TW201000567A - Azo compound or salt thereof - Google Patents

Abstract

An azo compound represented by a formula (I), or a salt thereof: wherein A represents either a phenyl group having two or more of at least one type of group selected from the group consisting of halogen atoms, a methyl group, a methoxy group, a nitro group, a sulfo group, a sulfamoyl group and N-substituted sulfamoyl groups, or a naphthyl group having one or more of at least one type of group selected from the group consisting of halogen atoms, a methyl group, a methoxy group, a nitro group, a sulfo group, a sulfamoyl group and N-substituted sulfamoyl groups, R1 represents a hydrogen atom, a C1 to C12 aliphatic hydrocarbon group, a C7 to C20 aralkyl group, or a C6 to C20 aryl group, and R2 represents a C1 to C5 aliphatic hydrocarbon group or a trifluoromethyl group.

Description

201000567 VI. Description of the Invention: [Technical Field to Be Invented by the Invention] The present invention relates to a compound of (4) a salt thereof. [Prior Art] A plasma display panel or the like is used, for example, in the case where the dye of Patent Document 1 is used for a liquid crystal display panel, electroluminescence, or as a color filter or a coloring agent. The dye is an azo compound represented by the formula (d-1;).

[Prior Art Document] [Patent Document 1] JP-A-2006-124634 [Patent Document 2] Japanese Patent Publication No. 2〇〇3 - 51〇398 [Patent Document 3] Japanese Special Fair 7-88633 [Patent Document 4] Japanese Laid-Open Patent Publication No. Hei. No. Hei. No. Hei. No. Hei. No. Hei. Dissolution of the sex-reducing cryptic complex or its axis. The present invention provides the following [1] to [6]. [1] An azo compound or a salt thereof, which is represented by Formula 1. (i) 201000567

* [In the formula (I), A represents at least an anthracene group selected from the group consisting of a halogen atom, a methyl group, a methoxy group, a nitro group, a sulfo group, an aminesulfonyl group and an N-substituted amine sulfonyl group. a phenyl group of 2 or more, or a group selected from the group consisting of a γ atom, a methyl group, a decyloxy group, a nitro group, a sulfo group, an amine sulfonyl group, and an N-substituted amine sulfonyl group; More than one naphthyl group. Table ^ Hydrogen atom, C--- 2 aliphatic hydrocarbon group, 〇ν2 () aralkyl group or c6-2Q aryl group. R represents a C!-5 aliphatic hydrocarbon group or a trifluoromethyl group. [2] The azo compound of [1] or a salt thereof, wherein A is a phenyl group or a naphthyl group having at least one n-substituted amine sulfonyl group. [3] The azo compound or a salt thereof according to [1] or [2], wherein the aforementioned N-substituted amine-S〇2NHR3*' Ra is a Cl_12 aliphatic hydrocarbon group ((: 12 12 aliphatic hydrocarbon group 3 The hydrogen atom ' may be substituted with an alkoxy group, and the m i' of the Ci i2 aliphatic hydrocarbon group may be substituted with -0-), C6-20 aryl, C7-20 aryl fluorenyl or C2-1 citric acid. [4] A binary compound of the azo compound or a salt thereof according to any one of [1] to [3]. [5] an azo compound or a salt thereof, the azo compound Expressed by the formula (1〇:

(II) [In the formula (II), A1 represents at least one of the group consisting of a halogen atom, a methyl group, a group, or a phenyl group or a group of 2 A Cs-m aliphatic nicotyl group, a substituted c-group or a substituted C6-2G aryl group. 1 square large 201000567 R1/ represents a C substituted -5 aliphatic hydrocarbon group or trifluoromethyl group. R13 represents a hydrogen atom, an amine carbenyl group or a cyano group; [6] The azo compound of the formula (II) or a salt thereof, wherein the azo compound represented by the formula (II) or a salt thereof is an azo compound represented by the formula (m) or Salt.

3(m) t ' R11, R12 and R13 are the same as in the formula (II).

Ri6 and ^ each independently represent a hydrogen atom, a halogen atom, a fluorenyl group or a decyloxy group. ^, R, and R18' each independently represent a nitrogen atom, a dentate atom, a methyl group, a thiol group or a fluorenyl group, but at least one of R16, RP and Ri8 represents a carboxyl group. ] ^, sometimes, an azo compound or a salt thereof represented by Formula 1, hereinafter referred to as "^^^口物®", an azo compound represented by the formula (Π) or a salt thereof, hereinafter referred to as θ".化 鳞 鳞 * 之 之 之 无 无 无 , , , , , , , , , , , , , , , , , , , , The azo compound of the present invention represented by the formula (1) (the azo compound represents the azo compound of the invention or the azo group thereof, characterized in that the naphthyl group of A is a phenyl group having two or more substituents or In addition to more than one substituent, the part of the ring of ί 吼 吼 , , 四 四 , , , , , 四 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010 2010

^ [In the formula (1), A represents at least an anthracene group selected from the group consisting of a halogen atom, a methyl group, a decyloxy group, a nitro group, a sulfo group, an amine sulfonyl group and an N-substituted amine sulfonyl group. 2 or more phenyl groups, or at least 族^ or more selected from the group consisting of a halogen atom, a methyl group, a decyloxy group, a nitrate group, a sulfo group, an amine sulfonyl group, and an N-substituted amine sulfonyl group Naphthyl. However, the earth ^ represents a hydrogen atom, a C?-^ aliphatic hydrocarbon group, a CVm aralkyl group or a 2〇 aryl group. R represents a Q-5 aliphatic hydrocarbon group or a trifluoromethyl group. The compound represented by the formula (I) or a salt thereof may be bonded to the body at any position. The azo compound or a salt thereof of the present invention has both a water-soluble and oil-soluble property by having a sulfo group, a sulfanyl group, and an N-substituted amine sulfonyl group. In order to improve the oil solubility, it is preferable that in the formula 1, 'A has one or more n-substituted amine sulfonyl groups. Among A, a specific example of a phenyl group having a basal group, for example, a phenyl group having only one thiol (2-, 3- or 4- phenyl), having two contigs a benzenedisulfonylphenyl group, etc.; a group having a sulfo group and one other substituent, for example, methyl sulfonium sulfonate (4-methyl-2-oxophenyl, 4-indolyl-3-sulfophenyl, 2-—甲^~—3—Shihuang benzene^, 2-methyl-5-sulfophenyl, 2-indenyl-4-oxophenyl, 3-methyl-4%, etc.), dimercapto- Rhubarb phenyl (4,6-didecyl-2-pyrrolylphenyl, 2,4-mercapto '-6-sulfophenyl, etc.), decyloxy-sulfophenyl (4-methoxyl-2) - sulfophenyl, 4 dimethoxy-3-thiophenyl, 2-methoxy-3-thiophenyl, 2-methoxyphenyl, etc.), hydroxy-sulfophenyl (2-hydroxy-3) - sulfophenyl, 2-hydroxyl-phenyl, 2-hydroxy-5-sulfophenyl, etc.; and having a sulfo group and two or more other substituents, t, for example: hydroxy-nitro-sulfophenyl (2 Monohydroxy-3-1-nitro-5-sulfonyl, etc.). Among them, from the viewpoint of water solubility, a phenyl group having a sulfo group and a fluorenyl group is preferred, and 201000567 2 - a phenyl group and a 3-methyl group + a phenyl phenyl group are more preferable.

-, 7- or 4, for example 5: one, naphthyl (5-, 6-yl, etc.), with 2 sulfo-groups of cold-, 4,8-,; Qiao-di-J-naphthyl (10) ― or 4, 三茏专), and 3 sulfo-based f1 base m-l base, 2-mercapto-, dimethyl-3-based (4,6-dimethyl- 2 sulfonaphthyl f base about 3 t : rhyme (4-methoxy-nonylnaphthyl) oximeoxy 3 j phenyl, 2-methoxy- 3 - naphthyl, 2-methoxy sulphate 5 - dinaphthoquinone and Having a county ί~ nitro-stone yellow naphthyl (2-woven - 3 - secret - 5:: ί = ί, for example: warp base ~

3 26 8 naphthyl groups (also known as disulfonaphthyl dihydrazide superior 2 ί A better '6,8-disulfo-2-naphthyl is better. ', not based on ·4ί^ ί ^ Ν - amine weiji phenylene naphthalene red, for example, in the case of X-negyl, the sulfo group is substituted with an amine sulfonyl group or an N-substituted group, shi Yin ' 醯 base. Ν - substituted amine 基 基, such as Ν - Substituted for expression. R3 represents a Cl-12 aliphatic hydrocarbon group (the "H atom contained in the group" may be substituted into a silk group or may be linear or branched. Any one of the ring-shaped aliphatic hydrocarbons, the number of which does not contain a substituent, and the number thereof is usually an aliphatic hydrocarbon group of 丨~12, R, for example, may be substituted with a thiol group, an ethyl group, a n-propyl group: Ripropyl, n-butyl, isobutyl, t-butyl, tert-butyl, mono; tetramethyl T-based, etc., methylhexyl (1—▼-ylhexyl, anthracene, 5-dimethyl) $" ίί "ethylhexyl, etc.", cyclofilament, cyclohexyl, methylmethyl% hexyl, cyclohexylalkyl, etc. Aliphatic hydrocarbon group, for example: alkoxypropyl (2-ethylhexyloxy) )propyl, etc.), tetrahydrofuranyl hydrazine, tetrahydrotetramine methyl group ^), 201000567 A glyceryl group, a propyl group (2-hydroxypropyl group, a 3-propylidyl group, etc.), etc. The base of R may be unsubstituted, and may have an aliphatic hydrocarbon group or a substituent such as a radical. The carbon number of the base, which is calculated by the carbon number of the substituent, is usually 6 to 2 Å, preferably 6 to 10. The aryl group is, for example, a phenyl group, a hydroxyphenyl group (4-hydroxyphenyl group, etc.), or a trifluoroantimony. A substituted or unsubstituted phenyl group such as a phenyl group (such as 4-trifluoromethylphenyl group), etc. The alkyl group of the base of the R may be linear, branched or cyclic. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 1 Torr. The aralkyl group is a group of a base group, a benzyl group (1-methyl-3-phenylpropyl group, etc.), A phenylalkyl group such as phenylbutyl (3-monoamino-1-phenylene), etc. is represented by a group. ^ The fluorenyl group of R3 may be unsubstituted, or may be bonded with an aliphatic hydrocarbon group or an oxygen-burning odor group. The calculation of the carbon number of the carbon-containing substituent is preferably from 6 to 10. The above-mentioned mercapto group is, for example, an ethyl fluorenyl group, a benzamidine group, a (p-methoxyphenyl fluorenyl group, etc.), etc. T ^ The above r3 is preferably methylated from the viewpoint of improving oil solubility. (m3-tetramethylbutyl group, etc.), mercaptohexyl (1,5-dimercaptohexyl, etc.), ethylhexyl (2_-ethylammonyl, etc.), methylcyclohexyl (2-nonylcyclohexyl) Etc.), phenylpropyl (1-methyl-an-1), etc. 2, phenylbutyl (3-amino-p-phenylbutyl, etc.), alkoxypropyl propyl (3-(2-ethyl) An aliphatic hydrocarbon having a branched carbon such as hexyloxypropyl or the like, or an aralkyl is preferred. The earth represents a hydrogen atom, a Cl-12 fatty hydrocarbon group, a c7-2G silk group or 2. A R. fat. The hydrocarbon group may be linear, branched or cyclic. The carbon number of the aliphatic hydrocarbon group includes the carbon number of all the substituents, and the number thereof is usually 丨~□, ^ is 2~11. The aliphatic hydrocarbon group of R1 includes, for example, n-octyl group, methylhexyl j-methylhexyl group, etc., ethylhexyl (2-ethylhexyl group, etc.), cyclooctyl group, indolylcyclohexane = didecylcyclohexyl group Etc.), cyclohexyl silk, and the like. The aliphatic hydrocarbon group of Ri may have a substituent such as a ^C!-6 alkoxy group. The substituted aliphatic hydrocarbon group, for example, alkoxypropyldiethylhexyl)propyl, etc.). The R1 aliphatic hydrocarbon group terminal may be substituted with a carboxyl group. Deuterated aliphatic hydrocarbon groups, for example: 8 (rebel) octyl and the like. The portion of the silk of the aryl group of '^ can be linear, branched or ring-shaped. The carbon number of the aralkyl group is usually from 7 to 20, preferably from 7 to 1 Torr. In the aryl group, 9 201000567 R1 二二ί soil I group (3 -amino group -1 - * butyl group, etc.) and other phenyl group. • -η可可,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,,, The base is, for example, an unsubstituted phenyl group such as a phenyl group, a thiol phenylene-diphenyl group (4-trifluoromethylphenyl group, etc.), etc., an aliphatic thiol group or a trimethyl group. Spectral concentration and hue observation =, in this book, Ca-b means that the carbon number is a or more, & When the two kinds of azo compounds (1) are used in combination, the oil solubility is from the viewpoint of oil solubility, and two or more types of mouthpieces of the azo compound (1) are used, and the liquid is aa, „, 贞The pigment of the pigment is preferred. The combination of oil-soluble improvement 1 '1 ^: ί 2 N-substituted amine stone yellow azo compounds (diamine sulphate) and two 1 stone ΗN-substituted amine 4 fluorenyl azo compound (combination of monoamines. Further, the monoamine sulfonyl group is more preferable from the diamine sulfonyl group in terms of solubility. From the viewpoint of oil solubility, Rl records the larger base in the above example. Hunting chooses a large volume base from k, which can reduce the azo color weight stack interaction. (4) f=n) 'Improve the nature. It can protect the azo group and the light resistance. The large volume of Ri, for example, branched from 2_ethylhexyl, aliphatic hydrocarbon group (especially grade 3 waxy aliphatic hydrocarbon group), trifluoromethyl group, etc. Two or more (especially three or more) aliphatic hydrocarbon groups of a halogen atom, etc. The azo compound (I) or a salt thereof may be bonded to form a binary body at any position. : The compound represented by a compound represented by the formula (I-A) and formula (I_B) 10 201000567

