TW200401010A - Bisazo and trisazo copper complex dyestuffs - Google Patents

Abstract

This invention relates to coppered bis-or trisazo dyestuffs containing at least two (for bisazo) and at least three (for trisazo) alkyl-, alkoxy- or aryl- ammonium sulfonate groups or sulfonate groups with Rhodamine B type or Rosinamine D type counterions. The invention also relates to various intermediates used in the preparation of the metallized dyes, to compositions, and to processes for preparing the metallized dyestuffs. The compounds are particularly suited for the application in lacquers.

Description

200401010 (1) Description of the invention: (1) The technical field to which the invention belongs The present invention relates to a compound containing at least two (about disazo) and at least three (about paraazo) alkyl, alkoxy or aryl ammonium sulfonates Group or copper-containing bis or azo dye containing sulfonate groups of Rhodamine B or Rosinamine D counter ions. The present invention also relates to various intermediates used in the preparation of metallized dyes', to its composition, and to a method for the preparation of metallized dyes. One type of solvent-soluble dyes known in the art is a complex dye based on chromium, which is extremely soluble in solvents such as alcohols and ketones but practically insoluble in water. On the one hand, soluble dyes in chromium-based solvents have extremely beneficial properties, especially high light resistance, but on the other hand, chromium-based solvents are becoming a concern due to environmental issues. Therefore, there is a need for solvent-soluble dyes that are not based on chromium. Solvent-soluble dyes as defined in this application are defined as being highly soluble in solvents such as alcohols and ketones and practically insoluble in water. Regarding solvent-soluble dyes, the fully specified test in this technique is the so-called "water resistance". Bisazo compounds, especially azo, tetrasazo and higher azo compounds due to their potential The use as a black dye is well known in the art. Many combinations of well-known diazo compounds and coupling components regarding coupling reactions are possible, while the components used in industrial azo coupling are mainly due to access The choice of degree and price. A very important argument when synthesizing azo and higher azo compounds is the dissolution of the components' and the intermediates in the entire process. 5 200401010. -No. 3 1 1 0 8 5 reveals copper complex dyes based on bisazo, ginsenothermal or tetradox® dye compounds, in which the _th—, phenyl type, and diazo component system are described If necessary, it is especially substituted by an internal C, _4 alkylsulfonamido group. In addition, the first diazo component and the first, phenyl, and coupling components may be halogen, c 1_4 alkyl, c] _4 Substituted by alkoxy and sulfonic acid 2 residue groups. Second Naphthol-type, coupling components are from 0 to 2 luteinic acid groups optionally substituted 'in the example (compound [π]) it exists as an internal amine sulfonate. If necessary,' the coupling product is converted to copper complex Materials, internal salts, acid addition salts, metal test salts or amine salts. The obtained dyes are characterized by black dyes with strong dyeing ability, which are used in colored paper, fibers and leather for surface dyeing and printing. Surprisingly, it was found that starting from non-sulfo (acid) amido-substituted diazo compounds and coupling components, copperized bis and ginsazo dyes can be characterized by high coloring or black Dyes, high weather and light resistance 'and their use in particular as solvent-soluble dyes. (3) Summary of the invention The present invention relates to containing at least two (about disazo) and at least three (about paraazo) alkyl, alkane Copper-based bis or ginsazo dyes containing oxy or aryl ammonium sulfonate groups or rhodium salt type rhodium B or rosinamine D counter ions. The compounds of the present invention are particularly suitable for application Solvent-based spraying And solvent-based resin systems and in non-watermarking and inkjet applications. 200401010. Double or · azo: 1: 1 copper complex inclusions. Residues of the bis or reference azo dye compound: D + N = N-ΚΐΝ = Ν ～ Κ. (I) where AE D is the residue of the diazo component D 1 The ethnic group formed: the end

, Or substituted phenyl, substituted or unsubstituted naphthyl, and 疋 κ 疋 residues are selected from the group consisting of: substituted or:: substituted phenol, substituted or unsubstituted naphthalene酣, replaced or not

In lieu of 1-phenyl-5-zhuang "ketone, substituted or unsubstituted pyrazolinone, the residue" 4K "is selected from the group consisting of:" Disubstituted phenol " , Substituted or unsubstituted naphthol,-,

