy, aryl, aralkyl or acyl. R<3> to R<6> are independent respectively, and represent hydrogen atom, halogen atom, aliphatic saturated hydrocarbon, alkoxy, carboxyl group, sulfo group, sulfamoyl or N-substituted sulfamoyl.

Description

200911928 九、發明說明： 【兔明所屬之技術領域】 本發明係關於有用於作 、作為色素之偶氮化合物及其鹽。 【先前技術】 先前偶氮化合物等的色 如，纖維材料，液曰&quot;罢 各式各樣的領域(例 M不裝置等）使用於利用反射光或穿透 光顯示顏色，例如，已知右目士 乂穿透 已知有具有巴比妥酸骨架之偶氮化合 …1文獻1 具體而言’於專利文獻卜揭示2個 本~酸與i個巴比妥酸以2個偶氮基連結之色素。但是， ^玄專利文獻1，關於該色素之色特性，僅顯示，並 未記載任何其以外之特徵。 [專利文獻1]歐州專利申請公開第0163113號 【發明内容】 [發明所欲解決的課題] 、、近年，關於染色物的色濃度及色相，由需求客戶的要 求變嚴’特料要求色濃度高的新穎偶氮化合物及其鹽。 因此本發日月《目的係在於提供顯示高&amp;濃度之新穎偶氮化 合物及其鹽。 [用以解決課題的手段] 本發明者們，為改良偶氮化合物及其鹽之色濃度銳意 研九的Ί，發現具冑1)苯基或萘基、2)亞苯基、及3) 巴比女酸（包含硫代巴比妥酸）骨架的3個，經由2個偶氮 2226-9741-PF；Ahddub 5 200911928 基連結之構造之化合物及其鹽，顯示高的色濃度。由如此 之見識，達成上述目的之本發明之偶氮化合物及其鹽，係 以式（I)表示者。再者，於以下有將式（I)所示偶氮化合物 及其鹽，簡稱為「偶氮化合物（I )」之情形。以其他的化學 式表示之化合物或其鹽’亦有同樣地簡稱之情形。200911928 IX. Description of the invention: [Technical field to which the rabbit is attached] The present invention relates to an azo compound and a salt thereof which are used as a pigment. [Prior Art] Colors such as azo compounds and the like, such as fiber materials, liquid helium, etc., are used in various fields (for example, M is not used, etc.) for displaying colors by using reflected light or penetrating light, for example, known. The right eye of the scorpion is known to have a nitridation with a barbituric acid skeleton. 1 Document 1 Specifically, in the patent literature, it is revealed that two of the acids are linked to two barbiturates with two azo groups. Pigment. However, in the patent document 1, the color characteristics of the dye are only shown, and no other features are described. [Patent Document 1] European Patent Application Publication No. 0163113 [Draft of the Invention] [Problems to be Solved by the Invention] In recent years, the color density and hue of the dyed product have been tightened by the requirements of the demanding customer. High novel azo compounds and salts thereof. Therefore, the purpose of the present invention is to provide novel azo compounds and salts thereof which exhibit high & concentration. [Means for Solving the Problem] The present inventors have found that 胄1) phenyl or naphthyl, 2) phenylene, and 3) are known for improving the color concentration of azo compounds and their salts. Three of Barbie's female acid (including thiobarbituric acid) skeletons showed high color concentrations via two azo 2226-9741-PF; Ahddub 5 200911928-linked compounds and salts thereof. From the above, the azo compound and its salt of the present invention which achieve the above object are represented by the formula (I). In the following, the azo compound and its salt represented by the formula (I) are simply referred to as "azo compound (I)". The compound represented by another chemical formula or its salt' is also abbreviated as such.

式（I)中，Z係表示氧原子或硫原子； A係表示具有1個或2個選自由羧基、磺基、磺醯基 及N-取代續基所組成之群之至少1種基之苯基，或者具 有1〜3個選自Μ基及N_取代伽基所組成之群 之至少1種基之萘基； 基 之 R1及R2係分別獨立地表示，氫原子、 、有經基取代之Cl-ίο餘和脂肪煙基、有 C1 -1 α飽和脂肪烴 Cl-8院氧基取代 C 1 - I D餘和脂肪烴基 脂肪烴基、碳數為6〜20之芳基 或碳數為2~10之醯基； 有CM硫代烷氧基取代之 C 1 - I D飽和 碳數為7〜20之芳烷基、 、鹵素原子、Cl-I。飽 Ci-8烷氧基、羧基、 a以上，b以下之意 R3〜R6係分別獨立地表示，氫原子 和脂肪烴基、鹵化Cl_1Q飽和脂肪烴基 磺基、磺醯基或N-取代磺醯基。 再者，於本發明，Ca_b係指碳數為 思0 2226-9741-Pp;Ahddub 200911928 式（I)令，A以具有i個N-取代磺醯基之苯基 個N-取代石黃醯基之萘基為佳。上述N一取代石黃 —S〇綱7基（“表旨㈣基ϋ氧美取代 之^飽和脂肪烴基、碳數為6〜2〇之芳基、碳數為㈣ 2〜10之醯基)為佳。本發明之偶氮化 物及其鹽，藉由具有Ν —取代績基（較佳的是—灿臓7 ：； 水溶性及油溶性萘基。又，Α為具有1個瑞基之 r \ 本基或具有2個石黃基之萘基偶氣化合物及其鹽，亦為本發 明之較佳的態樣。為提升油溶性，式⑴中1及R2之至小 L個其以碳數6以上為佳^2之至幻個以碳數6〜2〇^ 方基更佳。 再者，於本發明之偶氮化合物及其鹽，除了式⑴所示 者’亦包含其互變異構物。 ^ [發明效果] 本發明之偶氮化合物及其鹽，係顯示高的色濃度’有 用於作為例如用於纖維材料或液晶顯示裝置等之色素。 【實施方式] 本發明之偶氮化合物及其鹽，如式⑴所示，I特徵在 於：具有υ苯基或萘基、2)亞苯基，及3)巴比妥酸㈣ =代巴比妥酸㈣）骨架之3個，經由2個偶氮基連結之 k再者’於巴比妥酸或硫代巴比妥酸部分，在式⑴ 所示之_型之外，亦包含豨醇型。藉由如此之構造，本發 明之偶氮化合物及其鹽，顯示高的色濃度。又，本發明之 2226-9741-PF/Ahddub 7 200911928 偶氮化合物及其鹽，在於其較佳的態#，對溶劑之溶解性 (特別是油溶性）優良，亦極為適於利用穿透光之顯色。再 者於上述办劑，可選例如，經基叛酸醋類（乳酸乙酿等）、 毁基酮類（二丙_醇等），喊類（丙二醇單甲冑、丙二醇單曱 醚醋酸酯等）等揮發性低的水溶性溶劑。In the formula (I), Z represents an oxygen atom or a sulfur atom; and A represents at least one group having one or two groups selected from the group consisting of a carboxyl group, a sulfo group, a sulfonyl group and an N-substituted group. a phenyl group or a naphthyl group having 1 to 3 groups of at least one group selected from the group consisting of a fluorenyl group and an N-substituted gal group; the R1 and R2 groups of the group independently represent a hydrogen atom and a thiol group; Substituted Cl-ίο and fatty nicotinyl, C1 -1 α saturated aliphatic hydrocarbon Cl-8, oxime substituted C 1 - ID and aliphatic hydrocarbyl aliphatic hydrocarbon group, aryl group having 6 to 20 carbon atoms or carbon number a fluorenyl group of 2 to 10; an aralkyl group having a C 1 - ID saturated carbon number of 7 to 20 substituted with a CM thioalkoxy group, a halogen atom, and a Cl-I. Fully Ci-8 alkoxy group, carboxyl group, a or more, b or less, R3 to R6 are each independently represented, a hydrogen atom and an aliphatic hydrocarbon group, a halogenated Cl_1Q saturated aliphatic hydrocarbon group sulfo group, a sulfonyl group or an N-substituted sulfonyl group. . Further, in the present invention, Ca_b means that the carbon number is S0 2226-9741-Pp; Ahddub 200911928 is a formula (I), and A is a phenyl N-substituted sulphate group having i N-substituted sulfonyl groups. Naphthyl is preferred. The above-mentioned N-substituted sulphate-S 〇 7 7 base ("the (4) ϋ oxime substituted by a saturated aliphatic hydrocarbon group, an aryl group having a carbon number of 6 to 2 fluorene, and a carbon number of (four) 2 to 10 fluorenyl) Preferably, the azo nitride of the present invention and a salt thereof have a ruthenium-substituted phenyl group (preferably, 臓 臓 7 :; water-soluble and oil-soluble naphthyl group. Further, Α has one ruthenium group. r \ base or a naphthyl azo compound having 2 cherishyl groups and a salt thereof are also preferred aspects of the invention. To improve oil solubility, 1 and R2 in formula (1) are as small as L The carbon number of 6 or more is preferably 2 to 2, and the carbon number is 6 to 2 〇 ^ square base. Further, the azo compound and the salt thereof of the present invention, except for the formula (1), also contain each other. [Effect of the Invention] The azo compound and the salt thereof of the present invention exhibit a high color density, and are useful as, for example, a pigment for use in a fiber material or a liquid crystal display device. The nitrogen compound and its salt, as shown in the formula (1), are characterized by having a fluorenylphenyl group or a naphthyl group, 2) a phenylene group, and 3) a barbituric acid (tetra) = a barbituric acid (tetra) skeleton. Three, k-linked via two azo groups, in the barbituric acid or thiobarbituric acid moiety, in addition to the _ type shown in formula (1), also contains a sterol type. The azo compound of the present invention and a salt thereof exhibit a high color density. Further, the 2226-9741-PF/Ahddub 7 200911928 azo compound of the present invention and a salt thereof are in a preferred state #, for a solvent It is excellent in solubility (especially oil-soluble) and is also very suitable for the color development of penetrating light. Further, in the above-mentioned agent, for example, a base acid-repellent vinegar (lactic acid, etc.), ruthenium ketone (Dipropylene-alcohol, etc.), a low-volatility water-soluble solvent such as propylene glycol monomethacrylate or propylene glycol monoterpene ether acetate.