OH

- (4) - U a | - α2_ν = ν · The same meaning is not the same. R, and R2 represent the secret (Bu B) % stretch base. 2 Severe C represents a divalent C6_14 aromatic smog group which may have a substituent. ) Good.乙C6-14方香族烟基' For example: stretching phenyl and stretching Caiji, etc., stretching phenyl car ^ \ C ίίiQ stone = fragrant, base substituents, for example: halogen atom, ~ alkyl, base , shale base, amine continuation base and N-substituted amine tartaric acid base. The three H, i are, for example, a gas atom, a chlorine atom, an atom and an iodine atom, and a fluorine shoulder, a fluorine atom or a bromine atom is preferred. The original k-based group, for example: methyl, ethyl, propyl, isopropyl, butyl, decylbutyl, tert-butyl, pentyl and hexyl, etc., carbon number i~ base number 1~2 The alkyl group is better, and the sulfhydryl group is especially preferred.土土乂1 Earth anoxia Cm alkoxy, for example: methoxy, ethoxy, propoxy, isopropoxy, ΐ, isobutoxy: second butoxy, third butoxy, The pentyloxy group, the hexyloxy group and the like are preferably an alkoxy group having a number of from 1 to 4, more preferably an alkoxy group having a carbon number of 2, and particularly preferably a methoxy group. N-substituted (four) counties, preferably -s〇2NHr3 groups. R3 agrees with the above expression. 11 201000567 R''1 and Z cW2 alkyl, for example. Isopropyl, n-butyl, isobutylene, butyl (1,13,3-tetramethyl butyl) :J has a stretch; J consists of a methyl butyl butyl group, a dimethyl hexanyl group, an ethyl hexyl group (2_ethyl hexyl group, etc.).正 12 201000567

(卜 2) (Η)

(HI) (Η 2) (1-13) (1-14) (Μ 5) (Ι-1β) (1-17) (1-18) 0-19) 13 201000567

HOgS H03S H〇3S

Ho3s-^^-n=n-^)=o

OH HO

HOaS-? 5 N=N

HO^S

S03H HO Factory ΜβΟ-^Λ-Ν=Ν-^>=ι f ηκ:

OMe HO

h〇3S"''^3~n"n~^L^0 α-28) CN S〇3H HO N=N ^=〇 (1-29) CN

0 (1-30) OH HO —N N=N—? h〇 (1-31)

CN^ Me〇-/~\-N=N—)=0 (1-32)Hn

HO

HO

H03S-^~y-N=N-f )=0 (1-33)

O

HO

HOaS-^3-N=N—(,_34)Q-SO3H ^CN (1-35) CN Ο (1-27)

14 201000567

SO3H HO

H03S =0 (1-39) CN S03H HO ,, ^^-N=N-^>=0 (1-40)

H03S

So3h

^ -N^N-f^^O (1-50) HO3S /~CN Me〇-^^-N=N-^%=0 (1-51) H03S wide SN

-N=Nf ^=0 0-42) Cl HO H03S-^~^-N=N—^>=0 (1-43) (CN H〇^Λ-Ν=Ν-^>=0 ( 1-44)H〇3S-Q HO, —N=N-^7=0 (1-45) HO3S' ^CN SO3H HO , MeO-^^-N=N-^>=0 (1- 46)

CN

\ HO /-- ho3s-/~\-n=n-/~>=o

/ HO /~<H〇3S-^^N=N-^>=0

CN

OMe HO H〇3S-^^-N=N-f)==0 (1-47) /CN

SO3H HO , —^^-N=N-^^=0 (1-48)

H03S

HO3S

HO , =N—? )=0 0-52) CN

H〇 . N=N—(1-53) SO3H / CN

(1-54)

CN

(1-55)

S03H HO ,,H〇3s~^3_N=N_t!)=:〇 ii-56) /CN SO3H HO -N=N-^V=0 CI-57) HO3S /CN

15 201000567

HOaS

SO#

In the formula (I), preferred examples of the N-substituted amine sulfonyl group are, for example, the formula (I-58) to the formula (I-178), and the formula (1-180) to the formula (I-207). 16 201000567

17 201000567

18 201000567

19 201000567 / so2 ho 〆 / 严—^y^jHH^s〇2

(1-107>

Ci-106) "NH S02 HO H〇sS- -N=N (1-108)

CN

NH-S02-f ^N=N-^)-0 SOsH /TMCN CHIOS)

^:K:

(1-114) I Ψ

H_K M^~C^n=n_v3=0

Kj S〇2 HO /-^ ho^-〇-n=n·"^0 , NH-S〇2-f >-N=N-f>=0 S03H /~^cn (1-117)

CN

NH-S〇2 \ HO NH- CM 19)

CN (Ι-Π8) Τ"^ΝΗ 〇zS. HO . MeO—^^^N==N-^~N> (1-120)

HN-S

N=N o2s-nh

CN

CN 0-Ϊ21) 20 201000567

0-136) 21 201000567

02S-N (1-146)

CN <yy,y4H-Spa-Q^N=N-^>=〇 NH-SO: (H47)

CN

SO3H HO /— l"W"N=N-0S=0 Wide CM a-148) CN

N H〇3S"-^^-N=N-/~^=〇 (1-149) / CN

A-154) 〇2S-NH^^

0 CN 22 201000567

23 201000567

24 201000567

(hi SO) (Ηβυ

--182) α-183) (Μ 84) (Η 85)

0-186) ¢-187) 25 201000567

(Μ 88) (hi 89)

(Η 94) 0-Ϊ95) 26 201000567

/

27 201000567

NS=N α-207) ο

The present invention is not limited to the azo compound 1, and is also included. Further, the cation forming the salt is not specifically such as (IV), _, a metal salt of a potassium salt; a salt; and an ethanolamine salt, an organic amine salt or the like is preferred. In particular, the metal salt (preferably a sodium salt) is money when it is included in the film substrate. Further, since the organic layer is contained in the curable resin composition, it is useful, and since it is a non-metal salt, it is also useful in the field of importance in insulation. The azo compound of the present invention, as is well known in the art of dyes, can be produced by coupling a diazonium with a pyridone. For example, an amine (diazo component) represented by the formula (8) can be diazotized by nitrous acid, nitrite or nitrite to obtain a compound represented by the formula (b), which is used as the diazonium salt. 28 201000567 (8) (b) A—NH2 A—NS|sj+ χ· Machine anion. In (), A and (1) represent the same meaning. X- indicates inorganic or

For example, the chloride ion, the chloride ion, the CH3, the chloride ion, the perchlorate ion, the hypochlorite ion, the CHrCOO., and the fly are preferably chloride ions, bromide ions, and CH3. -CO(y. (Even ear Μ eight w,, = will be the heavy gas salt expressed by the formula (b) and the ratio of the ratio of the formula (6) to the bite _ ((= knives) may be miscellaneous on 2G~6 ( Rc reaction, manufacture of azo compounds

