# US 2014/0196630 A1 · Magenta dyes and their preparation methods and applications

> Agents: this data is available as JSON from the patentgrep API and MCP server — see https://patentgrep.com/llms.txt

- Number: US 2014/0196630 A1
- Document ID: US20140196630A1
- Status: Published application
- Kind: A1
- Application number: 14/216,906
- Filed: 2014-03-17
- Published: 2014-07-17
- Earliest claimed: 2012-03-20
- Assignees: Zhuhai Ninestar Management Co., Ltd.; Dalian University of Technology
- Applicants: Zhuhai Ninestar Management Co., Ltd.; Dalian University of Technology
- Inventors: Xiaojun Peng; Shiyu Li; Jinhe Wu; Fanming Meng; Rong Zhang; Jiangli Fan; Feng Wang; Shaolei Li
- Web page: https://patentgrep.com/patent/US20140196630A1

## CPC

- C09B 5/14: Benz-azabenzanthrones (anthrapyridones)
- C09D 11/02: Printing inks (C09D11/30 takes precedence)
- C09D 11/328: characterised by dyes
- C09B: ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES {, e.g. PIGMENTS}; MORDANTS; LAKES (fermentation or enzyme using processes to synthesise a desired chemical compound C12P)
- C09D: COATING COMPOSITIONS, e.g. PAINTS, VARNISHES OR LACQUERS; FILLING PASTES; CHEMICAL PAINT OR INK REMOVERS; INKS; CORRECTING FLUIDS; WOODSTAINS; PASTES OR SOLIDS FOR COLOURING OR PRINTING; USE OF MATERIALS THEREFOR (cosmetics A61K; processes for applying liquids or other fluent materials to surfaces, in general, B05D; staining wood B27K5/02; glazes or vitreous enamels C03C; natural resins, French polish, drying-oils, driers, turpentine, per se, C09F; polishing compositions other than French polish, ski waxes C09G; adhesives or use of materials as adhesives C09J; materials for sealing or packing joints or covers C09K3/10; materials for stopping leaks C09K3/12; processes for the electrolytic or electrophoretic production of coatings C25D)

## Abstract

The present invention relates to a class of magenta dyes, their preparation methods and applications. The magenta dyes include the compounds which simultaneously contain carboxyl group, sulfonic acid group and the carbonyl propyl sulfurylsulfonic acid on the anthrapyridone skeleton, showing in the form of general formula (I) or their mixtures. In the general formula (I): A may be cation M4, or substituted or unsubstituted benzyl group, or substituted or unsubstituted naphthyl methyl; M1, M2, M3 are respectively cation or cationic groups; Sulfonic acid group (SO3M2)m may located any position of the benzene ring, of which m is an integer of 0-2. As containing carboxyl (or carboxylic benzyl ester or naphthoate), sulfonic acid groups and carbonyl propyl sulfuryl simultaneously, the magenta dyes of the present invention feature outstanding tone, brightness, light resistance, water resistance, ozone resistance as well as solubility and solution stability, etc.

## Claims

### Claim 1

A class of magenta dyes, include the compounds which simultaneously contain carboxyl group, sulfonic acid group and the carbonyl propyl sulfurylsulfonic acid on the anthrapyridone skeleton, showing in the form of general formula (I) or their mixtures:
in the general formula (I): A may be cation M4, or substituted or unsubstituted benzyl group, or substituted or unsubstituted naphthyl methyl; M1, M2, M3 are respectively cation or cationic groups; Sulfonic acid group (SO3M2)m may located any position of the benzene ring, of which m is an integer of 0-2.

### Claim 2 (depends on 1)

The magenta dyes according to claim 1, wherein,
when A is cation M4, the general formula (I) is changed to the general formula (I′):
when A is substituted or unsubstituted benzyl group, the general formula (I) is changed to the general formula (II):
when A is substituted or unsubstituted naphthyl methyl, the general formula (I) is changed to the general formula (II′):
in the general formula (II) and (II′), R1 is H, C1-6alkyl group, CN, NO2, SO3H or SO3M5, F, Cl, Br, CO2H, CO2M6, CO2R2, or NHCOR3; R2 is H or C1-6alkyl group; R3 is H or C1-6alkyl group; (R1)n may located any position of the benzene ring, of which n is an integer of 0-3;
in the general formula (I′), (II) and (II′), M1, M2, M3, M4, M5, M6 are respectively cation or cationic groups; Sulfonic acid group (SO3M2)m may located any position of the benzene ring, of which m is an integer of 0-2.

### Claim 3 (depends on 2)

The magenta dyes according to claim 2, wherein M1, M2, M3, M4, M5, M6 are selected from the following cation: H+, Li+, Na+, K+, NH4+, or organic ammonium salts N+R4R5R6R7, of which R4, R5, R6, R7 are respectively the same or different H, C1-18 alkyl group, cyclohexyl group, CH2CH2OH, CH(CH3)CH2OH or benzyl group.

