TWI301501B - Monoazo reactive red dyestuff - Google Patents

Description

In particular, there are 1301501. V. INSTRUCTION DESCRIPTION (1) [Field of the Invention] The technical field of the present invention relates to a fiber-reactive dye with respect to a novel monoazo-reactive red dye. [Background of the Invention] When dyeing with a fiber-reactive dye, high-quality dyes and a dyed dyeing process are highly anticipated. Therefore, there is a need for novel fibers: Reactive dyes to continuously improve their quality are required by the industry. In particular, reactive dyes that can dye red high fastness properties. In the British Patent No. 836,248, U.S. Patent No. 2,979,498, and European Patent Publication No. G 〇7〇8G6, a number of red fiber reactive dyes are exposed, but the dye fastness properties obtainable by using these dyes are In particular, the fastness of the light and the fastness of the sun and the sun need to be improved. In addition, U.S. Patent No. 5,227,475 discloses a fiber-reactive dye of the following formula (π) which contributes to the improvement of dyeing quality and dyeing efficiency, which has the dyeing properties and fastness characteristics of general dyes to fibers. The daylight fastness of the crimson fiber reactive dye and the sun fastness of the sweat still need to be improved. ίPlease read the notes on the back and fill in the details on this page. 耵--------

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

NH-, _〇H, -sch2cooh, rebel 11-carboxypyridinium 1301501

The novel azo compound provided by the present invention improves the characteristics of this aspect, and the azo compound is as shown in the formula (I):

D-Z

X (I) wherein X is -NHCN NHS02CH3, -NHS 2 -C \ or halogen; preferably, X is -NHCN, 3-carboxypyridine or halogen 'wherein the halogen is preferably a fluorine atom or a chlorine Atom; D is a benzene or naphthalene ring having up to 3 substituents selected from the group consisting of halogen, Cl 4 alkyl, Ci 4 alkoxy, nitro, amine, hydroxy, carboxy , a phosphate group and a sulfonic acid group; preferably, the D system is a benzene ring having 〇 to 3 substituents; Z is -S02-CH = CH2 or _so2_ch2_ch2-u; U is -〇S03H, C1 or Br ,_0P03H2, _SS03H or ~Comparative, z is -S〇2-CH = CH2 or -S02-CH2-CH2-0S03H; R2 is sulfonic acid group, carboxyl group, _ element or C! -4 alkoxy group The preferred paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill in the pages)

1301501 V. INSTRUCTIONS (3) R 2 is a repeating acid group or a few groups, and η is 0 or 1. Preferably, when the X is a * atom, the hydrogen atom of the Ri material and the R 3 system are Cm. Or a group having at least one substituent; preferably, when X is a fluorine atom or a chlorine atom, 'R is a hydrogen atom and the system I is & an alkyl group; when X is -NHCN, _〇H , _SCH2C (10) Η, _ NHS02CH3, 3- # 咐 Μ 3 3 (3_carboxypyridinium) or —nhso2—^ ^, then Ri and R3 are independently selected from the group consisting of hydrogenogen/s〇3h, c μalkyl, benzene. a group or a C!·4 alkyl group having one or more substituents. The substituents are each selected from the group consisting of: a hydroxyl group, a carboxyl group (carb〇xyl), a sulfonate group, and an amine group. Carbamoyl or meth〇xy carbonyl; preferably 'when X is -NHCN, -OH, -SCH2C〇〇h, -NHS02CH3, 3-carboxypyridine or -, Ri and R3 is a hydrogen atom or a Ci_4 alkyl group. The monoazo reactive dye of the formula (I) of the present invention is preferably a monoazo reactive dye of the following formula (I a ). • n n n n n Pack --------- set------- (Please read the notes on the back and fill in the fields on this page)