__ K is K2 'residues are selected from the group consisting of: substituted I substituted phenols, substituted or unsubstituted naphthols, phenyl groups in s or ^, Chai Ji, Biao, Chai acid, The group of 5--5-pyrazolone and 1-naphthyl-5_pyrazolinone is selected from #, n-based hydroxyl group 5, methoxy group or halogen, and chlorine is preferred. And at least n + 1 of components D, K °, W, and K2 are at least ~

^ Or an aryl ammonium sulfonate group or a sulfonate group having a rhodamine B type 4 X & counter ion. According to the present invention, the bisazo-based 丨: 丨 copper complex dye 11 = 1 is included in the compound 7 200401010 The bisazo-based dye compound according to the general formula (1 a): D — N = N — Κι — Ν = Ν—Κ〇 (la) where D and K. And K 'are as defined above. According to the present invention, the "dual thermal group 1.1 copper complex dye compound includes a reference azo dye compound according to the general formula (1 b): (lb) D-Ν ~ N-K 2-Ν-N-K ] — N = N — K 〇 where D, Kc, K1 and K2 are as defined above. The counter ion system of the sulfonate group is selected from + NH4.m (Cl_12 alkyl) m, + NH4-m (CH 2 alkyloxy) m, + NH4.m (c6.1Q aryl) m (where m Is an integer from 1 to 4) 'Dendamycin type B or rosinamine type 0 cation. The preferred counterions are alkylammonium and alkoxyammonium ions where m is! , Especially + NH3 (i, i-zi-n-propylhexyl) or its isomers and + nh3 (2, · ethyl-hexyloxy-n-phenylene). Preferred rhodamine β- or amido-d cations have the following formulas:

Bisazo group A preferred aspect of the present invention is that the compound wherein η is 1, is: 1 copper complex dye

D is a residue of the diazo component D ′ is a residue of the Ke ′ component, a heart is a residue of the K 1 ′ component, and at least two components D ′ are naphthyl groups, and ^ methyl is substituted by 1-phenyl-based unsubstituted phenols, and / or K 1 with at least -5-flit triazolinone, an alkyl, alkane 8 200401010 oxy or aryl ammonium sulfonate group or with rhodamine The sulfonate group of type B or rosinamine D counter ion is substituted. Another preferred aspect of the present invention is the reference azo 1: 1 copper complex dye where η is 2, D is the residue of the diazo component D ', is an unsubstituted naphthyl group, and KQ is 1 ^' The residues of the component are selected from the group consisting of: amine substituted or unsubstituted naphthalenes, substituted or unsubstituted bphenyl-5_pyrazolinones, and κ 1 is the K component The residue is an unsubstituted naphthol, and K2 is a residue of the K21 component, which is selected from the group consisting of: methoxy substituted or unsubstituted phenol. And at least three components D, KG, K 1 and / or K 2 have at least one alkyl, phosoxy or aryl dibasic acid salt group or have rhodamine B or rosin amine D counter ions Sulfonate group. In particular, the phenol or naphthol residue K / may be further substituted by methyl or methoxy. The metallized dyes of the present invention can be rapidly treated with copper salts in aqueous or non-aqueous media by using well-known methods for the corresponding unmetallized 0, 〇 | -dihydroxyazo dyes or 0-methoxyhydroxyazo dyes. Preparation, for example, the reaction of azo dye with copper sulfate in the presence of water and sodium or ammonium acetate or with copper nitrate in the presence of alkali ash and a suitable solvent approaches the reflux temperature of the system until the reaction is complete. Unmetallated bisazo-based dyes can be prepared by diazotizing an aminobenzene compound of formula (Π) or naphthylamine of formula (ΠI) in the first step: 200401010

NH, (III) where x is hydrogen, hydroxy or methoxy in the ortho position with the amine group. In the second step, a diazo compound is coupled to a phenolic, methoxyphenolic, or naphthylamino compound, and if necessary, protected by an amine group. In a third step, a further diazotized compound is coupled to a naphthol or a phenylpyrrolidine compound by a well-known method. Unmetallized ginsazo dyes can be prepared in the first step by diazotizing the aminobenzene compound of formula (π) or the naphthylamine of formula (III):