### Claim 4 (depends on 2)

The magenta dyes according to claim 2, wherein m is an integer of 1-2.

### Claim 5 (depends on 3)

The magenta dyes according to claim 3, where inorganic ammonium salt N+R4R5R6R7 is selected from: monoethanolamine salt, diethanolamine salt, triethanolamine salt, monoisopropanolamine salt, diisopropanolamine salt or triisopropanolamine salt.

### Claim 6 (depends on 3)

The magenta dyes according to claim 3, wherein cation is selected from H+, Li+, Na+, K+, or NH4+.

### Claim 7 (depends on 2)

The magenta dyes according to claim 2, wherein the compound shown in the general formula (I) may be used in the form of mixture with any ration.

### Claim 8 (depends on 3)

The magenta dyes according to claim 3, wherein the compound shown in the general formula (I) may be used in the form of mixture with any ration.

### Claim 9 (depends on 1)

A method for preparing the compounds shown in the general formula (I) or their mixtures according to claim 1, comprising the following steps:
(1) synthesizing an intermediate compound shown in the general formula (IV):
in the general formula (IV), R8 is C1-C4 alkyl group;
the cyclization steps comprise: based on a compound shown in the general formula (III) or (III′) as a raw material, carrying out cyclization reaction on the compound shown in the general formula (III) or (III′) and malonic acid diester (R8OOC—C—COOR8) in an organic solvent at the temperature of 100° C.-250° C. for 2-10 h to form the intermediate compound shown in the general formula (IV);
cool the reaction system after the cyclization and filter the compound of general formula (IV) separated out from the liquid reaction system to obtain the solid intermediate (IV) compounds;
(2) sulfonation and decomposition step: the intermediate compound shown in the general formula (IV) is sulfonated with fuming sulfuric acid (SO3—H2SO4) containing 5-30% SO3 or chlorosulfonic acid under the temperature of 10° C.-120° C., and simultaneously decomposition reaction is carried out for 2-4 h to obtain a mixture; Said the mixture comprises one or more the compounds shown in the general formula (V), (VI), (VII);
(3) hydrolysis step: the sulfonation compounds obtained in the step (2) are hydrolyzed at the acid condition or the alkaline condition;
hydrolysis at acid condition: heated the sulfonation liquid obtained in the step (2) to 40° C.-80° C., and hydrolysis 1.5-5 h. Then neutralized the sulfuric acid in the sulfonation liquid using alkali, finally obtained solution of the compound shown in the general formula (I′) (M4 is H);
hydrolysis at alkaline condition: neutralized the sulfonation liquid obtained in the step (2) using alkali to neutral, then adjusted pH using alkali to 9-10 emerging alkalescence, then heated to 40° C.-80° C., hydrolyzed 1.5-5 h, finally obtained solution of the compound shown in the general formula (I′);
(4) benzylation (or naphthyl methylation) step: the compound shown in the general formula (II) (or the compound shown in the general formula (II′)) is obtained by benzylation (or naphthyl methylation) reaction using benzylation (or naphthyl methylation) reagent and solution of the compound shown in the general formula (I′) in the step (3) under the condition of definite temperature, pH, rate of charge, reaction time;
(5) salting-out step: the mixture obtained in the step (4) is salted out with a salt to generate a salt mixture, wherein the salt mixture comprises one or more salts of the compounds shown in the general formula (I);
(6) separation step: the salts of the compounds shown in the general formula (I) are separated out from the salt mixture by adopting stepwise salting out, reversed phase ion-pair chromatography etc., and the obtained salts of the compounds are respectively desalinated to generate the compounds shown in the general formula (I).

### Claim 10 (depends on 9)

A method for preparing the compounds shown in the general formula (I) or their mixtures according to claim 9, wherein,
in the step (1), said reaction temperature is 100° C.-200° C., said reaction time is 2-12 h, said organic solvent has the boiling point of 100° C.-300° C. and can dissolve or partially dissolve the reaction raw material (III) or (III′);
in the step (2), said reaction time is 3-4 h, said sulfonation temperature is 10° C.-100° C., and the content of sulfur trioxide in fuming sulfuric acid is 5-20%;
in the step (3), said hydrolysis temperature is 40° C.-80° C., hydrolysis time is 1.5-5 h; The alkali using in the hydrolysis reaction include but not limited to the following: sodium hydroxide, calcium hydroxide, potassium hydroxide, ferric hydroxide, copper hydroxide;
in the step (4), said temperature of benzylation reaction is 50° C.-150° C., said pH of benzylation reaction is 0-12, said mole rate of charge of benzylation reaction (I′:benzylation reagent) is 1:1-100, said reaction time of benzylation reaction is 1-120 h, said temperature of naphthyl methylation reaction is 70° C.-150° C., said pH of naphthyl methylation reaction is 0-12, said mole rate of charge of naphthyl methylation reaction (I′:naphthyl methylation reagent) is preferably 1:1-20, said reaction time of naphthyl methylation reaction is 0.5-10 h;
in the step (5), said salt used in the salting-out step is an inorganic salt, and the inorganic salt is selected from ammonium chloride, sodium chloride or lithium chloride.