Cc) (Formula (C) 7 'R1 and R2, which have the same meanings as in Formula (1)) The objective compound 1 having an aminesulfonyl group or an N-substituted amine sulfonyl group can also be used with an amine. The sulfhydryl AN-substituted amine hetero group amine (a) is produced by subjecting the amine group (a) of the cyano group to a coupling reaction, and then producing a sulfonyl group by sulfonylation. For example, it is first synthesized in a compound having a sulfo group of the formula (I) (hereinafter referred to as "azo sulfonic acid 1"), and the sulfo group (a S〇3H) is halogenated by a sulfite compound (-s 〇2X; x is a halogen atom), and the ruthenium halide compound is reacted with an amine (hereinafter sometimes referred to as "reactive amine"), whereby the sulfo group is sulfonated to give a sulfonamide compound (even) Nitrogen compound (I)). A preferred example of the azo acid (I) is, for example, a formula (1-1) to (1-3), preferably a formula (work-1) and (1-2). A sulfoxide halide compound, such as sulfinium fluoride, sulfoxide, sulfoxide, sulfite, etc., preferably a sulfurous chlorine, a sulfurous bromine, etc., especially a sub-29 201000567 sulfur Chlorine. The amount of the sulfonium halide compound used is, for example, about 1 to 10 moles relative to azo carboxylic acid (1) 1 mole. Further, when water is contained in the reaction system, it is preferred to use a sulfoxide halide in excess. Halogenation is usually carried out in a solvent. Solvents such as: 〗 〖, 4 - two hiring and other sewing (especially cyclic ethers); chloroform, dichlorodecane, carbon tetrachloride, hydrazine, 2 dichloroethane, dichloroethylene, trichloro Halogenated hydrocarbons such as ethylene, perchloroethylene, dichloropropane, chloropentane, hydrazine, and 2-dibromoethane. The amount of use of the solvent is, for example, about 3 parts by mass or more (preferably 5 parts by mass or more) and 1 part by mass or less (preferably 8 parts by mass or less) based on 1 part by mass of the azosulfonic acid (?). Further, it is preferred to use a N,N-dialkylcarbamide (e.g., n,N-dimethylformamide, N,N-diethylguanamine, etc.). When n,N-dialkylguanamine is used, it uses ruthenium relative to the sulfite-branched halide compound, for example, about 〜1 mole. After the azosulfonic acid (I) and the N,N-dialkyl T-amine are preliminarily mixed in a solvent, if a sulfinium halide compound is added, heat generation can be suppressed. The reaction temperature at which halogenation is inhibited is, for example, 〇 ° C or higher, preferably at least 7 〇 ° c or less, and more preferably 60. (The following: the reaction time is, for example, about 0.5 hours or longer, preferably 3 hours or longer, 8 hours or shorter, more preferably 5 hours or shorter. The halogenated sulfone compound prepared as described above may be isolated or reacted with a reactive amine, or may not be Separation and maintaining the state of the reaction mixture reacts with the reactive amine. Further, for isolation, for example, the reaction mixture may be mixed with water, and the precipitated crystals may be collected by filtration. The halogenation obtained, the crystallization of the compound, and the reaction with the reactive amine are visible. Water washing and drying are required. The reactive amines, such as the first-grade amines, are represented by the formula H2N-R3 (R3 is the same as the above). Specific examples of H2N-R include n-propylamine, n-butylamine and n-hexylamine. , decyl hexylamine (1,5-trimethylhexylamine, etc.), tetradecyl butylamine (m3 - tetramethylbutylamine, etc.), hexyl hexylamine (2: ethylhexylamine, etc.), amine Isophenylbutane (i-amino-p-phenylbutane, etc. i. isopropoxypropylamine, etc. The amount of reactive amine used is usually about 2 moles or more relative to the halogenating compound 1 \ ear 10 moles or less, preferably 7 moles or less. Addition of a halogenated sulfone compound and a reactive amine The order is not particularly limited, and more than the reactive amine is added (dropped) to the halogenating compound. Further, the reaction of the compound with the reactive amine 30 201000567 is usually carried out in a solvent. The solvent can be used and prepared for the ruthenium halide. The same solvent as the compound. The reaction of the ruthenium compound with the reactive amine is preferably carried out in the presence of a basic catalyst, such as a tertiary amine (triethylamine, triethanolamine, etc.). Group 3, an amine; an aromatic tertiary amine such as pyridine or mercaptopyridine; and a secondary amine (an aliphatic amine such as diethylamine or pyridine), etc. Among them, a tertiary amine, particularly triethylamine An aliphatic tertiary amine, preferably used. The amount of the basic catalyst used is generally about 1.1 moles or more, 6 moles or less, preferably less than the reactive amine (the amine reacted with the sulfone). When the reactive amine and the basic catalyst are added to the dentate compound, the addition of the basic catalyst is not particularly limited, and may be before or after the addition of the reactive amine. It can be added with a reactive amine. It can be added in advance with a reactive amine, also The reaction temperature of the sulfone compound and the reactive amine is, for example, the above, 5 or less, preferably 0 C or more and 30 ° C or less. Further, the reaction time is usually about 1 to 5 hours. The sulfonamide compound (azo compound 1) which is obtained from the reaction mixture is not limited, and various known methods can be employed. For example, the reaction is mixed with acetic acid and water, and the precipitated crystal is preferably filtered. After the acid solution is prepared, the multi-scale reaction mixture is added to the: aqueous solution. The addition temperature of the reaction mixture is usually above the wrist, preferably below the machine, preferably below the machine. The mixture is stirred for 4 hours at the same temperature. The day of the knot is usually washed with water or the like, followed by drying. Further, it can be further refined by a known method such as recrystallization. For example, the compound of the sun or the moon or its crane is highly versatile. Solvent, organic solvent. The above organic solvent may have various kinds of faces. For example, a solvent of ketone is preferably used, for example, ethyl trimethylacetate, dmcetonealcohol or the like, preferably diacetone alcohol. Therefore, the azo compound or its brain, due to the high solubility of the immersion solution, indicates that the fiber material of the color is displayed or the light is transmitted through the light, and the liquid crystal display device is specialized. Further, the compound of the present invention or its _, when the absorption spectrum 31 201000567 is measured, has a large absorption in the wavelength region of 400 to 450 nm, and therefore, it is preferably used as a yellow dye. Next, the azo compound (azo compound (8)) of the present invention represented by the formula (?) will be described. HQ R11

HOOC-A1—N two N

(10 R12, R« The azo compound of the present invention or a salt thereof represented by the formula (II), characterized in that the bond is a benzene ring of an azo group of a pyridone azo compound, and the azo group is at a meta position. Or a carboxyl group, and the substituent R1 on the nitrogen atom in the pyridone ring has a hydrocarbon group having a large carbon number. Further, a part of the pyridone ring represented by the formulas (II) and (III), except for the enol type And ketone type. By this structure, the azo dye compound of the present invention or a salt thereof exhibits an ancient solubility, a heat resistance, and a resistance to N., and a 'day-like azo-nitride J or its 5^ direction The solvent for solubility may be selected from, for example, New Lai (acetic acid ethyl acetate, etc.: acoustic J ketone (dilyl alcohol, etc.), _ (propylene glycol mono(tetra), propylene glycol mono(tetra)acetic acid) special low volatility solvent. In the formula (II), AI means at least one of a group consisting of one of its gas, methoxy, and carboxyl groups: i = or between phenyl groups. Even nitriding fine = has a carboxyl group at a specific part, can take into account the solubility of 2 2 ^ by improving the solubility, _ medium, Al has a 丨 。. In order to = table can not be replaced by Q 〇 〇 An aliphatic hydrocarbon group, a trans-group, or a C6-20 aryl group which may be substituted. The aliphatic hydrocarbon group of the exo-2-2 pentane may be a linear, aliphatic hydrocarbon-based carbon All rhyme, read--. ru aliphatic nicotine contains: for example, n-xin ^ 'methyl ^! 250 ' - dimethyl cyclohexyl, etc.), cyclohexyl alkyl, etc. J soil, per hexyl (2, 2 曰月曰 aliphatic nicotyl, can be substituted for 32 201000567 such as Cm alkoxy groups and other substituents. The substituted aliphatic hydrocarbon base: alkoxypropyl (3~ (2-ethylhexyloxy) propyl, etc. And the aliphatic hydrocarbon group of r11 may be substituted with a terminal group. The substituted aliphatic hydrocarbon group may be, for example, 8-(dethio)octyl group, etc. The alkyl moiety of the aromatic group of R may be linear, Any of a branched chain or a ring. The carbon number of the aralkyl group is usually 7 to 20, preferably 7 to 10. The aralkyl group is a benzyl group (3-amino group 1) A phenylalkyl group such as a phenylbutyl group, etc. is represented by a phenylalkyl group. The aryl group of the second R11 may be unsubstituted or may have a substituent such as an aliphatic hydrocarbon group or a carboxyl group. The carbon number of the above aryl group, including the carbon number of the substituent , usually 6~2 〇, more than 1 to 10. These aryl groups are unsubstituted or substituted, such as phenyl, carboxyphenyl (2-carboxyphenyl, etc.), trifluoromethylphenyl (4ιΓ trifluoromethylphenyl, etc.) Phenyl, etc. R12 represents a substituted Cy aliphatic hydrocarbon group or a trifluoromethyl group. From the viewpoint of color density and hue, a methyl group is preferred. Further, R represents a hydrogen atom, an amine carbenyl group or a cyano group. Ri3 is The hydrogen atom or the azo compound of the present invention or the azo compound of the present invention can exhibit a particularly high color concentration. I. Further, in the present invention, ca_b means that the carbon number is a or more and b or less. From the viewpoints of color density, solubility, heat resistance, and light resistance, it can be further defined. In particular, from the viewpoint of improving the solubility to a solvent, it is desirable that the azo group is in the para or meta position and has no carboxyl group adjacent to the azo group. That is, for example, a compound represented by the formula (ΠΙ). Eight

R10&Rl5' in R10>R each independently represents a hydrogen atom, a halogen atom, a fluorenyl group or a methyl group. In the case of 5-color rich gas, it is preferred to use a hydrogen atom or a sulfhydryl group. Alkoxy or fluorenyl. And, at least one of R10, R-, and Han is represented. By the 1?" Chen leads people to rebel and can improve solvent solubility. More preferably, one of .R16, R17, and R represents a carboxyl group. And R18 and R each independently represent a ruthenium atom, a halogen atom, a methyl group, U. Γ>16^T.17 « ^18 _ .. another azo compound or a salt thereof of the invention Π) and (111) represent, t, tautomer. The compounds represented by the formulae (Π) and (111) form a dimer having a ternary body or more. When two or more types of azo compounds (11) are used in combination, in the case where i is used alone, 33 201000567 °, therefore, a combination of two or more kinds of properties is added from the viewpoint of solubility, and the coloring matter is set. The azo compound which dissolves the filaments (single azo compound (dicarboxylic acid) has a lower molecular weight than the dicarboxylic acid having 1 degree of bis 3 monocarboxylic acid, and therefore, from color richness > ^The singular lUbf object's choice of Rn to select the base of the hybrid product can reduce the solubility. In addition, by selecting a large volume base, it can protect the 4 milty-based Nike. The aforementioned high volume Rll, for example: 2-ethylhexyl branched aliphatic hydrocarbon group (especially a tertiary aliphatic hydrocarbon group), etc. Preferred examples of the formula (II) are, for example, the formula (II-301) to (II-326).

COOH CONHa

34 201000567

35 201000567

Among the compounds represented by the formula (II), an azo compound represented by the formula (III) is more preferable from the viewpoints of improvement in color density, solubility, heat resistance, light resistance and the like. 36 201000567

Preferred examples of the formula (III) are the formulae (III-1) to (III-40). 37 201000567

HOOC

HOQC

38 201000567

39 201000567

40 201000567

HOOC

HQ

O

f

—^~^-Ν=Ν (III-26) HOOC

\ HO , (m.28) HOOC—f_VN==N-f > 〇

OMe HO /~· HOOC-/~\-N-N-/~>=0 -o

(III-29)

41 201000567

\ )-N=N-f >=〇 HOOd^Me ^ . The present invention is not limited to the compounds represented by the formulae (Π) and (III), and the salts thereof are also included. The cation for forming the salt of the salt agent X' is not particularly limited, and it is considered that the metal salt of the organic salt of the dissolved amine salt; and the ethanolamine salt are preferably used in the polarizing film. In particular, a metal salt (preferably a sodium salt) is useful in the case of a substance and is used again. In addition, the 'organic amine salt contained in the resin is sclerosing compound' because it is a non-metal salt, and in the field of importance of insulation, there is also a 42 201000567 compound ϋ ίί compound, as is well known in the field of dyes, Manufactured by coupling, for example, an amine represented by the formula (8) (diazonium: a compound obtained by the formula (b) can be obtained by re-gasification of a sulphur A into a 4 ct k, an acid or a nitrite. 'As the aforementioned recording. HOOC-A1 - NH2 ( a ) HOOC-A1-N£N ( h ^ e VD> f

Θ In the machine, A1 means the same meaning as in formula (II). Χ· indicates inorganic or woven or money anions, such as: vapor ions, chloride ions, desert ions, broken ions, perchlorate ions, chlorous acid ions, CH3 — c〇〇_ : c〇〇 is preferably a vapor ion, a bromide ion, or a ch3-coo-.

