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 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.

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.

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.

The 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)

\

(1-7) (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

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

N 0. 0 N )=〇 (卜11)

&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 200911928

(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 Ο

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 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) 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) 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 ^ / 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

The 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) 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;

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) 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) 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.

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%).

The 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 X. Patent application scope: 1. An azo compound and its salt The 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