、以下，詳細說明式⑴。式⑴中，A係表示具有^ 或2個l自由叛基、石頁基、續醯基及N_取代石黃酿基所組成 之群之至少1種基之苯基，或者具有卜3個選自由磺基、 磺醯基及N-取代磺醯基所組成之群之至少丨種基之萘基。 A之苯基或萘基，於上述必要取代基（苯基時，係羧基、 磺基、磺醯基及N-取代磺醯基之至少丨種；萘基時，磺基、 磺醯基及N-取代磺醯基之至少i種）以外，亦可具有}種 或2種以上其他的取代基，例如飽和脂肪烴基（甲基、 乙基等）、烷氧基（甲氧基，乙氧基等）、羥基或硝基。 但是，由色濃度的觀點，由於分子量小者較有利，故其他 的取代基，以僅具有C! _4飽和脂肪烴基，特別是僅具有甲 基或乙基者為佳，不具有其他的取代基者更佳。 A的苯基亦可具有2種上述必要之基，a的萘基亦可具 有2種以上上述必要之基，A的苯基或萘基’以具有磺基 及N-取代磺醯基之一方或雙方者為佳，僅具有磺基或僅具 有N-取代磺醯基者更佳。只要有磺基之存在則水溶性會變 尚’本發明之偶氮化合物及其鹽，可廣泛地使用於衣料領 域之色素。又只要有N-取代石黃醯基之存在，則本發明之偶 氮化合物及其鹽，優於水溶性及油溶性之雙方，可提高作 2226-974l-PF;Ahddub 8 200911928 為液晶表示裝置領域之 具有磺基之苯基A之I:有用性。 如具有1個磺基之苯基(2、_例’可舉僅具有磺基者’例 石黃基之苯基（2,4一二績酸Μ —或4'韻苯基）、具有2個 取代基者，例如甲基’具有石黃基與1種其他的 甲基-3-磺酸苯基、2_甲 ：基-2-磺酸苯基、4- 苯AU w —石頁醆苯基等），二甲基-磺酸 本基（4,6-二f基_2-磺酸 φ . 9 本基#)，甲氧基-磺酸苯基（4- 甲乳基-2-磺酸苯基、4_甲 0 氧基—飧酸苯基、2-甲氧基-3- 〜酉夂本基、2_甲氧基-4_ „ . q ^夂本基卓）；羥基-磺酸苯基（2 - 匕基-3-¾酸苯基、2_羥基—扣碏 -敲本基#);及具有磺基與 種上/、他取代基者，例如声其&amp; ,, L暴—确基-磺酸苯基（2-羥基 -3-硝基-5-磺酸苯基等）等。^ ^ — 7、r，以具有1個磺基之 笨基（亦稱為單磺酸苯基及 次具另石買基與C〗-4飽和脂肪烴 :之：基為佳’以3-磺酸苯基、4_磺酸苯基及4_甲基-3_ 磺酸苯基更佳，以4-磺酸苯基特別佳。 具有項基之萘基A之具體例，可舉具有1個確基之蔡 基（5-、6-、7-或8_磺基_2_萘基；4_、5_、6_或7—磺基_卜 萘基等）；具有2個磺酸苯基之萘基（6,8_、4,8_、5,7一或 3, 6-二磺基-2-萘基、3, 6-或4, 6-二磺基—卜萘基等）；及 具有3個磺基之萘基（3,6,8-或4,6,8-三磺基—2-萘基等） 等。該等之中，以具有2個磺酸苯基之萘基（亦稱為二磺酸 萘基）為佳，以二磺基-2-萘基更佳。 具有磺醯基或N-取代磺醯基之苯基或萘基之例，可舉 於具有績基之苯基或萘基之例’將項基以磺醯基或取代 2226-9741-PF;Ahddub 9 200911928 磺醯基取代者。N_取代磺醯基，可舉例如N_單取代$酿其 可以式-S〇2NHR7表示。具有N-取代磺酿基之A，、， 〜Λ，U於4位 具有-S〇2NHR7基之苯基特別佳。該R7係表示Γ 一 飽和脂肪 烴基（包含於該Cl —1()飽和脂肪烴基鍵結Ci 8^氧義者）石山 數為6〜20之芳基、碳數為7〜20之芳烷基、或碳數為 之醯基。 R7之飽和脂肪烴基以直鏈狀、分枝狀或環狀均可。於 飽和脂肪煙基之碳數並不包含取代基之碳數。其碳數之下 限，通常為1，較佳的是2,更佳的是6,其上限通常為， 較佳的是8。於R7之飽和脂肪烴基，包含例如，甲基、乙 基、正丙基、異丙基、正丁基、異丁基、第二丁基、第三 丁基、甲基丁基UH3-四甲基丁基等）、甲基土己基 J基己基' U —二甲基己基等）、乙基己基(2—乙基己基 等）、環戊基、環己基、甲基環己基（2_甲基環己基等）、環 己基烧基等。之縣，可以如上所述，^(較佳的是Μ ，氧基等^取代基取代。即[，亦可為^炫氧基（較佳的 疋c】-4烷氧基）取代之Ci…飽和脂肪烴基（較佳的是烷 基，更佳的是W基)。該取代烧基，可例示，丙氧基： 基（3-(異丙氧基）丙基等）等。 、R?之芳基，可為無取代，亦可具有烷基或羥基等之取 代基。上述芳基之碳數，以包含取代基之碳數數之，通常 編。’較佳的是6]〇。該等芳基，可舉例如，苯基、經 基苯基（4-羥基苯基等）、二氟 十；一齓r基本基（4 —二鼠甲基苯基等） 專之取代或無取代苯基等。 10 2226-974l-PF;Ahddub 200911928 κ7之芳烷基（芳基烷基）之 ,,+, — 疋基部分，以直鏈狀或分枝 狀均可。方烷基之碳數，通常為 _ 勺卜20 ’杈佳的是7〜10。該Hereinafter, the formula (1) will be described in detail. In the formula (1), the A system represents a phenyl group having at least one group of ^ or 2 l-free radicals, a sulphate group, a fluorenyl group, and an N-substituted schistosyl group, or has 3 groups of A naphthyl group of at least an anthracene group selected from the group consisting of a sulfo group, a sulfonyl group and an N-substituted sulfonyl group. A phenyl or naphthyl group of A, in the above-mentioned essential substituent (phenyl group, at least a sulfonium group, a sulfo group, a sulfonyl group, and an N-substituted sulfonyl group; a naphthyl group, a sulfo group, a sulfonyl group and In addition to at least one of the N-substituted sulfonyl groups, there may be one or two or more other substituents such as a saturated aliphatic hydrocarbon group (methyl group, ethyl group, etc.), an alkoxy group (methoxy group, ethoxy group). Base, etc.), hydroxyl or nitro. However, from the viewpoint of color density, since the molecular weight is small, other substituents have a C! _4 saturated aliphatic hydrocarbon group, and particularly only a methyl group or an ethyl group, and have no other substituents. Better. The phenyl group of A may have two kinds of the above-mentioned essential groups, and the naphthyl group of a may have two or more kinds of the above-mentioned essential groups, and the phenyl or naphthyl group of A has one of a sulfo group and an N-substituted sulfonyl group. It is preferred that both of them are preferred, and those having only a sulfo group or only an N-substituted sulfonyl group are preferred. As long as the sulfo group is present, the water solubility is changed. The azo compound of the present invention and a salt thereof can be widely used as a pigment in the field of clothing. Further, as long as the N-substituted sulphate group is present, the azo compound and the salt thereof of the present invention are superior to both water-soluble and oil-soluble, and can be made into 2226-974l-PF; Ahddub 8 200911928 is in the field of liquid crystal display devices. I of phenyl group A having a sulfo group: usefulness. For example, a phenyl group having 1 sulfo group (2, - for example, a phenyl group having only a sulfo group), a phenyl group (2, 4 - 2 - oxo- or 4'-phenyl), having 2 Substituents such as methyl 'has a diphthyl group with one other methyl-3-sulfonic acid phenyl group, 2-methyl-2-yl sulfonic acid phenyl group, 4-phenyl AU w — shale Phenyl, etc.), dimethyl-sulfonic acid base (4,6-dif-based-2-sulfonic acid φ. 9 base #), methoxy-sulfonic acid phenyl (4-methyllacyl-2) - phenyl sulfonate, 4-methyloxy-decanoic acid phenyl, 2-methoxy-3- oxime-based, 2-methoxy-4_ „. q^夂本基卓); hydroxy - sulfonic acid phenyl (2- fluorenyl-3-3⁄4 acid phenyl, 2-hydroxyl-oxime-knock base #); and those having a sulfo group and a species/, a substituent thereof, for example, acoustic &amp; , L violence - succinyl-sulfonic acid phenyl (2-hydroxy-3-nitro-5-sulfonic acid phenyl, etc.), etc. ^ ^ - 7, r, with a sulfo group of stupid (also It is called phenyl monosulfonate and sub-stone and C--4 saturated aliphatic hydrocarbon: it is better than 3-sulfonic acid phenyl, 4-sulfonic acid phenyl and 4-methyl-3_ The phenyl sulfonate is more preferred, and the 4-sulfonic acid phenyl group is particularly preferred. Specific examples of the naphthyl group A include a decyl group (5-, 6-, 7- or 8-sulfo-2-naphthyl group; 4_, 5_, 6- or 7-sulfo-p-naphthyl group). And other naphthyl groups having 2 sulfonic acid phenyl groups (6,8-, 4,8-, 5,7- or 3,6-disulfo-2-naphthyl, 3,6- or 4,6-di a sulfo-naphthyl group; and a naphthyl group having 3 sulfo groups (3,6,8- or 4,6,8-trisulphenyl-2-naphthyl, etc.), etc. Preferably, the naphthyl group of the phenyl sulfonate (also known as naphthyl disulfonate) is more preferably a disulfo-2-naphthyl group. The phenyl or naphthyl group having a sulfonyl group or an N-substituted sulfonyl group. For example, it may be exemplified by a phenyl or naphthyl group having a base of 'sulfonyl group or substituted 2226-9741-PF; Ahddub 9 200911928 sulfonyl group substituted. N_substituted sulfonyl group, For example, N_monosubstituted can be represented by the formula -S〇2NHR7. A,,, Λ, U having an N-substituted sulfonyl group is particularly preferred as a phenyl group having a -S〇2NHR7 group at the 4-position. Γ represents a saturated aliphatic hydrocarbon group (included in the Cl-1 () saturated aliphatic hydrocarbon group bonded Ci 8 ^ oxygen sense) stone mountain number of 6 to 20 aryl, carbon number of 7 to 20 aralkyl, The carbon number is the sulfhydryl group. The saturated aliphatic hydrocarbon group of R7 may be linear, branched or cyclic. The carbon number of the saturated fatty tobacco group does not include the carbon number of the substituent. The lower limit of the carbon number is usually 1 is preferably 2, more preferably 6, and the upper limit is usually 8, preferably 8. The saturated aliphatic hydrocarbon group at R7 contains, for example, methyl, ethyl, n-propyl, isopropyl, n-Butyl, isobutyl, t-butyl, tert-butyl, methylbutyl UH3-tetramethylbutyl, etc.), methyl hexyl J-hexyl group 'U-dimethylhexyl, etc.), B A hexyl group (2-ethylhexyl group, etc.), a cyclopentyl group, a cyclohexyl group, a methylcyclohexyl group (2-methylcyclohexyl group, etc.), a cyclohexyl group, and the like. The county may be substituted as described above, (preferably, an anthracene, an oxy group, etc., which is substituted by a substituent such as [, may also be a methoxy group (preferably 疋c]-4 alkoxy group). a saturated aliphatic hydrocarbon group (preferably an alkyl group, more preferably a W group). Examples of the substituted alkyl group include a propoxy group: a group (3-(isopropoxy)propyl group, etc.), and R. The aryl group may be unsubstituted or may have a substituent such as an alkyl group or a hydroxyl group, etc. The carbon number of the above aryl group is usually a number of carbons including a substituent, and is preferably 6] The aryl group may, for example, be a phenyl group, a phenyl group (4-hydroxyphenyl group or the like), a difluoro-decene group; a fluorenyl group (4-dimethylmethylphenyl group, etc.) or Unsubstituted phenyl, etc. 10 2226-974l-PF; Ahddub 200911928 κ7 aralkyl (arylalkyl),, +, — fluorenyl moiety, either linear or branched. The carbon number is usually _ spoon b 20 ' 杈 good is 7~10.