R12 R« 成八,又: The diazonium salt represented by the formula (b) and the formula (c) indicate the ratio of the salt to the singularity (coupled into a knife) 'pass ten in an aqueous solvent at 20~6 (rc reaction, Production of azo compounds HO R«

(In the formula (C), R11 to rU are not the same as those in the other tables.) A The method of obtaining the azo compound of the target compound from the reaction mixture is not particularly 'required, and the known method such as recrystallization may be further carried out. The crystals obtained by salt filtration are usually purified by a stepwise purification of the pyridones represented by the formula (C), and can be produced by a known production method. For example, the technique β disclosed in Patent Document 1, Patent Document 3, or Japanese Patent Publication No. 49-40474 is used. The azo compound (I) of the present invention or a salt thereof is highly soluble in a solvent. The present invention discloses an azo compound (II) or a salt thereof which is highly soluble in a solvent. (Embodiment) Hereinafter, the present invention will be described more specifically with respect to the present invention. In the 'Examples and Comparative Examples', "%" and "Participate are mass% and mass parts." If there is no special 5, the present example 1 is used in the formula (a-1), which is represented by the formula (a-1). Add hydric acid to water 25. Part and N_ 曱 转 转 ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( ( 35%_ Gaya is brown and secret, and it is 2 hours. Add the kein #acid to the water after the addition, and add it to the reaction to dissolve the two ho3s ~NH2 (a-1) 4 = by the formula (c-1) i) butyl-3 chloro group

After the liquid is shown, the secret is mixed with the water-soluble solution. The solution is adjusted to PH8~9 ’-side with a solution of sodium di-sodium sulphate and a small dark solution. The suspension will be made. After the completion of the dropwise addition, stirring was further carried out for 2 hours, and filtration was carried out to obtain 140 parts of the dragon: clothing and added to the reaction solution, and the mixture was mixed for 5 hours. The azo compound 35 "8 thief, shot 36) Table 44 201000567

The structure of the compound (1 - 36) is determined by mass analysis. Quality Analysis JMS — 7〇0 (made by Nippon Electronics Co., Ltd.). In the texture, the ionization mode = FD +: m / z = 460 The obtained azo compound (I - 36) 0.35 g is dissolved in N, N-dimethylformamidine to make the volume 250 cm3 '2cm3 of which is The water was diluted to a volume of 1 〇 plus degree: 0.028 g/L), and the absorption spectrum was measured using a spectrophotometer (quartz cuvette, long sound of cuvette 1). The obtained absorption spectrum is shown in Fig. 。. , ej kmax=441nm shows an absorbance of 3.1 (arbitrary units). 〇; Example 2 - In a flask equipped with a cooling tube and a stirring device, put azonitride 36) 5.0 parts, 50 parts of chloroform and hydrazine, Ν - 2.1 parts of dimethylformamide, and 3.5 parts of chlorine sulfite was added dropwise in a state of 20 ° C or less. After the completion of the dropwise addition, f 50 〇 C ' was maintained at the same temperature for 5 hours to allow the reaction, and then cooled to 2 Torr. A,, = main reaction solution, maintained at 2 (TC below) with stirring, add 2% (., 8.0 parts and 15 parts of triethylamine mixture. After that, stir at the same temperature for 5 hours to ^ The reaction mixture is obtained by adding a small amount of the solvent to the reaction mixture by a rotary evaporator, and then vigorously mixing the mixture. The mixture is added to the surface and added to a mixture of 29 parts and 300 parts of ion-exchanged water. Crystallization was carried out, and the crystals were separated and washed with ion-exchanged water, and dried under reduced pressure at 6 CTC, and 5.0 parts (yield 78%) of azo compound represented by (1-111).

45 201000567 The structure of the compound (I-ill) is determined by qualitative analysis. The mass spectrometer used JMS-700 (manufactured by JEOL Ltd.). Mass analysis: ionization mode = FD +: m / z = 571 The obtained azo compound (I - 11 l) 〇. 35 g dissolved in ethyl lactate to a volume of 250 cm 3 , wherein 2 cm 3 was diluted with ion-exchanged water to a volume of 1 〇〇 cm 3 (concentration: 0.028 g/L), and an absorption spectrum was measured using a spectrophotometer (quartz cuvette, optical path length; lcm). The absorption spectrum obtained is shown in Fig. 2. This compound showed an absorbance of 2.5 (arbitrary unit) at λ Μχ = 434 ηιη. Example 3

Adding 2 parts of water and 50 parts of N-decylpyrrolidone to 25.0 parts of f aniline-tetrahydro acid represented by formula (a-2), and then cooling with 3〇% sodium hydroxide under ice cooling The aqueous solution is carefully adjusted to pH 7-8. The following operations were carried out under ice cooling. 27 parts of sodium nitrite was added and stirred for 30 minutes. A small amount of 97.3 parts of 35% hydrochloric acid was gradually added to make a brown solution, followed by stirring for 2 hours. An aqueous solution of 251 parts of guanamine-based sulfuric acid dissolved in 25 parts of water was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt.

..."^八小ζου物, and 丞pyridone 28 9 ^, under 30% sodium hydroxide aqueous solution adjusted to ρΗ8~9. Adjusted with 30% aqueous sodium hydroxide to ρΗ8 3 -cyano-4-indolyl-6-hydroxyl and JN- Τ丞0 to 唂0^:ketone 28.9 parts

CN is carried out under the ice with Zf. The above-mentioned pyridone water-soluble aqueous solution of sodium iodide was adjusted to pH 8 to 9, and after the solution, a dark solution containing diazonium salt was added by pumping with 30% hydrogen peroxide. Let ^ r 1' proceed. The aqueous solution of the pyridone was stirred to adjust the aqueous solution of the colorless sodium oxide to pH ρ8 to 9 while taking 2 liters of the suspension of the nitrogen salt L fc. After the completion of the dropwise addition, 140 parts of the purified salt was added to the reaction solution by stirring 2, and the mixture was stirred for 5 hours. 46 201000567 Obtained by the formula (1 - 35), the obtained yellow solid was decompressed at 6 Torr. The azo compound was dried to give 46.7 parts (yield: 79%). ,

The structure of the compound (1 - 35) is determined by mass analysis. The quality division uses JMS-700 (manufactured by JEOL Ltd.). Qualitative analysis: ionization mode = FD +: m / z = 460 The obtained azo compound (I - 35) 〇. 35g was dissolved in N, N - dimethylformamide to make the volume 2cm3 of 250cm3' The water was diluted to a volume of 1 〇〇 cm 3 (concentration: 0.028 g/L), and the absorption spectrum was measured using a spectrophotometer (quartz colorimetric suit, colorimetric length lcm). The absorption spectrum obtained is shown in Fig. 1. The compound showed an absorbance of 3.2 (arbitrary units) at Xmax = 435 nm. Example 4 In a flask equipped with a cooling tube and a stirring device, 5.0 parts of an azo compound (I - 35), 50 parts of a gas, and 2.1 parts of N,N-dimethyl decylamine were charged and maintained under scramble. In the state below 20 ° C, 3.5 parts of sulfite chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 ° C. The reaction was maintained at the same temperature for 5 hours, and then cooled to 2 ° C. The cooled reaction solution was maintained at 20 ° C or lower under stirring, and tetrahydroanthracene was added dropwise. Mixture of 8 parts of sulphate and 15 parts of triethylamine. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. Next, the obtained reaction mixture was distilled off by a rotary evaporator, and then a small amount of decyl alcohol was added, followed by vigorous stirring: mixing. The mixture was added to a mixture of 29 parts of acetic acid and 300 parts of ion-exchanged water while being disturbed to precipitate crystals. The precipitated crystals were separated and washed with ion-exchanged water and dried under reduced pressure at 60 ° C to obtain 5.7 parts (yield: 90%) of the azo compound represented by formula (1-151). 47 201000567

The structure of the compound (I-151) was determined by mass analysis JMS~7〇〇 (manufactured by Sakamoto Electronics Co., Ltd.). . Mass analysis equipment using mass analysis: ionization mode = FD +: m / z = 543 Μ gas mixture f (I - 151) 〇. 35g dissolved in ethyl lactate to make the volume 25 〇 cm 'I will exchange ionized water Dilute to make the volume of rattan ^ (Han: 0.028g / L) 'Use a spectrophotometer (quartz colorimetric summer, light path length; 1 ring to determine the absorption spectrum. The obtained absorption spectrum is shown in Figure 2. The compound, in λιη &χ=438ηιη The absorbance was 2.6 (arbitrary unit). Example 5 In a flask equipped with a cooling tube and a stirring device, 5 parts of azo compound (1-35), 30 parts of methoxycyclopentane and N were charged. 5.8 parts of N-dibutyl decylamine, maintained at a temperature below 20 ° C under the disturbance, and added 4 parts of sulphur chlorinated chlorine. After the completion of the dropwise addition, ' ^ warm to 40 ° C, maintain at the same temperature 5 After the reaction, the reaction was cooled to 2 ° C. After cooling, the reaction solution was kept at a temperature of 20 ° C or lower under stirring, and 3.7 parts of 1-amino 7-propanol and 4 parts of triethylamine were added dropwise. The mixture is mixed. Then, the mixture is stirred at the same temperature for 5 hours to carry out the reaction. Secondly, the obtained reaction mixture is distilled off by a rotary evaporator, and then added. The amount of methanol was stirred vigorously, and the mixture was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water while stirring to precipitate crystals. The crystals were separated by filtration and thoroughly washed with ion-exchanged water at 60 ° C. Drying was carried out to obtain 4.2 parts of an azo compound represented by the formula (1 to 184) (yield 74%).

48 201000567 The structure of compound (I-151) is determined by mass analysis. The mass spectrometer used JMS-700 (manufactured by JEOL Ltd.). " Mass Analysis: Ionization Mode = FD+: m/z = 517 The obtained azo compound (I-184) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm 3 '2 cm 3 of which was diluted with ion-exchanged water to make the volume 1 〇〇 cm 3 (concentration: 0.028 g/L) 'The absorption spectrum was measured using a spectrophotometer (quartz cuvette, optical path length; lcm). The absorption spectrum obtained is shown in Fig. 2. The compound showed an absorbance of 2.4 (arbitrary units) at ^max = 432 nm. Example 6 f : In a flask equipped with a cooling tube and a stirring device, 3 parts of azo compound (I-35), 45 parts of tetrahydrofuran and N,N-didecylamine were added, and the mixture was maintained under stirring for 20 parts. In the state below C, 2.4 parts of sulphurized milk was added dropwise. After the completion of the dropwise addition, the temperature was raised to 4 Torr. (^', the reaction was stirred at the same temperature for 5 hours, and then cooled to 2 ° C. The cooled reaction solution was maintained at 20 ° C or lower under stirring, and ethylenediamine 5·8 and triethyl were added dropwise. A mixture of amines. Thereafter, the reaction was stirred at the same temperature for 5 hours to effect the reaction. Secondly, the obtained reaction mixture was subjected to a rotary evaporator to remove the solvent, and then a small amount of sterol was added thereto, followed by vigorously stirring. The mixture was mixed with 20 parts of acetic acid and 2 parts of ion-exchanged water to precipitate crystals. The crystals were separated by filtration, washed well with ion-exchanged water, and dried under reduced pressure at 6 ° C to obtain the formula (I). 204) azo compound represented! 5 I parts (yield 48%).

The structure of the compound (I-204) is determined by mass analysis. The mass spectrometer used JMS-700 (manufactured by JEOL Ltd.). Berry for analysis. Ionization weight formula ^ρχ^ιηι/ζ^δόΟ 1 obtained azo compound (I - 204) 0.35g dissolved in ethyl acetate to make the volume 250cm3 '2cm3 of which is diluted with ion-exchanged water, Make the volume 1 〇〇cm3 (concentration: 0.028 g/L), and use a spectrophotometer (quartz colorimetric, optical path length; lcm) to measure the absorption spectrum of the absorption spectrum 2010 49 201000567 as shown in Fig. 2. This compound showed an absorbance of 2.5 (arbitrary unit) at λ Μχ = 43 〇 ηη. Example 7 μ was added with water 200 = 10.0 parts of streptoamine-4-hemeic acid represented by formula (b), and then adjusted to pH 7-8 with 30% aqueous sodium hydroxide solution under ice cooling. The following operations were carried out under ice cold. Add a guar sodium and mix for 3G minutes. A small amount of acid 39 was added, and the G portion was allowed to form a brown solution for 2 hours. An aqueous solution in which the hetero-sulfide = 0.1 wound is dissolved in 101 parts of water is added to the reaction solution to contain a solution of heavy _. ^ ^

H〇3S NH2 (a-2) 9 after 'under ice 77 ' with 30% aqueous sodium hydroxide adjusted to PH8'

(c-2) After the solution, the above-mentioned ratio _ aqueous solution is mixed to form a colorless solution containing the diazonium salt. After the drop is over, the mixture is mixed with J. ί Filter 'The color of the system is 嶋 under reduced pressure at 6°. . Dry welding was carried out, and 18.6 parts of the compound represented by the formula (I-210) was obtained (yield 92 8%).