Where X is hydrogen, hydroxy or methoxy in an ortho position with the amine group. In the second step, a diazonium compound is coupled to an o-aminophenolic compound having an optionally protected amine group for further diazotization. In the third step, the amine group is deprotected, diazotized and coupled to a phenolic or naphthalene amine compound. In the fourth step, a further diazotized compound is coupled to a naphthol or a phenyl-11 sialine compound by a well-known method. Alternatively, the coupling can be done in reverse order, that is, the diazotized o-aminohydroxy- or o-aminomethoxynaphthalene compound with the phenolic compound of formula (IV), Combination of naphthalene compounds of formula (V): 10 200401010

Where the hydroxyl group is at the 1 or 2 position and the sulfonic acid group is attached to any position except 1 or 2. The diazo component of formula (II) or (III) and the aforementioned coupling agent of formula (IV) or (V) are well known compounds and can be prepared by methods well known to those skilled in the art. The synthesis of the bisazo compound of the present invention is shown by the following reaction scheme:

Where R is hydrogen, methyl or methoxy and k and 1 · are 1 or 2. With regard to the first coupling, a protecting group on the amine is as needed. If the 200401010 group R (see formula (vIII) below is hydrogen or methyl, a protecting group is required. If R is a methoxy or sulfonate group, a protecting group is not required. The protecting group should preferably be omega- Methyl extended acid group:

The synthesis of para-azo compounds is shown by the following reaction scheme: ρα, (S03H) k 1) Diazotization 2) First coupling

12 200401010 where R is hydrogen, methyl or methoxy and k and r are 1 or 2. Preferred compounds for the first diazotization have the formula (V I or (V 11): ho3s

(VI) (VII) A particularly preferred coupling component suitable for the first coupling at the time of synthesis is a compound according to formula (VIII) where R is hydrogen. ^ W0Me

^ S03H (VIII) A particularly preferred coupling component suitable for the second coupling is a compound known as a gamma-acid (formula IX), j-acid (formula X) or h-acid (formula XI).

(IX) (X) (XI) The novel soluble dye compound according to the present invention is suitable for dyeing plastics (particularly overall dyeing) including solvent-free and solvent-containing plastic wholes and solvent-free or solvent-containing plastic resins. . In addition, they are suitable for coatings, oil-based or water-based paints, spray paints, spinning dyeing of viscose fibers or cellulose acetate, natural or synthetic polyamide 'polyester, polyethylene, polystyrene, pvc, Dyeing of rubber or synthetic leather. These novel chemical compounds can also be used for printing including textiles and paper, dyeing the body of paper, and coating textiles and leather. _ Dyeing with novel compounds has good properties, such as high light resistance, good heat resistance, 'good weather resistance, good chemical resistance, good migration properties, low fogging, good overcoat properties, good fastness in solvents Degree, high color strength, and good application properties (such as resistance to flocculation). The dye compound according to the present invention is suitable as a colorant in a solvent-based inkjet ink for printing paper or paper substrates, textile fiber substances, plastic films, and plastic transparent objects. · The dye compound according to the present invention is also suitable as a colorant in toners and developers of facsimile machines, such as one- or two-component powder toners (also known as ~ · or two-component developers), Magnetic toner, liquid toner, polymerized toner, and special toner. The dye compound according to the present invention is additionally suitable as a charge control agent. (Iv) Embodiments The following examples illustrate the present invention. Unless stated otherwise, the parts and percentages used in these examples are based on weight: weight. Example 1 a) Stir 22.9 parts of 4- (6,8-disulfonaphthyl-2-ylazo) -2-methoxyaniline into 300 parts of water and 1 2.9 parts of 30 % HC 1 in a mixture. After 30 parts of ice was added, the amine was diazotized by adding 1 2.0 vol. Parts of a 4N NaNO 2 solution. The resulting suspension was stirred at 5 ° C for 1 hour, and then slowly poured into 33 parts of water and 6.4 parts of 30% NaOΗ 1 1.4 parts of 2-amino-8-hydroxynaphthalene-6- Solution of sulfonic acid (gamma acid). 200401010 P Η 値 was increased to 9.5 to 10 by simultaneously adding another 10.6 parts of 30% Na 〇 Η. The resulting mixture was then stirred at room temperature for 8 hours and ρ Η 値 was reduced to 1.5 by adding 30% H C 1. 120 parts of sodium chloride were added and the resulting precipitate was accumulated and filtered and dried. b) Stir 16.4 parts of the above part a), the bisazo-based dye into a mixture of 150 parts of water, 5.3 parts of 30% NaOH, and 6.2 parts by volume of a 4N NaN02 solution. The resulting solution was slowly poured into a suspension of 50 parts of ice and 18.8 parts of 30 H C 1 to generate a diazonium salt and stirred at 5 ° C for 2 hours. This slurry was slowly poured into a solution of 12 parts of water and 3.2 parts of 30% NaOH, 3.4 parts of 2-naphthol-8-sulfonic acid. By simultaneously adding another 2 6.6 parts of 30% N a Ο Η, ρ Η 値 was raised to 9 · 5 to 10. The resulting mixture was then stirred at room temperature for 3 hours and the pH was reduced to 1.5 by the addition of 30% HCI. Then 160.0 parts of solid sodium chloride was added, resulting in a lot of precipitate accumulation (filtered and dried). c) Suspend 19.9 parts of the parasazo dye in part b) above in 100 parts of water, 1 0.0 parts of dipropylene glycol monomethyl ether, and 4.8 parts of sodium acetate. After warming at 9 61 for 1 hour, 5.9 parts of copper sulfate was added in portions over 1 hour, followed by 2 0.0 parts of 25% NΗ3. The mixture was heated to reflux for 12 hours ' thus producing many suspensions of copper complex. Allow the temperature to drop to 45 ° C (while stirring well) within 2 hours, and make this suspension with 70 parts of water and 8.3 parts of 30% HC 1 in 13.3 parts, 3-[ A solution of (2-ethylhexyl) oxy] -1 -propylamine reacted slowly. The resulting precipitate was stirred at room temperature for an additional hour ', filtered and washed to make it salt-free and dried. A compound of the formula (where R is methoxy) is obtained: 15 200401010