方烧基’代表性的有苄基、！I 裳、1 &quot; 本基丙基(卜甲基-3-苯基丙基 4)、本基丁基（3-胺基—1 —苯基 n7 丞丁基等）等之苯基烷基。 R之醯基，可為無取代， Γ有飽和脂肪烴基、烷氧 土寺之取代基鍵結。醯基之碳數， 以包含取代基之碳數數 之，其數，通常為2〜10,較佳的县 的疋6〜1 0。上述醯基，係例 如乙醯基、苯甲基、甲氧基苯甲基 升τ丞qp-甲虱基苯甲基等）等。 上述由更加提高U度、油溶性等之觀點，亦可 進-步限定。於如此之R、可舉例如，甲基丁基(m3— 四甲基丁基等）、甲基己基(1，5_二甲基己基等）、乙基己基 (2-乙基己基等）、f基環己基（2_甲基環己基等）、笨基丙 基（1-甲基-3-苯基丙基等）、苯基丁基（3_胺基_丨_苯基丁基 荨）等之分枝狀飽和脂肪烴基、或芳院基。 式（I)中，R1及R2係分別獨立地表示，氫原子、 )飽和脂肪烴基、羥基取代之c,,飽和脂肪烴基、Ci_8烷氧基 取代之Ci-iO飽和脂肪烴基、C,-8硫代烷氧基取代之Ci !。飽 和脂肪烴基、碳數為6〜20之芳基、碳數為7〜20之芳烧基、 或碳數為2~10之醯基。 R1及R2之飽和脂肪烴基以直鏈狀、分枝狀或環狀均 可。於飽和脂肪烴基之碳數，不含取代基之碳數。該碳數 之下限’通常為1，較佳的是2，更佳的是3，其上限，通 常為10，較佳的是8，更佳的是6，進一步以4為佳。於 餘和脂肪烴基’例如，曱基、乙基、正丙基、異丙美、正 2226-974l_PF;Ahddub 11 200911928 土異丁基、第二丁基、第三丁基、乙基己基（2 -乙基己 基等）、裱戊基、環己基、環己基烷基等。又在於飽和脂肪 烴基，如上所述，亦可以羥基、(較佳的是C!-4)烷氧基、 或匕-8(較佳的是c^)硫代烷氧基等的取代基取代。該取代 釦彳月曰肪烃基，可舉例如，羥基乙基（2 _羥基乙基等）、乙 氧基乙基（2—乙氧基乙基等），乙基己基氧基丙基（3-(2-乙 基己基氧基）丙基等），甲基硫代丙基（3 一甲基硫代丙基等） 等。 R及K2之芳基，可為無取代，亦可具有飽和脂肪烴基、 烷氧基、羧基、磺基或酯基等之取代基。上述芳基之碳數， 以包含取代基之碳數數之，通常為6〜2〇，較佳的是。 該等芳基，可舉例如，苯基；2-、3-、4—曱基苯基；2_、 3-、4-磺酸苯基等之取代或無取代苯基等。 R1及R2之芳烷基之烷基部分，以直鏈狀或分枝狀均 可。芳烷基之碳數，以包含取代基之碳數數之，通常為 7〜20，較佳的是7~1〇。該芳烷基，代表性的有节基等的苯 基烷基。 R及R之酿基’可為無取代，亦可與飽和脂肪烴基、 烷氧基等之取代基鍵結。醯基之碳數，以包含取代基之碳 數數之，其數，通常為2〜10，較佳的是6〜1〇。上述醯基， 係例如，乙醯基、苯甲基、甲氧基笨甲基(p—甲氧基苯甲基 等）等。 為進一步提高色濃度，建議於R1及R2之至少一個（較 佳的是雙方），選擇碳數為5以下（較佳的是3以下）之基（例 2226-9741-PF;Ahddub 12 200911928 甲基、乙基等），或氫原子。— 人物纟n 一 u 方面，為技高偶氮化 口物（I)對洛劑之溶解性， 雙方），撰煜、κ及R之至少1個（較佳的是 万）選擇奴數為6以上之其盔 代之若美… 之基為佳，特別是以取代或未取 代之方基（較佳的是苯基）為佳。 μ式⑴中U6係分別獨立地表示，氫原子、_素原 ==則、氯㈣原子）、“飽和脂肪 石 =子 該^飽和脂肪煙基者）、l烧氧基、缓基、 尹、基、石尹、醯基或N_取代磺醯基。 〜6之餘和脂肪烴基，與R、R2之情形同樣地，以直 鏈狀、分枝狀或環狀均可，1 #垂i 狀0了其石反數，通常為1〜10 ,較佳的 疋1~8，更佳的是1〜 R之飽和脂肪烴基之具體例， 矣R及R之情形相同。K3〜V夕奶*此 ^ K之飽和脂肪烴基，可以鹵素原 子，車父佳的是以截眉石衝处 . ’、取代。豳化飽和脂肪煙基之具體例， 可舉三氟甲基等。 R3〜R6之絲基之碳數，通常為卜8,較佳的是卜4。 該烧氧基’可舉例如、甲氧基、乙氧基，#丙氧基、正丙 氧基、正丁氧基、異丁氧基、第二丁氧基、及第三丁氧基 等。 R〜R6之N-取代磺醯基，可舉已於式⑴，的a所說明 者0 *上述R R由提南色漠度、水溶性、油溶性、财光性 等之觀點，亦可進_步限定。例如由提高水溶性之觀點， 採用石黃基作為為卢。益+ _ 马仏猎由燊而水溶性，可在衣料領域 廣泛地使用作為色音。旦本 ^ , 巴京·再者’為提咼色濃度及水溶性之雙 2226-9741-pp；Ahddub 13 200911928 方5建議於P3 η 6 , R之中採用1個確基，於剩下的r 3〜r e採用 風原子。惟，# _y_ 本基或萘基A具有磺基時，由提高色濃度之 觀點，較佳&amp; β ^ ^ 、疋R〜R虱原子或C卜*飽和脂肪烴基， 是R3〜R1之中！加* r 1個為c 1 _4飽和脂肪烴基（特別是甲基或乙 土）而剩下的為氫原子，進一步使R3〜R&lt;5之全部以氫原子 為佳。 由提间色濃度與油溶性之觀點，建議於之 個或2個以上，接 採用二氟甲基、N —取代磺醯基。 於剩下的捏&amp;甘 可稽田 ^ 擇S基以外之基，可更加提高油溶性。 、由提高对光性之觀點，建議靖1之中的Η固或2個 以上，選擇體積大的基。由於 w K K對偶虱基均位於鄰位 位置，故藉由採用體積大的基 徒间本發明之偶氮化合 一之耐光性。上述體積大的R3~RS可 等的分枝狀飽和脂肪烴基（特 弟—丁基 / ，]疋3級飽和脂肪烴基），二 氣甲基等與2個以上（特別是 ；一 2226-974l-PF;Ahddub 14 1 &lt; p W 乂上）的鹵素原子鍵结之 飽和知肪烴基、N-取代磺醯基等。 具有磺基之偶氮化合物（1)， 刖甘工、Λ Ζ為乳原子或硫原子（特 別疋巩原子），Α為磺酸苯基（特 行別疋4-磺酸苯基），Ri月 R係分別獨立地為Ch烷基（特 ,, 、 j疋Ch烷基），R3〜ν # 別獨立地為氫原子或3烷基— ” 、荷別疋虱原子）之化合物 別佳。A具有磺基之較佳的化口物特 風*化合物（丨），可舉例 (1-1)~(1-10)所示化合物： 式 200911928The square base is representative of benzyl,! I Benzene, 1 &quot; phenylalkyl group such as propylidene (p-methyl-3-phenylpropyl 4), benzylidene (3-amino-1-phenyl n7 fluorenyl butyl, etc.). The thiol group of R may be unsubstituted, and has a saturated aliphatic hydrocarbon group and a substituent of alkoxylate temple. The carbon number of the thiol group, which is the number of carbon atoms including the substituent, is usually 2 to 10, preferably 疋6 to 1 0 of the county. The above mercapto group is, for example, an ethyl hydrazino group, a benzyl group, a methoxybenzyl group, a τ丞qp-methylmercaptobenzyl group or the like. The above may be further limited by the viewpoint of further improving the U degree, oil solubility, and the like. Examples of such R include methylbutyl (m3-tetramethylbutyl or the like), methylhexyl (1,5-dimethylhexyl, etc.), and ethylhexyl (2-ethylhexyl). , f-cyclohexyl (2-methylcyclohexyl, etc.), stupidylpropyl (1-methyl-3-phenylpropyl, etc.), phenylbutyl (3-amino-indole-phenylbutyl)分)) a branched saturated aliphatic hydrocarbon group, or a aryl group. In the formula (I), R1 and R2 each independently represent a hydrogen atom, a saturated aliphatic hydrocarbon group, a hydroxyl group substituted c, a saturated aliphatic hydrocarbon group, a Ci_8 alkoxy-substituted Ci-iO saturated aliphatic hydrocarbon group, C, -8. Substituting thioalkoxy for Ci!. The saturated aliphatic hydrocarbon group, the aryl group having a carbon number of 6 to 20, the aryl group having a carbon number of 7 to 20, or the fluorenyl group having a carbon number of 2 to 10. The saturated aliphatic hydrocarbon group of R1 and R2 may be linear, branched or cyclic. The carbon number of the saturated aliphatic hydrocarbon group does not contain the carbon number of the substituent. The lower limit ' of the carbon number is usually 1, preferably 2, more preferably 3, and the upper limit is usually 10, preferably 8, more preferably 6, and further preferably 4. And an aliphatic hydrocarbon group 'e.g., decyl, ethyl, n-propyl, isopropyl, n- 2226-974l_PF; Ahddub 11 200911928, tert-butyl, t-butyl, tert-butyl, ethylhexyl (2 -ethylhexyl or the like), indolyl, cyclohexyl, cyclohexylalkyl and the like. Further, in the case of a saturated aliphatic hydrocarbon group, as described above, a substituent such as a hydroxyl group, (preferably C!-4) alkoxy group, or a fluorene-8 (preferably c^) thioalkoxy group may be substituted. . The substituted fluorene hydrocarbon group may, for example, be a hydroxyethyl group (2-hydroxyethyl group, etc.), an ethoxyethyl group (2-ethoxyethyl group, etc.), or an ethylhexyloxypropyl group (3). -(2-ethylhexyloxy)propyl, etc.), methylthiopropyl (3-methylthiopropyl, etc.) and the like. The aryl group of R and K2 may be unsubstituted or may have a substituent such as a saturated aliphatic hydrocarbon group, an alkoxy group, a carboxyl group, a sulfo group or an ester group. The carbon number of the above aryl group is usually 6 to 2 Å, preferably 6 to 2 Å, based on the number of carbon atoms of the substituent. Examples of the aryl group include a phenyl group; a 2-, 3-, 4-nonylphenyl group; a substituted or unsubstituted phenyl group such as a 2-, 3-, 4-sulfonic acid phenyl group or the like. The alkyl moiety of the aralkyl group of R1 and R2 may be linear or branched. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 1 Torr, based on the number of carbon atoms including the substituent. The aralkyl group is typically a phenylalkyl group having a group or the like. The R and R aryl groups may be unsubstituted or may be bonded to a substituent such as a saturated aliphatic hydrocarbon group or an alkoxy group. The carbon number of the fluorenyl group, which is a number of carbon atoms including a substituent, is usually 2 to 10, preferably 6 to 1 Å. The above mercapto group is, for example, an ethyl benzyl group, a benzyl group, a methoxymethyl group (p-methoxybenzyl group, etc.). In order to further increase the color density, it is recommended to select at least one of R1 and R2 (preferably both), and select a base having a carbon number of 5 or less (preferably 3 or less) (Example 2226-9741-PF; Ahddub 12 200911928 A Base, ethyl, etc.), or a hydrogen atom. — the character 纟n u, in terms of the solubility of the technically high nitriding mouth (I) to the agent, both sides), at least one (preferably 10,000) of the 煜, κ, and R More preferably, the helmet is more preferably a base, especially a substituted or unsubstituted square group (preferably a phenyl group). In the formula (1), the U6 system is independently represented by a hydrogen atom, a γ element ===, a chlorine (tetra) atom, a "saturated fat stone = a sub-saturated fatty smoky base", an alkoxy group, a slow base, and Yin. , base, stone Yin, sulfhydryl or N_ substituted sulfonyl group. 〜6 and aliphatic hydrocarbon group, as in the case of R, R2, linear, branched or cyclic, 1 #垂i has a stone inverse number, usually 1 to 10, preferably 疋1 to 8, more preferably a specific example of a saturated aliphatic hydrocarbon group of 1 to R, and the case of 矣R and R is the same. K3~V Milk * This is a saturated aliphatic hydrocarbon group of K, which can be a halogen atom, and the car father is rushed with an eyebrow. ', a substitute. A specific example of a saturated fatty acid group, such as trifluoromethyl. R3~ The carbon number of the filament of R6 is usually VIII, preferably 卜. The alkoxy group may, for example, be methoxy, ethoxy, #propoxy, n-propoxy or n-butoxy a group, an isobutoxy group, a second butoxy group, a third butoxy group, etc. The N-substituted sulfonyl group of R to R6 is exemplified by a of the formula (1), and the above RR is Southern color, water solubility, oil solubility, wealth The viewpoint can also be defined in steps. For example, from the viewpoint of improving water solubility, the stone yellow base is used as the Lu. The benefit + _ horse hunting is water-soluble and can be widely used as a color tone in the field of clothing. This ^, Bajing · Again' for the color concentration and water solubility of the double 2226-9741-pp; Ahddub 13 200911928 square 5 is recommended to use P3 η 6 , R in the 1 basis, the rest of the r 3~re uses a wind atom. However, when the #_y_benyl or naphthyl A has a sulfo group, it is preferably &amp; , is R3 to R1! Adding * r 1 is c 1 _4 saturated aliphatic hydrocarbon group (especially methyl or ethyl) and the remaining one is a hydrogen atom, further making all of R3~R&lt;5 From the viewpoint of color concentration and oil solubility, it is recommended to use difluoromethyl or N-substituted sulfonyl groups for one or more of them. For the remaining pinch &amp; Gan Keji field The base other than the base can further improve the oil solubility. From the viewpoint of improving the lightness, it is recommended to tamping or two or more in Jing 1 and selecting a large base. Since the w KK pair fluorenyl group is located at the ortho position, the light susceptibility of the azo-nitride of the present invention is large by using a bulky R3~RS, and the branched saturated aliphatic hydrocarbon group can be equalized. a halogen atom bond of two or more (particularly; a 2226-974l-PF; Ahddub 14 1 &lt; p W 乂) with a diter-butyl/,] 疋3 saturated aliphatic hydrocarbon group) A saturated aliphatic hydrocarbon group, an N-substituted sulfonyl group, etc. an azo compound having a sulfo group (1), a ruthenium or a sulfonium atom (a sulfonium atom), and a sulfonate benzene The base (specially different from 4-sulfonic acid phenyl), Ri month R is independently Ch alkyl (special, j, Ch alkyl), R3 ~ ν # are independently hydrogen or 3 alkane The compounds of the base — ” and the Hebrew atoms are better. A preferred compound having a sulfo group is a compound (丨), which can be exemplified by the compounds of the formula (1-1) to (1-10): Formula 200911928