0-21O) 50 201000567 The structure of the compound (I-210) is determined by mass analysis. The mass spectrometer used JMS — 7〇0 (manufactured by Sakamoto Electronics Co., Ltd.). Mass analysis: ionization mode = FD +: m / z = = 750 0.35 g of the obtained compound (I-210) was dissolved in N,N-dimethylformamide to make the volume 250 cm3, and 2 cm3 of the solution was diluted with water. The volume was made 1 〇〇cm3 (concentration: 0.028 g/L). The absorption spectrum was measured using a spectrophotometer (quartz colorimetric, colorimetric length is icm). The compound showed an absorbance of 3.1 (arbitrary unit) at lmax = 435 nm. Example 8 In a flask equipped with a cooling tube and a stirring device, a compound aliquot, 50 parts of acetonitrile, and 1.5 parts of hydrazine, hydrazine-dimethyl decylamine were added, and the mixture was maintained at 2 〇 ° C or less under stirring. 'Drip addition of sulfite brewed 3·7 parts. After completion of the dropwise addition, the temperature was raised to 4 ° C, and the reaction was maintained at the same temperature for 2 hours, and then cooled to 2 (rc. The cooled reaction solution was poured into 150 parts of ice water while stirring, and then stirred for 3 minutes. The yellow crystals separated by filtration were thoroughly washed with tap water at 6 Torr. (: Drying under reduced pressure for 2 hours. Prepare a flask equipped with a cooling tube and a stirring device, and put 2 parts of 2-aminopropanol and N- 20 parts of decylpyrrolidone is maintained at a temperature of 2 〇t or less with stirring. The yellow crystals adjusted as described above are charged for 1 hour. After the yellow solid is charged, the temperature of the solution is raised to room temperature, and then the reaction solution is added. After stirring for 30 minutes, 40 parts of decyl alcohol was added to the reaction solution and the mixture was stirred, and the mixed solution was added to a mixture of 29 parts of acetic acid and ion-exchanged water lion's parts while stirring to precipitate crystals, and the precipitated crystals were separated. The ion-exchanged water was sufficiently washed, and dried under reduced pressure at 603⁄4 to obtain 3.9 parts (yield 69%) of the compound of formula (1 - 198).

The structure of the compound (1 - 210) is determined by mass analysis. Quality JMS_7〇0 (made by Nippon Electronics Co., Ltd.). From the quality analysis: ionization mode == FD +: m / z = 864 201000567 , $ obtained compound (1 - 198) 0.35g dissolved in ethyl lactate, so that the volume is '2cm3 of which is ion exchange The water was diluted to make the volume a chirped sputum concentration: f, 28 g/L), and the absorption spectrum was measured using a spectrophotometer (quartz colorimetric, optical path length; lcm). The compound showed an absorbance of 2·6 at λιϊ^χ=433ηιη (any comparative example 1 was synthesized by the method described in Patent Document 1 to synthesize the following azo compound. The azo compound (d:l) 〇.35g was dissolved in lactate B. The ester has a volume of 25 〇 cm 3 , and 2 cm 3 of it is separated, diluted with water to make a volume of 1 〇〇 cm 3 (concentration: 〇〇 28 g / L), and a spectrophotometer (stone, cuvette, light path length; The absorption spectrum is determined by lcm). The absorption spectrum obtained is shown in Figure 2. The compound shows an absorbance of 22 (arbitrary units) at λιη3χ=425ηιη.

(d-1) <Evaluation of Solubility of Solvent> The solubility of the azo compound of Examples i to 8 and Comparative Example with respect to the agent was determined in the following manner. Mixing each azo compound with diacetone alcohol in a 50 mL sample tube to obtain a mixing ratio of 1% (W/V) and 3% (W/V), after sealing at 4〇t: The sonic oscillator oscillates for 10 minutes. Then, after standing at room temperature for 3 minutes, the presence or absence of insoluble matter was recognized. k, in the mixed solution prepared as 1% (W / V) 'insoluble matter is determined to be dissolved Lu 1 / / (X), in the preparation of 1% (W / V) mixed solution, no insoluble The solubility of the insoluble matter in the mixed solution of 3% (W/V) is determined as 丨~不& 3%(Λ)' in the preparation of a mixed solution of 3% (W/V) without insolubilization. The object is fixed at 3% or more (〇). The results are shown in Table 1. Table 1 52 201000567

4 定·J ^ 么丄 — 2^ _I ~ one ____| Two ____ concentration. It can be seen that the compound of the present invention has both high solubility and high spectroscopic activity. Example 9: 4-aminobenzoic acid represented by formula (a-3) 5. After adding 25 parts of water, = ice-cold I, adjusted to pH 7-8 with 30% aqueous sodium hydroxide solution. The following operations are performed under ice and under. 7.6 parts of sodium nitrite was added and stirred for 30 minutes. A small amount was gradually added to 35%, and 22.8 parts of an acid was allowed to form a brown solution, followed by stirring for 2 hours. An aqueous solution of 6 9 parts of decylamine sulfuric acid dissolved in water of 69 parts was added to the reaction solution and stirred to obtain a suspension containing a diazonium salt. H〇〇C \_/NH2 (a~3) is represented by the formula (c-3) 1-(2-ethylhexyl)~3-cyano-4-methyl-6-hydroxypyridine-2. After adding N-methylpyrrolidine g^1〇5 parts and 53 parts of water to the ketone 10^=, it was adjusted to ρΉ8~9 with 30 °/° sodium hydroxide aqueous solution under ice cooling.

53 201000567 ή The following ^ is carried out under 'water cooling' mixing the above-mentioned t-fine aqueous solution to make it into color, and after liquid-filling, the surface is adjusted to pH 8~9 with 30% sodium hydroxide aqueous solution;; The pump drops the suspension containing the money and salt. Small drops gave a brown suspension. If you have a good time, you will get a small amount of ffr cake. η本-Γ Γ Only the color solid is dried at 60 ° C under reduced pressure, and the azo compound 1 〇 9 is represented by formula (III-1).

HOOC

The structure of the azo compound formula (III-1) is determined by 1H_]sny [R, and mass analysis. EIA_5〇〇 (manufactured by JASCO Corporation) was used for the NMR apparatus, and MS-7〇0 (manufactured by Sakamoto Electronics Co., Ltd.) was used as the mass spectrometer. H-NMR (500 MHz, δ value (ppm, TMS basis), 〇1^〇). 0 84 — 0.88 (6H, m), 1.19-1.33 (8H, m), 1.77 (1Η, m), 2.51 (3H, . s), 3.71 - 3.79 (2H, m), 7.76 (2H, br. d, J = 8.8 Hz), 7.97 (2H, br. d, J = 8.8 Hz), 13.81 (1H, Br. s), 14.3 (1H, br. s) C-NMR (125 MHz, δ (ppm, TMS basis), DMSO): 10.30, 13.93, 16.43, 21.03, 22.47, 23.26, 28.01, 29.91, 36.83, 43.12 , 101.54, 114.88, 117.12, 123.97, 128.22, 130.87, 144.64, 159.16, 160.23, 160, 56, 166.54, 171.98 Mass analysis: ionization mode = FD+: m/z = 410 The azo compound (III) obtained — l) 35.35g dissolved in ethyl lactate to a volume of 250cm3 '2cm3 of which is diluted with ethyl lactate to make the volume 100cm3 (concentration: 0.028g/L)' using a spectrophotometer (quartz colorimetric) colorimetric The length of the dish is icm) The absorption spectrum is measured. The compound showed 2.4 (any unit) in absorbance at Ainax = 431 nm. Example 10 54 201000567 After adding 25 parts of water to the 4-aminobenzene benzene acid 5 〇 represented by the formula (a-3), it was adjusted to 30 7% by using 30% sodium hydroxide aqueous solution under ice cooling. . The following operations were carried out under ice. 7.6 parts of sodium sulfite was added and stirred for 30 minutes. A small amount was gradually added to 22.8 parts of 35% hydrochloric acid to make a brown solution, and then scrambled for 2 hours. An aqueous solution of 6 9 parts of decylamine sulfuric acid dissolved in 69 parts of water was added to the reaction solution and stirred to obtain a suspension. ^ I, expressed by the formula (c-4) [3,-propyl(2,-ethylhexyloxy)]-3 —imyl-4-f-yl-6-yl-based bite-2 - ketone 12 9 parts to add methyl hydrazine

After J嗣I29 parts and 64 parts of water, it was dissolved in 3〇% sodium hydroxide water to pH 8~9 under ice cooling.

Luo connected the following ί to the cold. The above-mentioned aqueous solution of ton is made into a colorless solution. The aqueous solution of sodium hydroxide is adjusted to ΡΗ8~9, and the surface takes 2 hours. ιϊίίί contains a suspension of diazonium salt. After the end of the addition, the mixture was mixed for 2 hours to obtain a sputum. The transition "drys the yellow solid at 60 ° C under reduced pressure, > (-6) represents 5 parts of the azo compound (yield 73%).

55 201000567 The structure of the azo compound (III-6) is determined by mass analysis. The mass spectrometer was JMS-7 〇0 (manufactured by JEOL Ltd.). , mass analysis: ionization mode = FD +: m / z = 468 3 of the azo compound (in-6) 0.35g dissolved in ethyl lactate to make the volume into 250cm3, 2cm3 of which was diluted with ethyl lactate to make the volume It is 1 〇〇cm3 (concentration: 0.028 g/L) using a spectrophotometer (quartz colorimetric, the length of the cuvette is km) j疋 absorption spectrum. This compound has an absorbance at Xmax = 431 nm for any soap position). Example 11 Under ice cooling, 25 parts of water was added to 5.0 parts of 3-aminobenzoic acid represented by the formula (a-4), and then V was adjusted to pH 7 to 8 with a 30% aqueous sodium hydroxide solution. The following operations are performed on ice below the ice.

A suspension of nitrogen salts.

After i- 6-hydroxypyridine-2-_53 parts represented by formula (c-3), under ice cooling,

NOC-pyridylpyrrole is added to 5 parts of HOOC No. (2-ethylhexyl)-3-carbyl-4-methyl- 1 〇'. Set 1〇5 parts and water to 30°/. The sodium hydroxide aqueous solution was adjusted to pH 8 to 9.

The following is known as ice; after the liquid, the surface is 30 〇 /.

- Surface cost 2 56 201000567 hours Add a suspension containing diazonium salt to Lipu. After the completion of the dropwise addition, a brown suspension was obtained after another 2 hours of dropping. The resulting yellow solid was filtered under reduced pressure at 6 Torr. The crucible was dried to obtain 12.3 parts (yield 82%) of the azo compound represented by the formula (III-11).