### Claim 11 (depends on 9)

A method for preparing the compounds shown in the general formula (I) or their mixtures according to claim 9, wherein, the number m of sulfonic group of compounds in the step (2) is relation to the content of sulfur trioxide in fuming sulfuric acid and the sulfonation temperature; When at the low content and low temperature, obtaining the compound with m is 1; When at the higher content and temperature, obtaining the compound with m is 2.

### Claim 12 (depends on 10)

A method for preparing the compounds shown in the general formula (I) or their mixtures according to claim 10, wherein,
in the step (1), said reaction temperature is 130° C.-190° C., said reaction time is 2-10 h, said organic solvent has the boiling point of 140° C.-250° C.;
in the step (2), said content of sulfur trioxide in fuming sulfuric acid is 6-15%;
in the step (3), said hydrolysis temperature is 40° C.-70° C., hydrolysis time is 1.5-4 h;
in the step (4), said temperature of benzylation reaction is 60° C.-130° C., said pH of benzylation reaction is 3-12, said mole rate of charge of benzylation reaction (I′:benzylation reagent) is 1:1-80, said reaction time of benzylation reaction is 1-96 h, said temperature of naphthyl methylation reaction is 70° C.-130° C., said pH of naphthyl methylation reaction is 3-12, said mole rate of charge of naphthyl methylation reaction (I′:naphthyl methylation reagent) is preferably 1:1-10, said reaction time of naphthyl methylation reaction is 1-5 h.

### Claim 13 (depends on 12)

A method for preparing the compounds shown in the general formula (I) or their mixtures according to claim 12, wherein,
in the step (1), said reaction time is 2-8 h, said organic solvent has the boiling point of 140° C.-200° C.;
in the step (3), said hydrolysis temperature is 50° C.-70° C., hydrolysis time is 1.5-3 h;
in the step (4), said temperature of benzylation reaction is 70° C.-80° C., said pH of benzylation reaction is 5-10, said mole rate of charge of benzylation reaction (I′:benzylation reagent) is 1:1-70, said reaction time of benzylation reaction is 1-72 h, said temperature of naphthyl methylation reaction is 70° C.-120° C., said pH of naphthyl methylation reaction is 4-9, said mole rate of charge of naphthyl methylation reaction (I′:naphthyl methylation reagent) is preferably 1:1-5, said reaction time of naphthyl methylation reaction is 1-3 h.

### Claim 14 (depends on 13)

A method for preparing the compounds shown in the general formula (I) or their mixtures according to claim 13, wherein,
in the step (4), said pH of benzylation reaction is 6-10, said mole rate of charge of benzylation reaction (I′:benzylation reagent) is 1:1-60, said reaction time of benzylation reaction is 1-48 h, said temperature of naphthyl methylation reaction is 50° C.-110° C., said pH of naphthyl methylation reaction is 5-7, said mole rate of charge of naphthyl methylation reaction (I′:naphthyl methylation reagent) is preferably 1:1-3.

### Claim 15 (depends on 14)

A method for preparing the compounds shown in the general formula (I) or their mixtures according to claim 14, wherein,
in the step (4), said pH of benzylation reaction is 7-9, said mole rate of charge of benzylation reaction (I′:benzylation reagent) is 1:1-50, said reaction time of benzylation reaction is 1-24 h, said temperature of naphthyl methylation reaction is 50° C.-100° C.

### Claim 16 (depends on 15)

A method for preparing the compounds shown in the general formula (I) or their mixtures according to claim 15, wherein, in the step (4) said mole rate of charge of benzylation reaction (I′:benzylation reagent) is 1:1-40.

### Claim 17 (depends on 1, 5, 6, 7, 8, 9, 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, 21, 22, 23, 24, 25, 26, 27, 28, 29, 30, 31, 32, 33, 34, 35, 36, 37, 38, 39, 40, 41, 42, 43, 44, 45, 46, 47, 48, 49, 50)

An ink-jet water-based ink composition, comprising 1-20 wt % of the magenta dyes according to claim 1, 5-50 wt % of organic solvent miscible with water and 30-94 wt % of water, based on the total weight of the composition.

### Claim 18 (depends on 17)

An ink-jet water-based ink composition according to claim 17, wherein the sum of the component contents is 100%.

### Claim 19 (depends on 17)

An ink-jet water-based ink composition according to claim 17, wherein said water-miscible organic solvents are selected from one or more of the followings: ethanol, n-propanol, Isopropanol, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, ethylene glycol monobutyl ether, diethylene glycolmonobutyl ether, triethylene glycol monobutyl ether, propylene glycol, butanediol, pentanediol, hexanediol, diglycerol, 2-pyrrolidone and N-methyl-2-pyrrolidone.

### Claim 20 (depends on 1)

An application of the magenta dyes according to claim 1, serving as a colorant for the following materials: ink, coating, paint, laser printing toner, marker, paper, fabric, glass, or ceramic.