(1-2) (1-3) (Μ)(1-2) (1-3) (Μ)

\\

(1-7) (1-8) (1-9) (1-10) 具有Ν-取代磺醯基之偶氮化合物（I )，可舉Ζ 為氧原 2226-9741-PF；Ahddub 15 200911928 # 子（特別是氧原子），A係於4位具有-SChNHR7蟇之 本基，R7氧r 马Cl,烷基（較佳的是C6…烷基）、或有Ch烷氧 基C特C 4徐备·《、 虱基）取代之Cl,烷基（較佳的是Ch烷基、特 別疋 Ll - 4搶装、 ^ 1(1-7) (1-8) (1-9) (1-10) The azo compound (I) having an anthracene-substituted sulfonyl group, exemplified by an oxygen source 2226-9741-PF; Ahddub 15 200911928 #子(especially an oxygen atom), A is a group having -SChNHR7蟇 at the 4-position, R7 oxygen r-maCl, an alkyl group (preferably a C6...alkyl group), or a Ch alkoxy group C 4 Xu Bei · ", thiol" substituted Cl, alkyl (preferably Ch alkyl, especially 疋 Ll - 4 grab, ^ 1

Ci3烧基），^ ，及R2係分別獨立地為Cl-6炫基（特別是 氫原子)之化合：分別獨立地為氫原子或C&quot;烧基(特別是 特別佳。A為具有N-取代續醯基之較私^ 偶氮化合物议位的 可舉例如式（I -11)〜（I -20)所示之化合物·The Ci3 alkyl group, ^, and R2 are each independently a compound of a Cl-6 leukox group (particularly a hydrogen atom): each independently a hydrogen atom or a C&quot;alkyl group (especially particularly preferred. A is N-) The compound represented by the formula (I -11) to (I -20) may be mentioned as a compound of the arsenic compound which is substituted for the thiol group.

〇〇

N 0. 0 N )=〇 (卜11)N 0. 0 N )=〇 (卜11)

&gt;=〇 -N6' q (Η 2)&gt;=〇 -N6' q (Η 2)

N Ο i&quot;^C_3&gt;~~N=N )=〇 (1-13) ^_/~^N、S〇2^0^N=NO~N=N~^}=〇 (Η4) 2226-9741-PF;Ahddub 16 200911928N Ο i&quot;^C_3&gt;~~N=N )=〇(1-13) ^_/~^N, S〇2^0^N=NO~N=N~^}=〇(Η4) 2226- 9741-PF; Ahddub 16 200911928

(1-15) (Μ 6) (Μ7) / 〇(1-15) (Μ 6) (Μ7) / 〇

NH~S〇2~^ ^~Ν=Ν~~〈〉—Ν=Ν—)=0 α-18) 〇 ^3~NH's〇2〇~N=N^3~r ΟNH~S〇2~^ ^~Ν=Ν~~〈〉—Ν=Ν—)=0 α-18) 〇 ^3~NH's〇2〇~N=N^3~r Ο

Ν Η Ν=Ν—( )=0 (1-19) •Ν 〇 NH~~S02~^~^—Ν=Ν—〈 ^―Ν=Ν-\^~ y=〇 (Ι~20) Ο 本發明，並非限定於式（I)所示之化合物，亦包含其 鹽。鹽，可舉磺酸鹽或羧酸鹽等。又，形成該等鹽之陽離 子並無特別限定，考慮對溶劑之溶解性，則以鋰鹽、鈉鹽、 鉀鹽等鹼金屬鹽；銨鹽；及乙醇胺鹽、烷基胺鹽等有機胺 鹽等為佳。特別是鹼金屬鹽（較佳的是鈉鹽），有用於含在 偏光膜基材之情形。又，有機胺鹽，有用於含在樹脂硬化 性化合物之情形，再者，由於是非金屬鹽，亦有用於重視 絕緣性之領域。 2226-9741-PF;Ahddub 17 200911928 本發明之偶氮化合 ’可如色素領域所習知，可葬由 使重氮鹽與巴比妥酸或栌 了籍由Ν Η Ν=Ν—( )=0 (1-19) •Ν 〇NH~~S02~^~^—Ν=Ν—< ^―Ν=Ν-\^~ y=〇(Ι~20) Ο The present invention is not limited to the compound represented by the formula (I), and also includes a salt thereof. The salt may, for example, be a sulfonate or a carboxylate. Further, the cation forming the salt is not particularly limited, and an alkali metal salt such as a lithium salt, a sodium salt or a potassium salt; an ammonium salt; and an organic amine salt such as an ethanolamine salt or an alkylamine salt are considered in consideration of solubility in a solvent. It is better. In particular, an alkali metal salt (preferably a sodium salt) is used in the case of being contained in a polarizing film substrate. Further, the organic amine salt is used in the case of a resin-curable compound, and further, it is a non-metal salt, and is also used in the field of insulating the insulating property. 2226-9741-PF; Ahddub 17 200911928 The diazotization of the present invention can be ruined by the use of diazonium salts and barbituric acid, as is known in the art of pigments.

Af Λ ，丨L代巴比女酸（以下將該等一併稱 马〔石瓜代）巴比女酸丨h里人 」^媽合而製造。例如可將藉由 亞硝酸鹽或亞硝酸酯侫 稭田m A 式（a)所示胺類（重氮成分）重氮化 而侍之式（b)之化合物 使用作為上述重氮Si (式m 中，Λ及R3〜R6，係表+访 扎里虱aC式Ca)及（b) y、與上述相同意思）。Af Λ 丨 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代 代For example, a compound of the formula (b) can be used as the above diazo Si by diazotizing the amine (diazo component) represented by the formula (a) by nitrite or nitrite. m, Λ and R3 to R6, the table + interview Zhali 虱 aC formula Ca) and (b) y, the same meaning as above).