a) 33.5 parts of 6-aminonaphthalene-2 -sulfonic acid are stirred into a mixture of 150.0 parts of water and 24.7 parts of 30% HC1. After adding loo.o parts of ice, the amine was diazotized by adding 4.10 parts by volume of a 4N NaNO2 solution. The resulting suspension was stirred at 45 ° C for 1 hour, the filtered sodium nitrite was "broken" with aminosulfonic acid, and the pH was raised to 4.5 by adding 3.5 parts of NaHC03. 32.6 parts of [(2-methoxyphenyl) amino] -methane acid were added in small portions while P Η 値 was adjusted to 4.3-4.5 by simultaneously adding 8.0 parts of NaHC03. The resulting mixture was then stirred at room temperature for 4 hours and pΗ 値 was increased to 9 · 5 by adding 150.0 parts of 30% n a Η. The resulting mixture was then heated to 85 ° C. for 5 hours, and 210 parts of sodium chloride was added, and the resulting orange precipitate was filtered and dried. b) Stir 38.0 parts of monoazo dye in part a) above; [50 parts of water and 2 8.2 parts of 30% H C 1 in a mixture. 10.0 parts of ice was added, followed by 29.0 parts (by volume) of a 4 N N a Ν 02 solution. The resulting brown slurry was stirred at 5 T: for 2 hours prior to "destroying" excess sodium nitrite with sulfamic acid. The diazonium salt suspension was then slowly poured into a solution of 20.8 parts of water and 25. 4 parts of amine-8-hydroxynaphthalene-6-sulfonic acid (gamma acid) in 190.0 parts of 30% NaOH. in. The pH was raised to 8.5-9.0 by simultaneous addition of 2 6.5 parts of Na2CO3. The resulting mixture was then stirred at 200401010 for 3 hours at room temperature and ρ Η 値 was reduced to 1.0 by adding 5 8.7 parts of 30% H C 1 to produce a brown precipitate, which was filtered and dried. c) Stir 24.3 parts of the bisazo dye in part b) above into a mixture of 70 parts of water and 12.2 parts of 30% H C 1. Add 5 0.0 parts of ice, followed by 1 1 · 0 parts (by volume) of a 4 N N aN 0 2 solution. The resulting dark brown suspension was stirred at 5 ° C for 2 hours before the excess sodium nitrite was "destroyed" with sulfamic acid. The diazonium salt suspension was then slowly poured into 80 parts of water and 13.6 parts of 4.7 parts of 30% NaOH, 1-amino-8-hydroxynaphthalene-3,6-disulfonic acid (acetic acid). In solution. The pH was raised to 4.5-5 · 0 by the simultaneous addition of 21.7 sodium acetate. The resulting mixture was then stirred at room temperature for 3 hours, resulting in a dark purple suspension. The reference azo-based dye is recovered by filtration and dried. d) Suspend 37.5 parts of the paraazo dye in part c) above in 60 parts of water, 9.7 parts of diethanolamine and 2 7.2 parts of sodium acetate. The mixture was heated to 9 8 before slowly adding a slurry of 10.0 parts of copper sulfate, 16 parts of water and 1 6.0 parts of 25% N Η 3 heated to 60 ° C. ° C. The reaction mixture was heated to reflux for 12 hours' and thus a black solution of the copper complex was produced. Allow the temperature to drop to 25 ° C over 2 hours (while stirring well) and allow the suspension with 85 parts of water and 18.8 parts of 30% HC 1 in '2 1 .1 parts of 2- Ethylhexylamine reacts slowly. The resulting precipitate was stirred for 1 hour, filtered and the residue was washed with deionized water to make it salt-free and dried. A compound having the following formula (4 6.0 g) was obtained: 200401010