P- HOOC

The structure of the f azo compound (III-11) is determined by mass analysis. The quality is divided into two parts: JMS-700 (manufactured by JEOL Ltd.). , mass analysis: ionization mode = FD +: m / z = 410, 0.35g of azo compound (III-1 l) was dissolved in ethyl lactate to make the volume 250cm3, 2cm3 of which was diluted with ethyl lactate The volume was made 1 〇〇 cm 3 (concentration: 2.028 g/L). The absorption spectrum was measured using a spectrophotometer (quartz cuvette 'the length of the cuvette is icm). The compound showed an absorbance of 2. 〇 (arbitrary unit) at Xmax = 427 nm. Comparative Example 2 After adding 225 parts of water to 45.1 parts of 4-aminobenzoic acid represented by the formula (a-3), it was adjusted to pH 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were carried out under ice cold. 68.0 parts of sodium nitrite was added and mixed for 3 minutes. A small amount of stepwise addition; ^ 35% hydrochloric acid 2 〇 5 · 4 parts 'after a brown solution was stirred' for 2 hours. An aqueous solution of 61.8 parts of amidino group and an acid dissolved in water of 6184 parts was added to the reaction solution and mixed to obtain a suspension containing a diazonium salt. After adding 629.7 parts of water to 63.0 parts of the base 唆3_cyano fluorenyl group 6 represented by the formula (c~1), after cooling with ice, 3 〇 0 / 〇 sodium hydride The aqueous solution was adjusted to ΡΗ8~9. 57 201000567

After the liquid 2 is carried out. When the above-mentioned aqueous solution is used for colorless dissolution, it is pumped and added. Ί1 is ρΗ8~9, and the surface is spent 2 small. After the end of the addition, stir for another 2 hours. 140 parts of the refined salt was added to the reaction solution, and the mixture was stirred for 5 hours. The coloring solid was dried at 6 (rc) under reduced pressure to give 98.4 parts (yield: 79%) of the compound of the formula (d-2).

The structure of the azo compound (d-2) is determined by mass analysis. The mass spectrometer was JMS-7 (manufactured by Sakamoto Electronics Co., Ltd.). Mass analysis: ionization mode = FD +: m / z = 354 0.35 g of the azo compound (d-2) obtained in 3 was dissolved in ethyl lactate to make the volume 250 cm 3 '2 cm 3 of which was diluted with ethyl acetate to make the volume 1 〇〇 3 3 (concentration: 0.028 g / L) 'The absorption spectrum was measured using a spectrophotometer (quartz colorimetric, colorimetric length is icm). The compound showed an absorbance of 2.5 (arbitrary units) at Xniaxilmn. Comparative Example 3 After 50 parts of water was added to the 4-aminobenzoic acid isobutyl ester loo portion represented by the formula (a-4), it was adjusted to pH 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. The following operations were carried out under ice cooling. Add 10.7 parts of sub->5 sodium sulphate and stir for 3 minutes. A small amount of 32.3 parts of 35% hydrochloric acid was added in a small amount to make a brown solution, followed by stirring for 2 hours. Adding an aqueous solution of guanamine 58 201000567 to a reaction solution and obtaining

NHj (a-4) ♦ D-butyl-3-cyano-4-methyl-6--is dissolved in the base water to pH^9卩".2 miscellaneous in the material 17 'money minus oxidation Then proceed with the cold. The 吼 _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ : 140 parts of the purified salt was added to the reaction solution, and the mixture was stirred for 5 hours. The yellow solid was subjected to a reduced pressure at 60 ° C. Drying to obtain 15.9 parts of the azo compound represented by the formula (d-3) (yield 75) %).

The structure of the azo compound (d-3) is determined by mass analysis. The mass spectrometer used JMS — 7〇0 (manufactured by Sakamoto Electronics Co., Ltd.). Qualitative analysis: ionization mode = FD +: m / z = 410 ^ 偶 azo compound (d-3) 〇. 35g dissolved in ethyl lactate to make the volume 250cm3 '2cm3 diluted with ethyl lactate The volume was made 1 〇〇 cm 3 (concentration: 0.028 g/L). The absorption spectrum was measured using a spectrophotometer (quartz cuvette, the length of the colorimetric icm). The compound showed an absorbance of 2.5 (any unit) at Xmax = 430 nm ' 'Comparative Example 4 59 201000567 Add water to the 2~-amino-3-methyl benzoic acid 15·9 part represented by the formula (a-5) After 9.3 parts, it was adjusted to ρΗ7~8 under ice cooling with a 3% aqueous sodium hydroxide solution under ice cooling. 21.7 parts of sodium nitrite was added and stirred for 30 minutes. A small amount of 65. 5 parts of hydrazine hydrochloride was allowed to form a brown solution, and then scrambled for 2 hours. An aqueous solution of cerium, sulfur, 19, dissolved in 197.3 parts of water is added to the reaction solution and given to the suspension containing the diazonium salt.

Adding 2 parts of water to 20.1 parts of 1-butyl-3-cyano-4-yl-6-one represented by formula (c-1), and then cooling with ice to make sodium salt The aqueous solution was adjusted to pH 8 to 9. After the milk hole solution, it is cold. After the above-mentioned ratio of the copper aqueous solution to a colorless solution, the aqueous solution was adjusted to pH Η8 to 9 with a 30/〇虱 emulsified sodium aqueous solution, and the fresh liquid containing the weight was added dropwise. Drop the field, then chick 2, ^, dark solution. 14 parts of the purified salt was subjected to a reaction, and the obtained yellow solid was dried (yield: 74%).句表

The structure of the secret couple is called the analysis of mosquitoes. The f-class extension uses the JMS 700 (manufactured by Sakamoto Electronics Co., Ltd.). Mass analysis: ionization mode = FD +: m / z: = 368 ί 4) 〇 35g dissolved in lactic acid to make the volume 2i =, and, in, Cm diluted with lactic acid to a volume of l〇〇cm3 (Concentration: 0.028 g/L) 'The absorption spectrum was measured using a spectrophotometer (quartz cuvette, the length of the cuvette was (4) 201000567. The compound showed an absorbance of 2.0 (arbitrary unit) at Xmax = 425 nm. In the method described in Example 17 of the patent document 1 (JP-A-2003-510398), the following azo compound was synthesized. The azo compound (d-5) 〇35 g was dissolved in ethyl lactate to make the volume 250 cm3'. 2cm3 was diluted with ion-exchanged water to a volume of 100cm3 (concentration: 〇.〇28g/L), and the absorption spectrum was measured using a spectrophotometer (quartz cuvette, optical path length; lcm). The compound was at λη^χ=422ηιη The absorbance is displayed as 2.1 (arbitrary units). (, '

<Evaluation of Solubility of Solvent> Odor Compound The solubility of the solvent in Examples 9 to 11 and Comparative Examples 2 to 5 was determined in the following manner:

In the entangled sample tube, the solvent shown in each of the reduced compound wires 2 is mixed to obtain a mixing ratio of 1% (w/v) and 3% (w/v), and after sealing, at 4 ° ° ^ 5 3 〇 ^ ^ = In the mixed solution of the system = 1% (Cao), the insoluble matter is determined to be 1% of the solubility, and it is prepared as a solution in the solution. 表 Table 2 61 201000567

Compound. Rod large wavelength light wave • · · · IS armor. Solubility of dipropanolone. 9 ΙΪΙ-1 43Inm 2. 4 〇〇 Example 1 〇III-6 431nm 2.2 〇〇Example 1 1 III-1 1 427ntn 2.0 〇Δ Comparative Example 2 d-2 431 run 2. 5 XX Comparative Example 3 1 d-3 430mn 2. 5 X △ Comparative Example 4 _ Comparative Example 5 d^4 425nm 2.0 X - X d"5 422nm 2. 1 XX As can be seen from the results of Table 1, the solubility of the azo compound can be improved by introducing a carboxyl group and a long-chain alkyl group at a specific site. The components used in the following examples are as follows, and the following description may be omitted. (III-1) Colorant: azo compound (A-1) coloring agent synthesized in Example 1 : Solvent Yellowl 62 (manufactured by BASF Corporation) (d-1) Coloring agent · Azo synthesized in Comparative Example 1 Compound (d-4) colorant: azo compound (F-1) synthesized in Comparative Example 4 Resin: HN-122 (manufactured by Takaoka Chemical Industry Co., Ltd.) (G-1) Solvent: N,N-dimercaptopurine Indoleamine Example 12 (Preparation of Colored Composition 1) Mixed (II-1) 0.51 parts by mass, (F-1) 1.19 parts by mass, (G-8 3 parts by mass to obtain a colored composition 1. ' [Coating Formation of film] Next, the above-obtained coloring composition 1 was applied by spin coating on glass (#1737; Coming), and then volatile components were volatilized at 10 (TC for 3 minutes to form a colored composition 1). Coating film. [Evaluation 1] Heat resistance evaluation method 62 4 201000567 The coating film of the coloring composition obtained in the above Example 12 was applied to a thief for 120 hours, and a color measuring machine (〇SP-SP~20〇) was used. 〇 〇 US 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 〇 △ △ △ △ 〇 〇 〇 〇 〇 〇 〇 〇 ["COLORED 0PTIcal aASS ul _YA (m system), which cuts light below 380 nm.] The light is tested by a light resistance tester (suntest cps+. manufactured by Toyo Seiki Co., Ltd.) for 48 hours. 'Second' using a color measuring machine (OSP) -SP-2〇0; 〇lympUS Co., Ltd.) Measurement of light resistance before test & poor (AEab*). 々 状 了 [ [Evaluation of coating film] For the obtained coating film, the above evaluation (============================================================================================================= The coloring composition 2 was obtained. [Formation and Evaluation of Coating Coating] The coating film was prepared and evaluated. As a result, the color difference (^b*) in the heat-resistant Uti was evaluated as 〇.6. [Coloring composition 3 Preparation] The coloring agent (Schedule 1-1) of Example 12 was changed to a coloring agent (d-Ι), and the same procedure as in Example 12 was carried out to obtain a colored composition 3. ', [Formation of coating film] And evaluation] The film was evaluated and evaluated, and the result was heat resistance i 6. The color difference (ΔΕαΙ)* of 83 ' in light resistance evaluation was Comparative Example 8 63 201000567 [Coloring composition 4 Preparation] In the same manner as in Example 12, the coloring agent (d-4) was changed in the same manner as in Example 12, except that [formation and evaluation of the coating film] was carried out in 1 coloring composition 4 Sexual evaluation id: Again, 'making a coating film and performing evaluation, the result was 35 ° 4 heat resistance. The shell (a) is 33,9, and the color difference (ΔEab*) in the evaluation of light resistance is as follows. From the above results, it is understood that the solubility of the azo compound of the present invention is higher than that of the conventional azo compound, and the solubility, heat resistance and light resistance are improved. . [Industrial Applicability] The azo compound of the present invention or a salt thereof is preferably used in a liquid crystal display panel, an electroluminescence, a plasma display panel, or the like, and is used for a color filter such as a liquid crystal display panel, an electroluminescence, or a plasma display panel. Colorant. [Simple description of the diagram] None [Key component symbol description] Benefit 64

Claims (1)