(b) NH2 (a) 然後可使重氮鹽（b)，鱼 一 人Λ、八A /、工（C)所示（硫代）巴比妥酸（偶 δ成刀）’通*在水性溶劑 〇 中乂 20~6〇c反應，而製槪尧 化合物（1)(式（c)中，Ri及R2^ 而k偶氣 〇. R1 κ係表示與上述相同意思）。 -Ν(b) NH2 (a) can then be used to make diazonium salt (b), fish one person 八, eight A /, work (C) (thio) barbituric acid (even δ into a knife) The solvent 〇 is reacted with ~20~6〇c, and the oxime compound (1) (in the formula (c), Ri and R2^ and k 〇 gas 〇. R1 κ system means the same meaning as above). -Ν

• Λ 〇 V (c) 於式（I)R3〜R6之至少] &amp;，祕士 + 彳固為項酿基或N-取代磺醯美目 的化合物，雖亦可藉由使用 &quot;醞基目 ”有蟥醯基或N-取代磺醯其夕 胺類（a)製造，但在使用具右 、-土 只基之胺類（a)進行偶人及庫 後，再磺醯胺化製造較確訾 叮堝口反應 例如先合成在於式（丨）具有磺 2226-9741-PF;Ahddub 18 200911928 基之化合物（以下，稱為「偶氮磺酸（ί)」），藉由亞硫酿齒 化合物將磺基（-S〇sH)變成磺醯鹵（-SOJ ; X為鹵素原子）， 接著藉由與胺反應而可將磺基磺醯胺化。 於偶氮磺酸（I)之較佳的例，可舉包含式 (1-1)~(1-10)，特別是式（Ι — υ、（I—2)、（卜5)、（I —6)及 (I-9)。亞硫醯鹵化合物，可例示亞硫醯氟、亞硫醯氣、亞 硫醯溴、亞硫醯碘等，較佳的是亞硫醯氯、亞硫醯溴等， 特別是亞硫醯氯。亞硫醯鹵之使用量，對偶氮磺酸π)ι莫 耳，例如為Η0莫耳程度。再者，於反應系、中帶入水時 過剩使用亞硫醯鹵化合物為佳。 磺醯由化，通常，係於溶劑中進行。溶劑，可使用例 如，1，4-二噁烷等醚類（特別是環狀醚類）；氣仿、二氯曱 烧、四氣化碳、；[，2_二氣 _ ^ 好 ^ ^ 一虱乙烯'三氣乙烯、全 氯乙烯、二氣丙燒、正戍其 土戊基虱、1,2-二溴乙烷等之鹵化烴 二。：劑之广用量，對偶氮化合物⑴1質量部，例如以 ，部：顺圭…質量部以上)，1〇質量部以下(較 佳的疋8質罝部以下）之程度。 又’在於石黃醯鹵化奢 ,w Μ φ . 建4並用N，N一二烷基甲醯胺（例 如N，N-二曱基甲醯胺，N _ ，N —乙基甲醯胺等使用N 二烷基曱醯胺時，且#用曰• Λ 〇V (c) at least in the formula (I) R3 to R6 &amp;, the priest + tamping is a compound based on N-substituted sulfonamides, although it can also be used by using Manufactured with sulfhydryl or N-substituted sulfonamides (a), but after the use of amines with a right-and-soil-based group (a), the sulfonamide The sputum reaction is, for example, first synthesized by a compound of the formula (丨) having a sulfo 2226-9741-PF; Ahddub 18 200911928 (hereinafter referred to as "azo sulfonic acid (")), which is brewed by sulphur. The dentate compound changes the sulfo group (-S〇sH) to a sulfonium halide (-SOJ; X is a halogen atom), and then the sulfosulfonium can be aminated by reacting with an amine. Preferred examples of the azosulfonic acid (I) include the formulae (1-1) to (1-10), particularly the formulas (Ι-υ, (I-2), (Bu 5), ( I—6) and (I-9). The sulfinium halide compound may, for example, be sulfinium fluoride, sulfoxide, sulfinium bromide, sulfinium iodide or the like, preferably sulfinium chloride, arylene Thiopurine bromide, etc., especially sulphur sulfonium chloride. The amount of sulfinium halide used, for azo sulfonate π) ι mole, for example, Η0 mole level. Further, it is preferred to use a sulfoxide halogen compound in excess of the reaction system and water. The sulfonium is catalyzed, usually, in a solvent. As the solvent, for example, an ether such as 1,4-dioxane (especially a cyclic ether); gas-form, dichlorohydrazine, tetra-carbonized carbon; [, 2_二气_^好^^ A halogenated hydrocarbon of ethylene, such as ethylene tris, perchloroethylene, dipropylene, orthoquinone, 1,2-dibromoethane or the like. The amount of the agent to be used is, for example, the mass of the azo compound (1), the mass portion of the azo compound (1), for example, the mass fraction of the azo compound (1), and the mass of the azo compound (1). Also 'in the scutellaria, halogenated luxury, w Μ φ. Build 4 and use N, N-dialkylformamide (such as N, N-dimercaptocaramine, N _ , N - ethyl formamide, etc. When using N-dialkyl decylamine, and #用曰

n ^ /用夏，對亞硫醯齒1莫耳，例如A 〇·〇5〜1莫耳程度。將偶氮 斗 為 乳尹、酉文（I)與Ν，Ν-二烷基曱醯脸子首 先於溶劑巾混合後，添力σ κ ^ 机丞Τ〜預 〜亞爪S&amp;鹵，則可抑制發埶。 。反應溫度，例如為代以上（較佳的是阶以上 C以下（較佳的是β 〇。〇以 )。反應時間，例如為0· 5小時 2226-974l-PF;Ahddub 19 200911928 以上(較佳的是3小時以上），8小時以下(較佳的是5小時 以下）之程度。 士上述凋製之〜醯_化合物，可單離再與胺反應，亦 可不單離而直接以反應混合物與胺反應。再者單離時，例 如，將反應混合物與水混合，渡取析出之結晶即可。取得 之石貧酿鹵化合物之結晶，亦可按照需要於與胺反應前，水 洗及乾燥。 / 上述胺，可舉例如，1級胺’該1級胺係式M-R7所 W與上述相同）。於M_R7之具體例’包含正丙基胺、 =丁基胺、正己基胺、二甲基己基胺(1，5-二甲基己基胺 仆四甲基丁基胺四甲基丁基胺等)、乙基己基 …等)、胺基苯基丁跡胺基+苯基丁炫 寺），、丙氧基丙基胺等。胺之佶用旦批** 草耳，福Μ 哥妝之使用里’封磺醯南化合物1 、 、吊為2莫耳以上，^ 〇莫耳 以下）之靜。$ i 莫耳乂下（較佳的是7莫耳 ^ 者，於本說明書，為將該胺，與 性觸媒區别，以下有稱為反應性胺之情形。〃 碩醯鹵化合物與胺之添加順 鹵化合物添加(滴入)胺之情形為多。：=一醯 胺之反應，通常於溶劑中進行。溶：=化合物與 鹵化合物時同樣的溶劑。 使用與調製磺醯 又，石黃酿齒與反應性胺之反應，的 白Γ子在下進行。驗性觸媒，可舉例如3級胺^ Γ觸媒 月女、二乙醇胺箄&amp; 、’ （知'別是三乙 ㈣專的脂肪族3級胺）、 。定鹼等。該等之中，以3級胺，特別是以定等的°比 疋以二乙胺等的脂肪 2226-9741-ρρ;α^ ⑺ 200911928 族3級胺為佳。驗性爲 田 萄媒之使用1，對反應性胺（與磺醯函 反應之上述胺），通當在 為.1 4耳以上，6莫耳以下（較佳 的疋5莫耳以下）程度。 對石黃酿齒化合物，、天Λ t丨 物添加反應性胺與鹼性觸媒時，鹼性觸 媒之添加時機並無特別限定，反應性胺之添加前及添加後 均可，亦可與反應性胺以相同時機添加。又，可預先與反 應性胺混合再添加，亦可與反應性mi添加。、 。石黃酿齒與反應性胺之反應溫度，例如為代以上，50 °C以下（較佳的是3 〇。「以丁、 ^以下）。又，反應時間，通常為卜5 小時程度。 由反應混合物取得目的化合物續醯胺體之方法並無特 別限定’可採用習知之各種手法，例如，將反應混合物與 酸(醋酸)及水一起混合，攄取析出之結晶。上述酸*水， 以預先調製酸的水溶液再使用為多’將反應混合物添加於 該酸水溶液為多。反應混合物之添加溫度，通常為邮以 上（較佳的是20t以上），5(rc以下（較佳的是帆以下）。 又，添加後，以一般以同溫度攪拌〇 5小時〜2小時程度。 濾取之結晶，通常，以水等清洗，接著乾燥之。又，亦可 按照需要’藉由再結晶等的習知手法，進一步純化。 [實施例] 以下’舉實施例更具體說明本發明，惟本發明並非受 限於以下實施例者’當然可以在符合上述.下述之趣旨之 範圍加以適當的變更實施，該等均包含於本發明之技術的 範圍。再者’實施例及比較例中的「％」及「部」，若無特 2226-9741-PF;Ahddub 21 200911928 別提及係質量％及質量部。 實施例1 气（1)所示4 胺基偶氮苯-4 -石黃酸2 〇部，力17八 水120部及N〜曱基吡咯烷酮12〇部後，於冰浴下，以3〇% 虱乳化納水洛液調節成pH7〜8。以下的操作係於冰浴卞進 仃。加入亞硝酸鈉9. 2部攪拌30分鐘。少量少量添加35% 鹽酸4 8 · 7部成褐声，、玄、、存德， 邑，谷液後攪拌2小日守。將硫酸醯胺6 · 3n ^ / with summer, for sulfite caries 1 mol, such as A 〇 · 〇 5 ~ 1 molar level. The azo bucket is used for milk Yin, 酉文(I) and Ν, Ν-dialkyl 曱醯 face first mixed with solvent towel, adding force σ κ ^ machine 丞Τ ~ pre ~ 亚 claw S &amp; halogen, then Suppress hair loss. . The reaction temperature is, for example, more than or equal to (preferably, the order is not more than C (preferably, β 〇. 反应). The reaction time is, for example, 0.5 hours 2226-974l-PF; Ahddub 19 200911928 or more (better) It is more than 3 hours), less than 8 hours (preferably less than 5 hours). The compound of the above-mentioned 醯~醯_ can be reacted with the amine separately or directly with the reaction mixture. The amine reaction may be carried out, for example, by mixing the reaction mixture with water and taking the precipitated crystals. The obtained crystals of the lean-lean halogen compound may be washed with water and dried before being reacted with the amine as needed. The above-mentioned amine may, for example, be a primary amine 'the first-order amine system M-R7 is the same as described above). Specific examples of M_R7 include n-propylamine, =butylamine, n-hexylamine, dimethylhexylamine (1,5-dimethylhexylamine, tetramethylbutylamine, tetramethylbutylamine, etc. ), ethylhexyl (etc.), aminophenyl phenylamino group + phenyl Dingxue Temple, and propoxypropylamine. The amine is used in the batch of ** grass ear, the use of the Μ 哥 哥 哥 ’ ’ ’ 封 ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ ’ $ i 莫耳乂 (preferably 7 moles), in this specification, the amine is distinguished from the sexual catalyst. The following is called a reactive amine. 〃 醯 醯 halogen compound and amine The addition of a per-halogen compound is added (dropped) to the amine. The reaction of monoamine is usually carried out in a solvent. Solubility: = the same solvent as the compound of the halogen compound. The reaction of the yellow brewing tooth with the reactive amine is carried out under the white scorpion. The catalyzed catalyst can be exemplified by a tertiary amine, a catalyzed surfactant, a diethanolamine hydrazine, and a 'different'. Dedicated aliphatic 3-grade amine), alkaloid, etc. Among these, a tertiary amine, especially a fat ratio of diethylamine, etc. 2226-9741-ρρ; α^ (7) 200911928 Group 3 amines are preferred. The testability is the use of the medium, and the reactive amine (the above amine reacted with the sulfonate) is generally above 14.4 ears, 6 moles or less (preferred疋5mol below). When adding reactive amines and basic catalysts to Shihuang brewing compounds, Tianzhu t丨, the timing of addition of alkaline catalysts The reactive amine may be added before or after the addition of the reactive amine, or may be added at the same time as the reactive amine. Further, it may be mixed with the reactive amine in advance, or may be added to the reactive mi. The reaction temperature of the yellow brewing tooth and the reactive amine is, for example, more than 50 ° C (preferably 3 〇. "in the range of butyl, ^ or less." Further, the reaction time is usually 5 hours. The method for obtaining the target compound to continue the guanamine is not particularly limited. Various conventional methods can be employed. For example, the reaction mixture is mixed with an acid (acetic acid) and water to extract the precipitated crystal. The above acid * water is used in advance. The aqueous solution of the prepared acid is reused as much. The reaction mixture is added to the aqueous acid solution. The addition temperature of the reaction mixture is usually above the post (preferably 20 t or more), and 5 (sec or less (preferably below the sail). Further, after the addition, the mixture is stirred at the same temperature for 5 hours to 2 hours. The crystals are collected by filtration, usually, washed with water or the like, followed by drying. Further, as needed, by recrystallization, etc. In the following, the present invention will be more specifically described by the following examples, but the present invention is not limited to the following examples. Of course, it can be appropriately changed within the scope of the above-mentioned contents. In addition, these are all included in the scope of the technology of the present invention. Further, in the examples and comparative examples, "%" and "part", if there is no special 2226-9741-PF; Ahddub 21 200911928 does not mention the mass% and Mass part. Example 1 Gas (1) shows 4 aminoazobenzene-4 -hemeic acid 2 anthracene, 120 parts of force 17 octahydrate and 12 parts of N~mercaptopyrrolidone, in an ice bath, The pH was adjusted to pH 7~8 with 3〇% 虱 emulsified Nasal Loose solution. The following operations were carried out in an ice bath. Add 2 parts of sodium nitrite and stir for 30 minutes. A small amount of 35% hydrochloric acid added 4 8 · 7 parts into brown sound, Xuan, Cunde, sputum, and the solution was stirred for 2 days. Ammonium sulfate 6 · 3