Example 3 a) 78.1 parts of 6-aminonaphthalene-2-sulfonic acid was stirred into a mixture of 750.0 parts of water and 54.1 parts of 30% HC1. After adding 3 00.0 parts of ice, the amine is diazotized by adding 8 8 0 parts by volume of a 4 N N a N 0 2 solution. The resulting suspension was stirred at 5 t for 1 hour.

NaN02 is "broken" with aminosulfonic acid. The diazonium salt suspension was then slowly poured into 5 5 · 3 parts of 2,5-dimethoxyaniline solution in 300 parts of water. P Η 値 was increased from the simultaneous addition of 2 9.7 parts of Na H C 0 3 to 4.3-4.5 ° and then the resulting mixture was stirred at room temperature for 4 hours. The resulting $ ® color precipitate was accumulated and filtered and dried. b) 23.0 parts of the monoazo dye in part a) above are stirred into a mixture of 10 ° C · 00 parts of water, 6.5 parts of 30% NaOH and 15.0 parts by volume of 4N NaN02 solution. This solution was slowly poured into 100 parts of ice and 51.7 parts of 30% H C 1 resulting in a suspension of diazonium salts, which was stirred at 5 ° C for 2 hours. The excess NaN02 was then "broken" with aminosulfonic acid. Slowly pour this slurry into 20 parts of water and 7.4 parts of 30% Na a OH, 13.2 parts of a solution of 2-amino-8-hydroxynaphthalene-6-sulfonic acid (gamma acid) in. Ρ Η 値 was increased to 8.5-9.0 by adding 5 5 5 parts of Na 2 C ◦ 3 ′ simultaneously. The resulting mixture was then stirred at room temperature for 3 hours and 91.7 parts of 30% HC was added to reduce the pH of 18 200401010 to 1.0, resulting in the accumulation of a dark purple precipitate, which was filtered and dried. O Stir 21.1 parts of the bisazo-based dye in part b) above into a mixture of 100.0 parts of water '1 5.0 parts of 30% NaOH and 9.0 parts by volume of a 4N NaN02 solution. This solution was slowly poured into a suspension of 50 parts of ice and 3 0.6 parts of 30% HC1 to produce a diazonium salt, and it was stirred at 5 ° C for 2 hours. The excess NaN02 was then "broken" with aminosulfonic acid. This slurry was slowly poured into a solution of 40 parts of water and 6.3 parts of 30% NaOH in 9.4 parts of 1- (4'-sulfophenyl) -3 -carboxy-5 -pyrazolinone . By adding 3 3.3 parts of sodium acetate at the same time, the pH was raised to 4.3 -4.5 to produce a dark purple suspension. The resulting mixture was stirred at room temperature for 3 hours and the pH was reduced to 1.5 by the addition of 30% HC1. 60.0 parts of solid sodium chloride were then added, resulting in the accumulation of many precipitates of the azo dyes, which were filtered and dried. d) Stir 24.7 parts of the paraazo dye in part c) above into 200 parts of water, 8.0 parts of diethanolamine and 24.9 parts of sodium acetate. Before slowly adding 8.3 parts of copper sulfate, 13 parts of water, and 1 3.0 parts of a slurry caused by heating to 60 ° C and 25% NH3, the mixture was heated in an autoclave to 98 ° C. The reaction mixture was then heated to 1 2 -1 3 0 ° C for 16 hours, thus producing a black solution of copper complex. Allow the temperature to drop to 25 ° C, make the suspension with 50 parts of water and 19.8 parts of C12.14 third alkylamine in 30% HC1 of 12.9 parts (for example, known as "Primene 8 1R " of Commercial product) solution slowly reacted. The resulting precipitate was stirred for 1 hour, filtered, the residue was washed with deionized water to make it salt-free, and dried to obtain a compound of the following formula (4 5.6 g): 19 200401010