201000567 VII. Patent application scope: 1. An azo compound or a salt thereof, the azo compound is represented by formula (1) R2 CN (I) (In the formula (I), A represents a group consisting of two or more selected from a halogen atom, a methyl group, a nitro group, a sulfo group, an amine sulfonyl group, and an N-substituted amine sulfonyl group. At least one phenyl group, or one or more groups selected from the group consisting of a dentate atom, a thiol group, a methoxy group, a nitro group, a sulfo group, an amine sulfonyl group, and an N-substituted amine sulfonyl group One less radical naphthyl; 'R1 represents a hydrogen atom, a Cw aliphatic hydrocarbon group, a Cw aralkyl group or a c(tetra)aryl group; R2 represents a Q_6 aliphatic hydrocarbon group or a trifluoromethyl group]. An azo compound or a salt thereof, wherein a is a phenyl group or a naphthyl group having at least one N-substituted amine sulfonyl group. 3. The azo compound according to claim 1 or 2 or a salt, wherein the N-substituted amine sulfonyl group is -S〇2NHR3 group 'R3 is a Cm2 aliphatic hydrocarbon group. The hydrogen atom contained in the seven-membered aliphatic hydrocarbon group may be substituted with an alkoxy group or a hydroxyl group, and the Cl 1 2 aliphatic hydrocarbon group The fluorenylene group may be substituted with a fluorene-), a C6-2 aryl group, a C7-2 aralkyl group or a c2_10 aryl group. 4. A binary body of an azo compound or a salt thereof according to any one of claims 1 to 3. 5. An azo compound or a salt thereof, the azo compound being represented by the formula: 1): (II) (In the formula (Π), A1 represents that there may be one or two selected from at least one of a group consisting of a halogen atom, a methyl group, 65 201000567 methylol 1 and a carboxyl group, or a phenyl group. R is an unsubstituted aliphatic hydrocarbon group, a substituted C7 2G aralkyl group or a substituted C6-2G aryl group; R represents a substitutable (^-5 aliphatic hydrocarbon group or trifluoromethyl group); R13 represents a hydrogen atom, an amine-methyl group or a cyano group. The earth azo compound or a salt thereof according to the fifth aspect of the patent application, wherein the compound represented by the formula: Private (IV) Table 2 azo compounds or their salts: R17 R1« [In the formula (III) (IID 'R12 and RD are the same as in the formula (11); 13 3 and each of them are represented by a money atom, a γ atom, a methyl group or a decyloxy group; a methoxy group or Silk, but W, RnARl8 at least the soil 66 201000567 Fourth, the designated representative map: (a) The representative representative of the case is: no (two) The representative symbol of the symbol is a simple description: No five, if the case has a chemical formula, please Reveal the chemical formula that best shows the characteristics of the invention: HO R1 R2 CN 201000567 L Li application Chinese manual amendment page (no secant version) ho3s (1-36) The structure of the compound (1 - 36) is determined by mass analysis. The mass spectrometer used JMS — 7〇0 (manufactured by JEOL Ltd.). Qualitative analysis: ionization mode = FD +: m / z = 460 0.35 g of the obtained azo compound (I-36) was dissolved in N,N-dimethylformamide to make a volume of 250 cm 3 , 2 cm 3 of which was 2 cm 3 Diluted with water to a volume of 100 cm3 (concentration: 0.028 g/L) 'The spectrophotometer (quartz colorimetric jbl, colorimetric fox length is icm) was used to measure the absorption spectrum. The compound showed an absorbance of 3.1 at hax=441 nm. (Any unit). Example 2 · In a flask equipped with a cooling tube and a mixing device, 5.0 parts of an azo compound (I-36), 50 parts of chloroform, and N,N-didecyl decanoic acid amine were charged. 2.1 parts, under the condition of 20 ° C or less, add 3.5 parts of sulfite chlorine. After the completion of the dropwise addition, the temperature is raised to 50 ° C, and the reaction is maintained at the same temperature for 5 hours, and then cooled to 2〇°c. The cooled reaction solution was maintained at 20 ° C or lower with stirring, and a mixture of 8.0 parts of 2-ethylhexylamine and 15 parts of triethylamine was added dropwise, followed by stirring at the same temperature. The reaction was stirred for an hour, and then the reaction mixture obtained was subjected to a rotary evaporator to remove the solvent. After adding a small amount of decyl alcohol, it was vigorously mixed. The mixture was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water to precipitate crystals, and the crystals were separated by filtration, washed thoroughly with ion-exchanged water, and dried at 60 ° C to obtain a mixture. The azo compound represented by the formula (1-111) is 5 parts (yield 78%). 45 201000567 The structure of the compound (I-111) is determined by mass analysis. The mass spectrometer used JMS-700 (manufactured by Sakamoto Electronics Co., Ltd.). Mass analysis: ionization mode = FD +: m / z = 571 The obtained azo compound (I - lll) 〇. 35 g dissolved in ethyl lactate to a volume of 250 cm 3 ' 2 cm 3 of which was diluted with ion-exchanged water to a volume of 1 〇〇cm3 (concentration: 0.028 g/L), the absorption spectrum was measured using a spectrophotometer (quartz cuvette, optical path length; lcm). This compound showed an absorbance of 2.5 (arbitrary unit) at Amax = 434 nm. Example 3 " After adding 50 parts of water, 2 parts of f N-mercaptoacridone, to 25.0 parts of anisidine 4-sulfonic acid, represented by formula (a-2), and then, under ice cooling, The aqueous solution of 3〇% sodium hydroxide was adjusted to pH 7~8. The following operations were carried out under ice cooling. Add 276 parts of sodium nitrite and stir for 30 minutes. A small amount of 97.3 parts of 35% hydrochloric acid was gradually added to make a brown solution, followed by stirring for 2 hours. An aqueous solution of 251 parts of guanamine-based sulfuric acid dissolved in 25 parts of water was added to the reaction solution and stirred to obtain a sputum containing a heavy hydrazine salt. 6 — Jingji/, Factory—“w Dingxun Bafen and N-methylpyrrolidone 28.9 parts' were adjusted to ρΗ8~9 with 3〇〇/0 hydroxide steel solution under ice cooling. Ν J^ 0 (c-1) CN The yellow solid thief obtained was pressed at 6 inches. (: Drying. 140 parts of the purified salt was added to the reaction solution, and the mixture was stirred for 5 hours. The color solid was dried under reduced pressure at 6 (TC to give 46. 7 parts of the azo compound of the formula (1 - 35), Table 46 201000567. Rate 79%). The structure in which the compound (1 - 35) is used is determined by mass analysis. Mass analysis cracked JMS-700 (manufactured by Sakamoto Electronics Co., Ltd.). Mass analysis: ionization mode = FD +: m / z = 460 The obtained azo compound (I - 35) 0.35 g was dissolved in N, N-dimethyl amide to make the volume 250 cm 3 ' 2 cm 3 of which was diluted with water To make the volume 1 degree: 0.028g/L), use a spectrophotometer (quartz colorimetric, the color length is j to determine the absorption spectrum. The compound shows the absorbance at Xmax=435nm (any unit) Example 4 Into a flask equipped with a cooling tube and a stirring device, 5.0 parts of azo compound 35), 50 parts of chloroform, and 2.1 parts of hydrazine and hydrazine-dimercaptocarbamide were charged and maintained under stirring. In the state below 20 ° C, 3·5 parts of sulfite chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 50 C, and the mixture was maintained at the same temperature for 5 hours to be cooled to 2 Torr after the reaction. After that, the reaction solution was maintained at a temperature of 20 ° C or lower under stirring, and a mixture of 8 parts of tetrahydrofuranamine and 15 parts of diethylamine was added dropwise. Thereafter, the reaction was carried out by stirring at the same temperature for 5 hours. It-people, the reaction mixture will be known to remove the solvent in a rotary evaporator, and a small amount of methanol is added and stirred vigorously. The mixture was added to a mixed solution of 29 parts of acetic acid and 300 parts of ion-exchanged water to precipitate crystals. The crystals which were precipitated were separated and washed thoroughly with ion-exchanged water to dryness under reduced pressure at 60 ° C to obtain 5.7 parts of an azo compound represented by the formula (I-151) (yield 90%). 201000567 The structure of the compound (I-151) was determined by mass analysis. Quality analysis Agricultural use JMS-700 (made by Nippon Electronics Co., Ltd.). Mass analysis: ionization mode = FD +: m / z = 543 0.35 g of the obtained azo compound (I - 151) was dissolved in ethyl acetate to make a volume of 250 cm 3 '2 cm 3 of which was diluted with ion-exchanged water to make a volume of 100 cm 3 (Concentration: 0.028 g/L) 'The absorption spectrum was measured using a spectrophotometer (quartz cuvette, optical path length; lcm). This compound showed an absorbance of 2.6 (arbitrary unit) at Ajnax = 438 nm. Example 5 In a flask equipped with a cooling tube and a mixing device, 5 parts of azo compound (1 - 35), 30 parts of methoxycyclopentane and 5.8 parts of N,N-dibutylformamide were placed under stirring. While maintaining the temperature below 20 ° C, 4 parts of sulfite chloride was added dropwise. After completion of the dropwise addition, the temperature was raised to 40 ° C, and the reaction was maintained at the same temperature for 5 hours, followed by cooling to 20. (: The reaction solution after cooling was maintained at a temperature of 20 ° C or lower under stirring, and a mixture of 1 -amino 2-propanol 3.7 parts and 4 parts of triethylamine was added dropwise. Then, the mixture was stirred at the same temperature. The reaction was carried out for 5 hours. Next, the obtained reaction mixture was subjected to a rotary evaporator to remove the solvent, and then a small amount of decyl alcohol was added thereto, followed by vigorous stirring. The mixture was added to a mixture of 29 parts of acetic acid and 300 parts of ion-exchanged water while stirring. The crystals were precipitated, and the precipitated crystals were sufficiently washed with ion-exchanged water and dried under reduced pressure at 60 ° C to obtain 4.2 parts of an azo compound represented by the formula (1 - 184) (yield 74%). — » 亀· „ The structure of the compound (1 - 184) is determined by mass analysis. The mass spectrometer is used. 48 201000567 JMS - 7〇0 (manufactured by Nippon Denshi Co., Ltd.). Mass analysis: ionization mode = FD + : m / z = 517 0.35 g of the azo compound (I - I84) obtained in 3 was dissolved in ethyl lactate to a volume of 250 cm 3 , and 2 cm 3 of the solution was diluted with ion-exchanged water to make the volume 1 〇〇 cm 3 (concentration: 0.028 g/L), and an absorption spectrum was measured using a spectrophotometer (quartz cuvette, optical path length; lcm). This compound showed an absorbance of 2.4 (any note, unit) at Xmax = 432 nm. Example 6 " Three parts of the azo compound (I-35) were placed in a flask equipped with a cooling tube and a stirring device. 