部溶解於水4〇 A u。卩之水浴液加入反應溶液，攪拌得到含重氮 鹽之懸濁液。 (a—1) h〇3s~^)_n=n_^^_NH2The part is dissolved in water 4〇 A u. The aqueous bath of hydrazine was added to the reaction solution, and stirred to obtain a suspension containing a diazonium salt. (a-1) h〇3s~^)_n=n_^^_NH2

(c-1) 性水；谷液授掉成無色溶液 節成PH8〜9以幫浦滴入含 邊恢復至室溫，藉由進一 將過濾所得黃色固體於減 示偶氮化合物2 6. 4部（產 冰浴下，將上述巴比妥酸鹼 後，邊以30%氫氧化鈉水溶液調 重氮鹽之懸濁液。滴入終了後， 步攪拌3小時得到黃色懸濁液。 壓下以6CTC乾燥，得到式（卜〗）所 率 89%) 〇 22 2226-974l-PF；Ahddub 200911928 H〇3S~h^)_n=n__^)_n=n_^n)=0 (H) /Λ 偶氮化5物（卜1 )之構造，係以1H-NMR及13c — NMR分析 鑑定。分析機器使用ECA-5 0 0 (日本電子（株）製）。 W-NMRaoOMHz，（5 值（ppm，TMS 基準），MS〇); 3.22(3H’ s) ’ 3.33(3H’ s) ’ 7 79(2h，brd，&gt;62如， 7.82(2H，br.d，J = 9.2Hz)，7·84(2Η，br.d，J = 6.2Hz)， 8.00(2H ’ br. d，J = 9.2Hz)，14. 16(2H，s) I3C-NMR(125MHz，6 值（ppm’ TMS 基準），DMSO): 27.3， M.2, 1Π. 5’ 118.6, 122.1，124.4, 126.7, 143.9, 149.4, 150. 5，150. 7，151. 7，158. 5，160. 2 將所得偶氮化合物（1-1)0· 35g溶解於n，n-二甲基甲 醯fe使體積為250cm3，將其中的2cm3以水稀釋成體積為 1 OOcin (》辰度：〇28g/L) ’使用分光光度計〔石英比色管， 比色管長1 cm〕測定吸收光譜。將所得吸收光譜示於圖1。 該化合物，於又max = 416nm顯示吸光度2. 75(任意單位）。 比較例1 對式（d-Ι)所示胺苯磺酸23· 2部加入水348部後，以 3 0 /鼠氧化納水溶液調卽成ρ η 7 ~ 8。以下的操作係於冰浴下 進行。加入亞硝酸鈉11. 1部攪拌30分鐘。少量少量添加 3 5 %鹽酸41 · 9部成乳白色懸濁液後，授拌2小時。將於水 25. 2部溶解硫酸醯胺2. 5部之水溶液加入反應溶液，授拌 得到含重氮鹽之懸濁液。 2226-9741-PF;Ahddub 23 200911928 (d-1) h〇3S~〇-nh2 邱^ )所不N，N —二甲基巴比妥酸24. 2部加入水 3 7 2部後，以3 f] 〇/与长 、、 ^ 。虱氧化鈉水溶液調節成pH8~9。冰浴下， '…,l 文馱鹼性水溶液攪拌成無色溶液後，邊以30% 鈉^ ’奋'夜调郎成pH8~9以幫浦滴入含重氮鹽之懸濁 液。滴入終了接，、鱼n &gt;(c-1) Sexual water; the trough liquid is transferred to a colorless solution to form PH8~9, and the pump is added dropwise to the room to recover to room temperature, and the yellow solid obtained by filtration is further reduced to the azo compound 2 6. 4 In the ice-making bath, after the above-mentioned barbituric acid and alkali, the suspension of the nitrogen salt was adjusted with a 30% aqueous sodium hydroxide solution. After the completion of the dropwise addition, the mixture was stirred for 3 hours to obtain a yellow suspension. Drying at 6CTC, yielding 89% of the formula (卜)) 〇22 2226-974l-PF; Ahddub 200911928 H〇3S~h^)_n=n__^)_n=n_^n)=0 (H) /Λ The structure of the azo nitride 5 (Bu 1) was identified by 1H-NMR and 13c-NMR analysis. The analysis machine used ECA-5 0 0 (manufactured by JEOL Ltd.). W-NMRaoOMHz, (5 values (ppm, TMS basis), MS〇); 3.22(3H's) ' 3.33(3H' s) ' 7 79(2h,brd,&gt;62, 7.82 (2H, br. d, J = 9.2 Hz), 7.84 (2 Η, br. d, J = 6.2 Hz), 8.00 (2H ' br. d, J = 9.2 Hz), 14. 16 (2H, s) I3C-NMR ( 125 MHz, 6 values (ppm' TMS basis), DMSO): 27.3, M.2, 1Π. 5' 118.6, 122.1, 124.4, 126.7, 143.9, 149.4, 150. 5,150. 7,151. 7,158. 5,160. 2 The obtained azo compound (1-1) 0·35g was dissolved in n, n-dimethylformamide to a volume of 250 cm 3 , and 2 cm 3 of the solution was diluted with water to a volume of 1 00 cin. Degree: 〇28g/L) 'The absorption spectrum was measured using a spectrophotometer [quartz colorimetric tube, colorimetric tube length 1 cm]. The obtained absorption spectrum is shown in Fig. 1. The compound showed an absorbance of 2.75 at max = 416 nm. (arbitrary unit) Comparative Example 1 After adding 348 parts of water to the 23 parts of the amine benzenesulfonic acid represented by the formula (d-Ι), the mixture was adjusted to ρ η 7 to 8 with a 30/rat sodium oxide aqueous solution. The operation was carried out in an ice bath. 11.1 part of sodium nitrite was added and stirred for 30 minutes. A small amount of 35% hydrochloric acid was added in a small amount. After the milky white suspension is added, the mixture is stirred for 2 hours. The aqueous solution of 2.5 parts of the dissolved ceric sulfate in water is added to the reaction solution, and the suspension is mixed to obtain a suspension containing the diazonium salt. 2226-9741-PF ; Ahdub 23 200911928 (d-1) h〇3S~〇-nh2 Qiu ^) N, N - dimethyl barbituric acid 24. 2 parts of water after adding 3 7 2 parts, 3 f] 〇 / With long, ^. The aqueous sodium hydroxide solution was adjusted to pH 8-9. Under the ice bath, '..., l 驮 驮 alkaline solution was stirred into a colorless solution, and then 30% sodium ^ ‘Feng’ night was adjusted to pH 8~9 to drip the suspension containing diazonium salt. Drip into the end, fish n &gt;

主，、灸邊恢後至室溫藉由進一步攪拌3小時得 J汽色心H將過遽所得黃色固體於減壓下以601乾 燥’得到式⑴'1)所示偶氮化合物36.2部。After the main moxibustion, the moxibustion was further stirred for 3 hours at room temperature to obtain a yellow solid obtained by passing the ruthenium to a yellow solid obtained under reduced pressure at 601 to give a portion 36.2 of the azo compound of the formula (1) '1).

(IH) 將式（I卜1)所示偶氮化合物之吸收光譜，以與實施例 1同樣的條件測定。冑所得吸收光譜示於_ 2。該化合物， 於λ max = 387nm顯示吸光度2. 〇3(任意單位）。 實鈀例1之偶氮化合物（1-1 )，雖分子量大卻同一濃度 (/辰度 0.028g/L)之吸光度，較比較例i之偶氮化合物 (Π 1)大，約〇. 7。此結果，係表示本發明之偶氮化合物 及其鹽具有南的色濃度。 實施例2 於具備冷卻管及攪拌裝置之反應瓶，投入偶氮化合物 (I-1)5部、氯仿50部及n，N-二甲基曱醯胺2. 1部，於攪 掉下邊維持於2(TC以下’滴入亞硫醯氯6部。滴入終了後’ 升溫為50°C，以同溫度維持5小時使之反應，之後冷卻成 2226-974l-PF;Ahddub 24 200911928 20°C。將冷卻後之反應溶液，於攪拌下邊維持於以下 滴入U，3, 3一四甲基丁基胺4部及三乙胺14部之混合液。 之後’以m 5小日㈣拌使之反應。接著將所得反應混 合物以減壓濃縮機餾除溶劑後，加入少量曱醇劇烈攪拌。 將該混合物，邊攪拌加入醋酸29部及去離子水部之混 合液令，使結晶析出。將析出之結晶濾別，以去離子水= 洗，以601減壓乾燥，得到式（1_19)所示偶氮化合物^ 部（產率80%)。 〇(IH) The absorption spectrum of the azo compound represented by the formula (I1) was measured under the same conditions as in Example 1. The absorption spectrum obtained by hydrazine is shown in _ 2. The compound exhibits an absorbance of 2. 〇3 (arbitrary unit) at λ max = 387 nm. The azo compound (1-1) of the palladium example 1 has a larger molecular weight but the same concentration (/28 degree 0.028 g/L) of the absorbance, which is larger than the azo compound of the comparative example i (Π 1), about 〇. 7 . As a result, it is shown that the azo compound of the present invention and its salt have a south color density. Example 2 In a reaction flask equipped with a cooling tube and a stirring device, 5 parts of azo compound (I-1), 50 parts of chloroform, and 2.1 parts of n,N-dimethyl decylamine were placed, and the mixture was maintained under stirring. At 2 (below TC, add 6 parts of sulfoxide. After the end of the dropwise addition, the temperature is raised to 50 ° C, and the reaction is maintained at the same temperature for 5 hours, then cooled to 2226-974l-PF; Ahddub 24 200911928 20° C. The cooled reaction solution was stirred while stirring, and a mixture of 4 parts of U,3,3-tetramethylbutylamine and 14 parts of triethylamine was added dropwise. Then, the mixture was mixed with m 5 small days (four). Then, the obtained reaction mixture was distilled off with a reduced pressure concentrator, and then a small amount of decyl alcohol was added and stirred vigorously. The mixture was stirred and a mixture of 29 parts of acetic acid and deionized water was added thereto to precipitate crystals. The precipitated crystals were filtered, washed with deionized water = dehydrated, and dried under reduced pressure at 601 to give an azo compound (yield: 80%) of formula (1-19).