Example 4 a) 2 4.2 parts of 1, 3 -naphthalenedisulfonic acid, 7-[(4-amino-3 -methoxyphenyl) azo] disodium salt (CAS registration code 65 1 5 1- 26-0) Stir into a mixture of 300 parts of water and M.1 of 30% HC1. After adding 100 parts of ice, the amine was diazotized by adding 1 3.0 parts by volume of a 4N NaN02 solution. The resulting diazonium salt solution was stirred at 5 ° C for 1 hour, and the excess NaN02 was "destroyed" with aminosulfonic acid. Then slowly pour the orange solution into 50 parts of water and 4.0 parts of 30% Na 2 O 1 2.7 parts of (4'-sulfophenyl) -3 -methyl-5 -pyridine Azolinone solution. The pH was raised to 4.3-4.5 by simultaneously adding another 15.0 parts of sodium acetate. The resulting mixture was then stirred at room temperature for 3 hours and 30% HC was added. The pH was reduced to 1.5 · '50 parts of sodium chloride were added, and the resulting orange precipitate was accumulated and filtered and dried. . b) 19.9 parts of the diazo dye in part a) above are stirred into 20 parts of water and 11.3 parts of diethanolamine. Heat the mixture to 9 before slowly adding a slurry of 1 -7 parts of copper sulfate, 19 parts of water, and 1 9.0 parts, heated to 60 ° C, 25% N Η 3 8 t. The reaction mixture was heated to reflux for 4 hours, thus producing a dark red solution of copper complex. The reaction mixture was cooled to 25 ° C and heated to 60 ° C. With 240 parts of water, 36.6 parts of 9- (2-carboxyphenyl) -3,6-bis (diethylamino) ) A solution of gluttonous iron chloride (known as a dye of 20 200401010 " Rhodamine B ") that produces a reaction. Slowly add 50 parts of water and 5.0 parts of acetic acid to 2 1.5 parts of hydrogenated rosinamine (known as "amine D", a commercial product of CAS RN 6 1 7 9 0-4 7-4). The solution produced many purple precipitates that accumulated. The pH of the resulting mixture was then reduced from the addition of 30% HC1 to 3.0-3.5 and the red dye with blue was filtered and dried. A compound of the following formula (7 7.6 g) was obtained:

twenty one

Claims (1)