45 parts of tetrahydrofuran and 1.3 parts of N,N-dimercaptocarboxamide were added to the mixture of 2.4 parts of sulfite-brewed chlorine at 20 C or less under stirring. After the completion of the dropwise addition, the temperature was raised to 4 ° C, and the reaction was stirred at the same temperature for 5 hours, followed by cooling to 2 ° C. The cooled reaction solution was maintained at a temperature of 20 ° C or lower under stirring, and a mixture of 5.8 parts of ethylenediamine and triethylamine and a wound was added dropwise. Thereafter, the reaction was carried out by mixing at the same temperature for 5 hours. Next, the reaction mixture obtained was subjected to a rotary evaporator to remove the solvent, and a small amount of methanol was added thereto, followed by vigorously disturbing. The mixture was stirred while adding a mixture of 2 parts of acetic acid and 2 parts of ion-exchanged water to precipitate crystals. The precipitated crystals were separated, washed thoroughly with ion-exchanged water, and dried under reduced pressure at 60 ° C to give 1.5 parts (yield 48%) of the azo compound represented by formula (1 - 204). · The structure of the compound (1 - 204) is determined by mass analysis. The mass spectrometer used JMS-700 (manufactured by JEOL Ltd.). Mass analysis: ionization mode = FD +: m / z = 860 The obtained azo compound (; I - 204) 0.35 g was dissolved in ethyl lactate to a volume of 250 cm 3 , and 2 cm 3 of the solution was diluted with ion-exchanged water to make the volume I00cm3 (concentration: 0.028 g/L) 'The absorption light If was measured using a spectrophotometer (quartz bismuth, optical path length; lcm). This compound showed an absorbance of 2.5 (arbitrary unit) at Xmax = 430 nm. Example 7 49 201000567 After a portion of toluidine-4-thanoic acid was added between the formula (a-2), it was adjusted to pH 7 to 8 with a 30% aqueous sodium hydroxide solution under ice cooling. I is carried out under ice cold. Add 1 U of sodium sulphate and ring for 3 G minutes, add 39.0 parts of 35% hydrochloric acid to make a brown solution, and then mix for 2 hours = acid 1 (U parts dissolved in water and then added to the reaction solution) ^ Containing diazo Fresh liquid. H03S~^ Wide NH 2 (a-2) is represented by formula (e-2), l- 4-bis(3-cyano-4-methyl-6) )] - 8.5 parts of butyl ketone added 85 parts of water and 10 parts of thiopyrrole, and then adjusted to pH 8~9 with 30% aqueous sodium hydroxide under ice cooling. The following operation was carried out under ice cooling. After the aqueous solution was made into a colorless solution, it was adjusted to pH 8 to 9 with a 30% aqueous sodium hydroxide solution, and it took 2 hours to add a suspension containing a diazonium salt. After the completion of the dropwise addition, stirring was continued for 2 hours, $ The yellow suspension was filtered, and the obtained yellow solid was dried under reduced pressure, and then dried to give the compound (yield: 92 8%). The structure of the & matter (1 - 210) is determined by mass analysis. Mass spectrometer JMS — 7〇〇 (manufactured by Sakamoto Electronics Co., Ltd.). (c-2) Mass analysis: ionization mode = FD +: m / z = 750 50 201000567 units). 0.35 g of the obtained compound (I-210) was dissolved in N,N-dimethylformamide to make the volume 25 〇cm 3 , and 2 of the coffee 3 was diluted with water to make the volume 1 〇〇 cm 3 (concentration: 0.028 g/L), the absorption spectrum was measured using a spectrophotometer (quartz cuvette, cuvette length lcm). The compound showed an absorbance of 3.1 at Xmax = 435 nm (any example 8 took the previously adjusted yellow crystals for 1 hour. After the temperature of the yellow solid was warmed to room temperature, the reaction solution was stirred for 30 minutes. After 40 parts of stirring and stirring 'The mixed solution was added to a mixture of 4 parts of acetic acid and 3 parts of water to stir the crystals. The precipitate was separated into a flask equipped with a cooling tube and a stirring device, and the compound (I-21) was introduced. 5 bruises, 50 acetonitrile and 1.5 parts of N,N-dimethylamine, maintained at 2 扰 under disturbing mixing. 匸 匸 匸 匸 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 3.7 The temperature was raised to 4 Torr. 〇, the reaction was maintained at the same temperature for 2 hours to allow the reaction to cool after i 2 (rc. After cooling the anti-corrosive solution-face-face was poured into 150 parts of ice water, stirring for 3 G minutes. g The yellow crystals are cleaned thoroughly with tap water. Prepare a flask equipped with a cooling tube and a stirring device in addition to the drying of Qingqing. Add 2 parts of amino 2-propanol and 20 parts of N-methylpyrrolidone. It is maintained at 2 〇 below it, after putting in a yellow solid The solution: The reaction solution in methanol was added 29 parts of acetic acid was added and do plasma fraction precipitated by filtration and crystallized from to -198) of the expressed The structure of the compound (1-198) was determined by mass analysis JMS~7〇〇 (manufactured by Nippon Denshi Co., Ltd.). The mass spectrometer was thoroughly washed with sub-exchange water and dried at 6 (TC under reduced pressure to obtain 3.9 parts (yield 69%) of the formula (1%). 工 罝 analysis: ionization mode = FD+: m/z = 864 The obtained compound (1 - 198) 0.35 g was dissolved in an empty 250 cm 3 '2 cm 3 of which was ion-exchanged water: 0.028 g / L) 'Dissolved using a spectrophotometer (quartz colorimetric - 198) 0.35 g Destroy one of them 2cm3 with ion exchange water thin 51 201000567 Received spectrum. This compound showed an absorbance of 2.6 (arbitrary unit) at Xmax = 433 nm. Comparative Example 1 The following azo compound was synthesized by the method described in Patent Document 1. 0.35 g of the azo compound (d-1) was dissolved in ethyl lactate to a volume of 250 cm 3 , and 2 cm 3 of the solution was diluted with ion-exchanged water to have a volume of 10 cm 3 (concentration: 0.028 g/L), and spectrophotometry was used. The absorption spectrum was measured (length in the quartz colorimetric path; lcm). The compound showed an absorbance of 2.2 (arbitrary unit) at Amax = 425 nm. <Evaluation of solubility of solvent> The solubility of the azo compound cross-linking agents of Examples 1 to 8 and Comparative Example 1 was determined in the following manner. In a 50 mL sample tube, each azo compound and diacetone alcohol were mixed to obtain a mixing ratio of 1% (W/V) and 3% (W/V), which was 4 Å after sealing. ^ Oscillate for 10 minutes with a chirp oscillator. Then, after standing at room temperature for 3 minutes, the presence or absence of insoluble matter was recognized. 'Yan Ya 1% in a mixed solution prepared as 1% (W / V), insoluble matter is determined to dissolve the following (X), in the preparation of 1% (W / V) mixed solution, no Insoluble matter: The solubility of the insoluble matter in the mixed solution of 3% (W/V) was determined as 丨, the damage was 3% (Δ), and it was prepared in a mixed solution of 3% (w/v). No insolubles, two T full 3% or more (〇). The results are shown in the table.疋为〉谷解度表1 52 201000567 Maximum wavelength spectroscopic concentration - Solubility for solvent 441nm 3.1 Δ 434nm 435nm 2.5 3.2 〇Δ 438nm 2.6 〇432nm 2.4 〇430nm 2.5 △ : 435mn 3.1 △ 433nm 2.6 △ 425nm 2.2 X , As a result of 1, it is understood that the compound of the present invention has both high solubility and high spectroscopic light. Example 9 Mil Example 1 Example 2 Example 3 Comparative Example Concentration of 4-aminobenzoic acid represented by Formula 13) After adding 25 parts of human water, y ♦ was adjusted to H7~8 with 30% aqueous sodium hydroxide solution. The following operations are performed in 7.6 parts and 3 minutes in Lin. A small amount of ^^ ϋ f ί color dissolving 'wins 2 hours. 6.9 parts ΐΪίί added to the reaction solution and obtained the diazonium salt HOOC NH2 (a-3) in the formula (c-3) 1-(2-ethylhexyl)-3-cyano_4 - 6 - After adding 5 parts of 曱 吡 吡 咯 〇 〇 及 ^ ^ ^ ^ ^ ^ 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 。 53 201000567 The following operations were carried out under ice cooling. After stirring the K-ketone water to a colorless solution, it was adjusted to ρΗ8 to 9 with a 30% aqueous sodium hydroxide solution, and it took 2 hours to add a salt containing Wei salt to the fruit. After dropping the county, it was won for another 2 hours to obtain a brown suspension. After filtration, the obtained yellow solid was dried under reduced pressure to give 10 parts (yield: 73%) of the azo compound represented by formula (III-1). HOOC The structure of the azo compound formula (ΠΙ-1) was determined by 1H-NMR, 3C-NMR and mass analysis. The NMR apparatus used ECA-500 (manufactured by JASCO Corporation), and the mass spectrometer used MS-7 (manufactured by JEOL Ltd.). NMR (500 MHz, δ (ppm, TMS basis), DMSO); 0.84 - 0.88 (6H, m), 1.19 - 1.33 (8H, m), 1.77 (1H, m), 2.51 (3H, s), 3.71 - 3.79 (2H, m), 7.76 (2H, br. d, J = 8.8 Hz), 7.97 (2H, br·d, J = 8.8 Hz), 13.81 (1H, br. s), 14.3 (1H, br. s) 13C-NMR (125MHz, δ (ppm, TMS basis), DMSO): 10.30, 13.93, 16.43, 21.03, 22.47, 23.26, 28. (U, 29.91, 36.83, 43.12, 101.54, 114.88, 117.12, 123.97 , 128.22, 130.87, 144.64, 159·16, 160.23, 160.56, 166.54, 171.98 Mass analysis: ionization mode = FD +: m / z = 410 The obtained azo compound (III - l) 〇. 35g dissolved in lactate B The ester has a volume of 250 cm. '2 cm of it is diluted with ethyl acetate to make the volume i〇〇cm3 (concentration: 0.028 g/L), and a spectrophotometer (quartz cuvette _, the length of the color suit is icm) is used. The absorption spectrum was measured. The absorbance at Xmax = 431 nm showed 2.4 (arbitrary unit) 〇 Example 10 54 201000567 The absorption spectrum was measured. The compound showed an absorbance of 2.0 (arbitrary unit) at Xmax = 425 nm. Comparative Example 5 Patent Document 1曰In the method described in Example π of the present invention, the following azo compound was synthesized, and 0.35 g of the azo compound (d-5) was dissolved in lactic acid to make the volume 250 cm3, and 2 cm3 of the azo compound was used. The ion-exchanged water was diluted to a volume of l〇〇cm (concentration: 〇.〇28g/L), and the absorption spectrum was measured using a spectrophotometer (quartz cuvette, optical path length; lcm). The compound showed absorbance at xmax=422mn. 2.1 (arbitrary unit). *' ^ <Evaluation of solubility of solvent> The azo compounds of Examples 9 to 11 and Comparative Examples 2 to 5 were determined in the following manner: Solubility of Solvent: In a 50 mL sample tube, each azo compound and Table 2 The dissolution shown is such that the waiters are mixed at a ratio of 1% (W/V) and 3% (W/V) and sealed at 4 〇f minutes. Then, after being allowed to stand at room temperature for one minute, it was filtered in a mixed solution of 1% (W/V) prepared by adding 1% (w/v) of the forest solubilized material, which was prepared to be 1% (W/V). And prepared as 0 3 〇 / Λ 1 The solubility of the insoluble matter in the solution is set to 1 ~ not i years old money towel no secrets are dissolved ^ Table 2 61 201000567 compound. Huada wave county split light 蚵 propylene glycol single armor Solubility Solubility Solubility Example 9 III-1 431mn 2.4 〇〇 Example 1 〇III-6 431ηια 2. 2 〇〇 Example 1 1 III-1 1 427nta 2.0 〇Δ Comparative Example 2 d-2 431nm 2.5 XX Comparative Example 3 d-3 430run 2. 5 X △ Comparative Example 4 425mn 2.0 XX Comparative Example 5 d-5 422nm 2. 1 XX From the results of Table 2, it is known that a carboxyl group and a long-chain alkane are introduced by a specific site. The base can improve the solubility of the azo compound. The components used in the following examples are as follows, and the following description may be omitted. (ΠΙ-1) Colorant: azo compound (A-1) coloring agent synthesized in Example 1 : Solvent Yellowl 62 (manufactured by BASF Corporation) (d-1) Colorant: azo compound synthesized in Comparative Example 1 (d-4) Colorant · The azo compound (F-1) synthesized in Comparative Example 4: HN-122 (manufactured by Tajika Chemical Industry Co., Ltd.) (G-1) Solvent: N,N-dimethylhydrazine Indoleamine Example 12 (Preparation of Colored Composition 1) Mixed (II-1) 0.51 parts by mass, (F-1) 1.19 parts by mass, (G-8 3 parts by mass to obtain colored composition 1), [Coating Formation of film] Next, the above-obtained color composition 1 was applied by spin coating on glass (#1737; Coming), and volatilization was volatilized in 10 (TC for 3 minutes, and coating of composition 1 was performed. Membrane. Ten, ~ 风者邑 [Evaluation 1] Heat resistance evaluation method 62