N )=0 N 〇 (1-19) 將所得偶氮化合物（I —19)0.35g溶解於n N 一二曱基甲 酿胺使體積為驗，將其中的w以乳酸㈣稀釋二體 積為m農度：（).G28g/L)，使用分光光度計〔石英比 色管，比色管長lcm〕測定吸收光，並。腺弘~ j &amp;及队亢》日。將所得吸收光譜示 於圖3。該化合物，於又_ max-420nm顯不吸光度2 74(任意 單位）。 比較例2 於具備冷卻管及授拌梦署夕θ施、,c f衮置之反應瓶，投入偶氮化合物 (Π-1)5部、氯仿5〇部及nn_ -甲其田Λ 、， 久1Ν，1Ν 一甲基甲醯胺2. 1部，於攪 拌下邊維持於2 0。(3以下，、、；$； λ π &amp; m &gt; 滴入亞硫醢氟6部。滴入終了後 升溫成5 0。(：，以同溫度維梏q |主 没维待5小時使之反應，之後冷卻成 JC。將冷卻後之反應溶液於㈣下邊維持於赃以下， I 1，3’ 3 —四曱基丁基胺4部及三乙胺14部之混合液。 2226-9741-pF;Ahddub 25 200911928 :後，以同溫度搜#5小時使之反應。接著將 =:嶋縮機餘除溶劑後，加入少量甲醇劇烈授：: 匕口 4勿’邊授掉加入醋酸29部及去離子纟300部之混 合液中’使結晶析4。將析出之結晶濾別，以去離子水： 洗，以阶減壓乾燥，得到式⑴一2)所示偶氮化合^，月 部（產率62%)。 · ΠN)=0 N 〇(1-19) 0.35 g of the obtained azo compound (I-19) was dissolved in n N-dimercaptoacetamide to measure the volume, and w was diluted with lactic acid (tetra) to two volumes. m agricultural degree: (). G28g / L), using a spectrophotometer [quartz colorimetric tube, colorimetric tube length lcm] to determine the absorbed light. Gland Hong ~ j &amp; and team 亢" day. The obtained absorption spectrum is shown in Fig. 3. This compound showed no absorbance of 2 74 (arbitrary unit) at _ max-420 nm. Comparative Example 2 In a reaction bottle equipped with a cooling tube and a 6.4 Hz solution, azo compound (Π-1), chloroform 5 及, and nn_-Kakita 、, 久久Ν 1 part of monomethylcarbamide, 1 part, maintained at 20 while stirring. (3,,,,;;; λ π & m &gt; Into the 6 parts of sulfoxide, the temperature is raised to 50 after the end of the instillation. (:, at the same temperature, the temperature is q | the main does not treat for 5 hours The reaction was carried out, and then cooled to JC. The cooled reaction solution was maintained under the enthalpy under (IV), and a mixture of 4,1,3'3-tetradecylbutylamine 4 and triethylamine 14 was added. 9741-pF; Ahddub 25 200911928: After that, react with the same temperature for #5 hours to make it react. Then, after removing the solvent from the shrinkage machine, add a small amount of methanol and give it vigorously:: 匕口4Do not add acetic acid In the mixture of 29 parts and 300 parts of deionized cesium, 'crystallizes 4'. The precipitated crystals are filtered, deionized water: washed, and dried under reduced pressure to obtain azo nitride as shown in formula (1)-2). , the month (yield 62%). · Π

N Ο 2~^(3_N=N~&lt;V_n^=0 (丨卜 2) 將式⑴-2)所示偶氮化合物之吸收光譜，以與實施例 2同樣的條件測定。將所得吸收光譜示於圖4。該化合物， 於；I max = 38 7nm顯示吸光度2. 0 7(任意單位）。 實施例2之偶氮化合物（I -19)’雖分子量大同一灌声 (濃度：0.028g/L)之吸光度，較比較例2之偶氮化合物 (11-2)，大〇. 6。該結果，表示本發明之偶氮化合物及其 鹽，具有高的色濃度。 實施例3 對式（a-1)所示4’ -胺基偶氮苯-4-磺酸12部加入水 72部及N-甲基吡咯烷酮72部後’以3〇%氫氧化鈉水溶液 調節成pH7〜8。以下的操作係於冰浴下進行。加入亞確酸 鈉5_ 5部攪拌30分鐘。少量少量添加35%鹽酸29. 2部成 褐色溶液後，攪拌2小時。將硫酸醯胺3. 8部溶解於水37 7 部之水溶液加入反應溶液’授拌得到含重氮鹽之懸濁液。 對式（c-2)所示N，N —二異丙基巴比妥酸6. 9部加入 2226-9741-PF;Ahddub 26 200911928 水68. 9部後，以30%氫氧化鈉水溶液調節成pH8〜9。N Ο 2~^(3_N=N~&lt;V_n^=0 (丨2) The absorption spectrum of the azo compound represented by the formula (1)-2) was measured under the same conditions as in Example 2. The obtained absorption spectrum is shown in Fig. 4 . The compound exhibits an absorbance of 2.07 (arbitrary unit) at; I max = 38 7 nm. The azo compound (I-19)' of Example 2 had a larger molecular weight than that of the azo compound (11-2) of Comparative Example 2, although it had a larger molecular weight than that of the azo compound (11-2) of Comparative Example 2. As a result, the azo compound of the present invention and a salt thereof have a high color density. Example 3 After adding 72 parts of water and 72 parts of N-methylpyrrolidone to the 4'-aminoazobenzene-4-sulfonic acid represented by the formula (a-1), it was adjusted with a 3 % sodium hydroxide aqueous solution. Into pH7~8. The following operations were carried out under an ice bath. Add 5 parts of sodium sulfite to stir for 30 minutes. After adding a small amount of 35% hydrochloric acid to 29.2 parts of a brown solution, it was stirred for 2 hours. An aqueous solution in which 38 parts of guanamine sulfate was dissolved in 37 parts of water was added to the reaction solution to obtain a suspension containing a diazonium salt. For the N,N-diisopropylbarbituric acid represented by formula (c-2), the hexazone is added to 2226-9741-PF; the Ahddub 26 200911928 water is 68. 9 and then adjusted with 30% aqueous sodium hydroxide solution. It is pH 8~9.

冰浴下，將上述巴比妥酸鹼性水溶液攪拌成無色溶液 後，邊以30%氫氧化鈉水溶液調節成PH8〜9以幫浦滴入含 重氮鹽之懸濁液。滴入終了後，邊恢復至室溫，藉由進一 步攪拌3小時得到黃色懸濁液。將過濾所得黃色固體於減 壓下以6(TC乾燥，定量地得到式（I —6)所示偶氮化合物 (1 8 · 2 部）。 〇、— hcd3S~^^n=n_^Q^=nJ^:&gt;=〇 ㈣ 於具備冷卻管及攪拌裝置之反應瓶，投入偶氮化合物 (I 6)5邛、氣仿50部及n，N-二甲基甲醯胺2.1部，授拌 下邊維持2(TC以下’滴入亞硫醯氯6部。滴入終了後，升 就為50 C，以同溫度維持5小時使之反應，之後冷卻成2〇 C將Q卻後之反應溶液於撥拌下邊維持於2 〇 以下，滴 入3-異丙氧基丙基胺4部及三乙胺14部之混合液。之後， 以同溫度攪拌5小時使之反應。接著將所得反應混合物以 減壓濃縮機餾除溶劑後’加入少量甲醇劇烈攪拌。將該混 合物，邊攪拌加入醋酸29部與去離子水3⑽部之混合液 27 2226-9741-PF/Ahddub 200911928 -中’使結晶析出。將析出之結晶濾別，以去離子水清洗， 以60°C減壓乾燥，得到式（1 — 2〇)所示偶氮化合物2. 6部（產 率 43%)。After the above aqueous solution of barbituric acid was stirred into a colorless solution in an ice bath, it was adjusted to pH 8 to 9 with a 30% aqueous sodium hydroxide solution to drip the suspension into the suspension containing the diazonium salt. After the completion of the dropwise addition, the mixture was returned to room temperature, and further stirred for 3 hours to obtain a yellow suspension. The yellow solid obtained by filtration was dried under reduced pressure at 6 (TC) to quantitatively obtain an azo compound (1 8 · 2) of the formula (I-6). 〇, - hcd3S~^^n=n_^Q^ =nJ^:&gt;=〇(4) In a reaction bottle equipped with a cooling tube and a stirring device, azo compound (I 6) 5 邛, 50 parts of gas and 2.1 parts of n,N-dimethylformamide were introduced. Mix 2 while maintaining 2 below the TC. Add 6 parts of sulfoxide. After the end of the dropwise addition, the temperature is 50 C. The reaction is maintained at the same temperature for 5 hours, and then cooled to 2 〇C to react with Q. The solution was maintained at a temperature of 2 Torr or less, and a mixture of 4 parts of 3-isopropoxypropylamine and 14 parts of triethylamine was added dropwise, and then the mixture was stirred at the same temperature for 5 hours to cause a reaction. After the mixture was distilled off with a vacuum condenser, the mixture was stirred vigorously with a small amount of methanol. The mixture was stirred and added to a mixture of 29 parts of acetic acid and 3 parts of deionized water (27 2226-9741-PF/Ahddub 200911928 - The azo compound of the formula (1-2) is obtained by filtration. The precipitated crystals are filtered, washed with deionized water, and dried under reduced pressure at 60 ° C. 43%).