~ Item 〇1〇I, patent applications: including Eugen, kinds of double-slit or an azo Reference 1:! Residue bis dye compounds I copper complex compound of the general formula or reference ⑴ azo compounds: D- • N = N—K -N = N-—κ (〇 where n is 1 or 2, the residues of the diazo component D ′ are selected from the group consisting of: lightly or unsubstituted. Phenyl, substituted or unsubstituted naphthyl, group, group {Residue 1 of knife K is selected from the group consisting of: unsubstituted phenol, Keshi? You ^ ^ substituted or Unsubstituted naphthol, via 仵 ¥ unsubstituted H 1t ^ -benzyl-5 -pyrazolinone, substituted or unsubstituted ^ naphthalene * _5-pyrazolinone, and by { The residue of 砠 ^ 'is selected from the group consisting of k-substituted phenols, substituted or unsubstituted naphthol, and the residue of 取 K is selected from the group consisting of: Substituted Phenols 'substituted or unsubstituted naphthols, # ^ phenyl, naphthyl, phenol' naphthol, 1-phenyl-5 -quinazolinone, and! · = 1_Guanyi radical , Methyl, fluorenyl, or dentin, 1 and parts D, KQ, K 1 and / or K: 2 (¾ f & + jh group UJ main 11 + 1 is a leaking group with at least one alkoxy group or aryl fluorene or with rhodamine B type or- The sulfonate group of the amine D-type counterion is substituted. 2 'Rushen g 范 Patent Model No. 1 a /// z Youshen Coupling 1: 1 copper complex dye ... Its characteristics are: The counter ion system of the acid salt group is selected from the group: 200401010 + Ν 4 _ m (C) _, 2 alkyl) m alkoxy) m + NH4_ni (C6.iC) aryl) m rhodamine B-type cation Or rosinamine D-type cation. Whereas m is an integer from 1 or 4, m is preferably 1. 3. The bis or sulphide 1: 1 copper complex dye compound according to item 1 or 2 of the scope of patent application, characterized in that: for the counter ion system of the sulfonate group res rfu · visit B. + NH3 (1,1-di-n-propylhexyl) + NH3 (2'-ethyl-hexyloxy-n-hexyl) 4. The bisazo 1: 1 copper complex dye compound as claimed in claims 1 to 3, characterized in that: η is 1, D is a residue of the diazo component D 1, which is naphthyl, 23 200401010 K0 is the residue of component κϋι, which is methyl taken from phenyl-5-pyrazolinone, κ 1 is the residue of component κ 1 1, which is an unsubstituted phenol, and the component is At least two of D, K0 and / or K1 are at least one alkyl, alkoxy or arylammonium sulfonate group or a sulfonate group having a rhodamine B or rosinamine D counter ion Mission replacement. 5. The bisazo 1: 1 copper complex dye compound as claimed in items 1 to 4 of the patent application, characterized in that = η is 1, D is at least one sulfonate group having the above formula as a counter ion Group to be replaced and The above formula is replaced by at least one sulfonate group having the following formula as a counter ion The following formula 6. The azo 1: 1 copper complex dye compound according to claims 1 to 3 of the scope of patent application, characterized in that η is 2, D is a residue of the diazo component D ', and is unsubstituted. Naphthyl, 24 200401010 is component κ "The residue is selected from the group consisting of: amino substituted or unsubstituted naphthol, substituted or unsubstituted 1-phenyl-5-pyrazole For the linones, K1 is a residue of K1 ', which is an unsubstituted naphthol, and K2 is a residue of component K21, which is selected from the group consisting of methoxy-substituted or unsubstituted phenolphenols, and At least three of components D, K0, K1, and / or K2 are at least one alkyl, alkoxy or aryl ammonium sulfonate group or have rhodamine B or rosinamine D type counter ions The sulfonate group is substituted. 7. For example, the reference azo group 1: 1 copper complex dye compound of the claims 1 to 3 and 6 is characterized in that η is 2, and D is represented by a single -(C ^ 12 alkyl) ammonium sulfonate is replaced by K0 is replaced by at least one mono- (C ^ u alkyl) ammonium sulfonate Replace it with salt. A method for preparing a bis or reference azo-based 1: 1 copper complex dye compound as described in claims 1 to 7 in the scope of patent application, characterized in that the bis or reference azo-based dye according to general formula (I) Compound: DN = N — Kn ~ —N = N——K〇⑴ where η, D, KG, K1 and K2 are all as defined in the scope of the patent application, using a copper salt to metallize, and Alkyl, alkoxy or arylamines, or react with rhodamine B or rosinamine D and precipitate from 200401010 from acidified aqueous or non-aqueous suspensions. 9. A use according to the scope of patent applications 1 to 1 The bis or ginseno 1: 1 copper complex dye compound of item 7 is used as a dye in the spray paint. 1 〇.-Uses a bis or azo 1: 1 according to the scope of application patents 1 to 7 Copper complex dye compounds are used as dyes or charge control agents in inkjet inks or as toners for facsimile machines. 200401010 柒 Designated representative map: (1) The designated representative map in this case is: (0). (II) ) A brief description of the representative symbols of the components in this representative diagram: 捌When, please show most features disclosed invention of the formula: D N = N—KntN = N——K0 (I)