將偶氣化合物（I - 2 0 )之吸收光譜，以與實施例1同樣 的條件測定。將所得吸收光譜示於圖5。該化合物，於 入max = 42 3nm顯示吸光度2· 20(任意單位）。 實施例4 將具有磺基之偶氮化合物（1-1)與具有N_取代磺醯基 之偶氮化合物（I -1 9)及（I - 2 0)之油溶性（對丙二醇單甲鍵 之溶解度），如下求得： 將偶氮化合物1 g及丙二醇單甲醚9g放入微量瓶攪拌 一晝夜後’將溶殘過濾去除（若偶氮化合物完全溶解時，遽 液濃度為1 〇質直％ )。將如此所得渡液之吸收光譜，使用淚 液3. 5g以外以與實施例1同樣地測定，求各偶氮化合物於 入1^乂之吸光度（1111：(3))。又使用各偶氮化合物〇.352,以 與實施例1同樣地’求各偶氮化合物於A max之吸光度 (Int(r))。然後由下式： 溶解度（質量 °/〇 = (Int(a)xlO)/lnt(r) 計算各偶氮化合物之溶解度。將結果示於表i。 2226-9741-PF;Ahddub 28 200911928 [表 1]_ 偶氮化合物 溶解度 (1-1) 0·04質量 rz— _(1-19) (1-20) Γ% ------ __A61質量％ 1.48^¾^ 本發明之偶氮化合物之油溶性 [產業上的可利性] 本發明之偶氮化合物及其鹽，顯示非常高的色濃产。 因此即使以报少的使用4，即可由本發明之偶氮化合物及 其鹽’得到具有與先前同樣的品質之染色物，在成本面有 利。又，在於製造液晶顯示零件之硬化性樹脂組成物中使 用本發明之偶氮化合物及里豳脖 , 27夂具鹽袴，由於可減少使用晉，因 此可得耐溶劑性及耐熱性箄 ^ 等之I&quot;生月b優良的零件。再者本發 明之偶氮化合物及其鹽，亦 x 乃J早獨使用作為優良的色素， 亦可作為調色用色素，盥复 ’、 一 ^ Z、他的色素併用。如此地色濃度 高的本發明之偶氮化合物 ^ ^ 又 从… 及其鹽’於染色物或液晶顯示零 件之製造料’亦可用於各式各樣的用途。 【圖式簡單說明】 圖1係表不式（1-1)所 光譜之圖。 圖2係表不式（ιι_ι)所 收光譜之圖。 圖3係表示式（Ι — ig)所示 收光譜之圓。 示偶氮化合物（實施例1)之吸收 示偶氮化合物（比較例1 )之 偶氮化合物（實施例2)之吸 2226-9741-PF;Ahddub 200911928 圖4係表示式（II —2)所示偶氮化合物（比較例2 收光譜之圖。 之 吸 圖5係表示式（卜2〇)所示偶氮化合物（實施例3)之 收光譜之圖。 【主要元件符號說明】 〇 2226-9741-PF;Ahddub 30The absorption spectrum of the azo compound (I - 2 0 ) was measured under the same conditions as in Example 1. The obtained absorption spectrum is shown in Fig. 5. The compound showed an absorbance of 2·20 (arbitrary unit) at a max = 42 3 nm. Example 4 Oil-soluble (p-propylene glycol monomethyl bond) of an azo compound (1-1) having a sulfo group and an azo compound (I-1 9) having an N-substituted sulfonyl group and (I - 2 0) Solubility), as follows: 1 g of azo compound and 9 g of propylene glycol monomethyl ether were placed in a micro vial and stirred for a day and night to remove the residue (if the azo compound is completely dissolved, the sputum concentration is 1 enamel) Straight %). The absorption spectrum of the thus obtained liquid was measured in the same manner as in Example 1 except that the tear liquid was 3.5 g, and the absorbance (1111: (3)) of each azo compound was measured. Further, in the same manner as in Example 1, the absorbance (Int(r)) of each azo compound at A max was determined using the respective azo compounds 〇.352. The solubility of each azo compound was then calculated from the solubility: mass ° / 〇 = (Int (a) x lO) / lnt (r). The results are shown in Table i. 2226-9741-PF; Ahddub 28 200911928 [Table 1]_ azo compound solubility (1-1) 0·04 mass rz_ _(1-19) (1-20) Γ% ------ __A61 mass% 1.48^3⁄4^ The azo compound of the present invention Oil-soluble property [Industrial Applicability] The azo compound and the salt thereof of the present invention exhibit a very high color concentration. Therefore, even if the use of 4 is reported, the azo compound of the present invention and its salt can be used. It is advantageous to obtain a dye having the same quality as before, and it is advantageous in terms of cost. Further, in the curable resin composition for producing a liquid crystal display part, the azo compound of the present invention and the 豳 豳 neck, 27 夂 袴 袴, By reducing the use of Jin, it is possible to obtain parts that are excellent in the solvent resistance and heat resistance, etc. I. The azo compound and its salt of the present invention are also used as an excellent pigment. It can also be used as a coloring agent for coloring, and it can be used together with a pigment. The azo compound of Ming Ming ^ ^ and its salt 'in the dyeing material or liquid crystal display parts manufacturing materials' can also be used for a variety of purposes. [Simple diagram of the diagram] Figure 1 is a formula (1-1 Fig. 2 is a diagram showing the spectrum of the spectrum obtained by the equation (ιι_ι). Fig. 3 is a graph showing the circle of the spectrum represented by the formula (Ι-ig). The absorption of the azo compound (Example 1) is shown. Azo compound (Comparative Example 1) azo compound (Example 2) 2226-9741-PF; Ahddub 200911928 Figure 4 shows the azo compound of the formula (II-2) (Comparative Example 2 Figure 5 is a diagram showing the spectrum of the azo compound (Example 3) shown in the formula (Example 2). [Key element symbol description] 〇2226-9741-PF; Ahddub 30

Claims (1)

200911928 十、申請專利範圍： 1. 一種偶氮化合物及其鹽200911928 X. Patent application scope: 1. An azo compound and its salt 以式（I)表示者： 式（I)中’ Z係表示氧原子或硫原子； A係表示具有i個或2個選自由㈣、項基、碍 及N-取代確醯基所組成之群之至少i種基之苯基，或者: 有卜3個選自由項基、石黃醯基A N —取代續酿基所組成之群 之至少1種基之萘基； f Rl: R2係分別獨立地表示’氫原子、Ch。飽和脂肪烴 基、有羥基取代之Cm。飽和脂肪烴基 '有CH烷氧基取代 之^飽和脂肪烴基1C&quot;硫代院氧基取代之CH。飽和 脂肪烴基、碳數為6〜20之芸其，#奴# 。 π 0 π之方基，碳數為7~2〇之芳烷基， 或碳數為2 ~ 1 0之酿基； 广&quot;'分別獨立地表示，氫原子、_素原子、。。飽 和脂肪烴基、鹵化“飽和脂肪烴基Α禮氧基、幾基、 磺基、磺醯基或N-取代續醯基。 2·如申請專利範圍第！項所述的偶氮化合物及其鹽， 其中A係具有1個取代績醯基之苯基或2個n—取代確醯 基之萘基。 偶氮化合物及其鹽， 、R7為Ch。飽和脂肪 3.如申請專利範圍第1項所述的 其中上述N-取代磺醯基為_s〇2NHR7基 2226-9741-PF;Ahddub 31 200911928 煙基、C1 -8院氧基取代之c 1 -1。德和脂肪煙基、碳數為6〜2 0 之芳基、碳數為7〜2〇之芳烷基、或碳數為2~10之醯基。 4.如申請專利範圍第1項所述的偶氮化合物及其鹽， 其中Α係表示具有1個Ν_取代磺醯基之苯基或具有2個ν- 取代績酿基之萘基，上述Ν-取代磺醯基係-S〇2NHR7基，R7 係C!’飽和脂肪烴基、Ci 8烷氧基取代之Ci 1()飽和脂肪烴 基、碳數為6〜20之芳基、碳數為7〜2〇之芳烷基、或碳數 為2〜1 0之醯基。 明專利乾圍第1項所述的偶氮化合物及苴踐， 其中A係表示具有丨個 /、孤 本基或具有2個磺基之萘基。 6. 如申請專利範圍第1 土 合物及其鹽，纟中只2之㉟中任-項所述的偶氮化 7. 如申請專利範圍第至少1個之碳數為6以上。 其中及R2之至少丨個 ^所述的偶氮化合物及其鹽， 固係衩數為6〜20之芳基。 2226-9741-PF；fthddub 32The formula (I): In the formula (I), the 'Z system represents an oxygen atom or a sulfur atom; and the A system has one or two selected from the group consisting of (4), a subunit, and an N-substituted thiol group. a phenyl group of at least one group of the group, or: a group of three naphthyl groups selected from the group consisting of a group of bases, a scutane-based AN-substituted aryl group; f Rl: R2 are independently Represents 'hydrogen atom, Ch. A saturated aliphatic hydrocarbon group having a hydroxyl group substituted with Cm. Saturated aliphatic hydrocarbon group 'CH saturated with alkoxy group substituted with a saturated aliphatic hydrocarbon group 1C&quot; Saturated aliphatic hydrocarbon group, carbon number is 6~20, it is #奴#. A square of π 0 π, an aralkyl group having a carbon number of 7 to 2 Å, or a aryl group having a carbon number of 2 to 10; broadly &quot;', respectively, independently represent a hydrogen atom, a _ atom, and a hydride atom. . a saturated aliphatic hydrocarbon group, a halogenated "saturated aliphatic hydrocarbon group, a sulfhydryl group, a aryl group, a sulfo group, a sulfonyl group or an N-substituted fluorenyl group. 2. The azo compound and its salt as described in the scope of claim [...] Wherein A is a phenyl group having one substituted fluorenyl group or two naphthyl groups having an n-substituted anthracene group. An azo compound and a salt thereof, and R7 is Ch. Saturated fat 3. As claimed in claim 1 Wherein the above N-substituted sulfonyl group is _s〇2NHR7 group 2226-9741-PF; Ahddub 31 200911928 is a nicotine group, and a C1-8 alkoxy group is substituted by c 1 -1. De and fatty nicotine groups, the carbon number is An aryl group of 6 to 20, an aralkyl group having a carbon number of 7 to 2 Å, or a fluorenyl group having a carbon number of 2 to 10. 4. The azo compound and a salt thereof according to claim 1 of the patent application, Wherein lanthanide is a phenyl group having one fluorene-substituted sulfonyl group or a naphthyl group having two ν-substituted aryl groups, the above fluorenyl-substituted sulfonyl-S〇2NHR7 group, R7 is C!' saturated An aliphatic hydrocarbon group, a Ci 8 alkoxy-substituted Ci 1 () saturated aliphatic hydrocarbon group, an aryl group having 6 to 20 carbon atoms, an aralkyl group having a carbon number of 7 to 2 Å, or a carbon number of 2 to 10 Patent The azo compound and the oxime described in the above item 1, wherein the A group represents a naphthyl group having a ruthenium, a solute group or a sulfo group. 6. The hydrate of the first aspect of the patent application and its salt, 纟The azo nitride according to any one of the above-mentioned items, wherein the carbon number is at least 6 or more, and at least one of R2 is an azo compound and a salt thereof. An aryl group with a solid number of 6 to 20. 2226-9741-PF; fthddub 32