so3H NH- "'ipN-D-Z N 丫 N R3

X This paper scale applies to China National Standard (CNS) A4 specification (210X297 public) 1301501 V. Invention description (4) (la) where X 4-nhcn, -〇h, _SCH2cqqh, _ S〇2CH3, 3-^^ aH^(3_carb〇xypyridinium), a nhso2-—one or a halogen; preferably, x is -NHCN, 3-carboxypyridinium, a fluorine atom or a gas atom; and D is a G to 3 substituents. a benzene ring or a naphthalene ring, the substituents being selected from the group consisting of: i, Cl, Gi, silk, nitro, amine R, sulfhydryl, phosphate, and acid reductive; preferably @, d is a benzene ring having up to 3 substituents; z is -S02-CH = CH2 or -SKKHrU; u is a face 〇S〇3H, C1 or Br, -〇p〇3h2, _ss〇3H or C5c〇 〇h; preferably, z is ·8〇2〇η=^η2 or _s〇2_Ch2_CH2_oso3h; n is 0 or 1, preferably, η is 1; when X is an atom of an element, 'R1 is Is a hydrogen atom and R3 is a 4-hospital group or a Ci 4 courtyard group having at least i substituents; preferably, when χ is a fluorine atom or a gas atom, R1 is a hydrogen atom and a R3(10) group; when X is _ NHCN, -0H, _SCH2C(10)Η, _NHS02CH3, 3-slow η ratio <(3_carb〇xyp Yridinium) or

-NHSO, -〇), then R! and R3 are independently selected from the original paper including hydrogen. The Chinese National Standard (CNS) A4 specification (21()><297 public order (please read the back of the note first) Please fill in the fields on this page again)

--------- Order---- 1301501 A7 B7 V. Description of the invention (5) s〇3h, CU4 alkyl, phenyl, -〇 or C with one or more substituents! _4 alkyl base, the substituents are respectively selected from the group consisting of: hydroxyl, carb〇Xyi, suif0, carbamoyl or methoxy carbonyl Preferably, when X is -NHCN, -OH, -SCH2COOH, -NHS02CH3, 3-carboxypyridyl or _2-{3, Ri and r3 are a hydrogen atom or a C?-4 alkyl group. The monoazo reactive dye of the formula (I) of the present invention is particularly preferably a monoazo reactive dye of the following formula (lb).

Z (Please read the notes on the back and fill in the fields on this page)

• ϋ ^^1 I—I 1^1 n ϋ n 丨 nose · X is -NHCN, ·〇Η, _SCH2CC)C)H, NHS02CH3, 3-carboxypyridine (3_carb〇xypyridinium), —NHS〇2— C \ — or _ prime; particularly good, X is -NHCN, 3 · carboxy ylide, chlorine or fluorine atom; z is -8 〇 2 rhyme, 2 or - s 〇 2-cH2_CH2_u; u is 〇 s 〇3H, cl or Br; especially good, z is sum

1301501

5. Description of the invention (6) OSO3H; η is 0 or 1, preferably ^ is ^ / when X is a chlorine atom or a fluorine atom, M Ri is a chlorine atom and R is a C" alkyl group; preferably 'When deuterium is a gas atom or a fluorine atom, R3 is a hydrogen atom and R3 is a methyl group or an ethyl group; 1 when X is -NHCN, -OH, -SCH2C00H, · NHS02CH3, 3-carboxyacridine (3_carb〇) Xypyridini is called or -nhso2-r \, then Rl and R3 are independently selected from the group consisting of a hydrogen atom, a C^4 alkyl group or a Ci "alkyl group having one or more substituents, and the substituents are selected separately. Self-contained: hydroxyl, carboxyl, sulfo, carbarn〇yl or methoxy carbonyl; preferably, when X is · NHCN When _〇H, _SCH2COOH, _NHS02CH3, 3·carboxypyridine or NHSCV^, Ri and R3 are a hydrogen atom, a methyl group or an ethyl group. The monoazo reactive red dye of the formula (lb) of the present invention is The best system is a reactive dye of the following formula (I -1): (Please read the notes on the back and fill in the details on this page.) --------丨-------- delicate_

So2ch2ch2oso3h This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 1-1 The monoazo reactive red dye of the formula (I b ) of the present invention is preferably the following formula (1- 2) Reactive dye:

S〇2CH2CH2〇S〇3H 1-2 (Please read the notes on the back and fill in the fields on this page)

The monoazo reactive red dye of the formula (Ib) of the present invention is preferably a reactive dye of the following formula (1-3).

1-3 The monoazo reactive red dye of the formula (lb) of the present invention is preferably a reactive dye of the following formula (I-4). ϋ I ϋ I ϋ « I · I— ^^1 n I— 11 1301501 A7 B7 V. Description of invention (8)

SO2CH2CH2OSO3H (1-4) The monoazo reactive red dye of the formula (Ib) of the present invention is preferably a reactive dye of the following formula (I-5).

S〇2CH2CH2OS03H 1-5 The monoazo reactive red dye of the formula (lb) of the present invention is preferably a reactive dye of the following formula (1-1):

NH-V-N-N CH3 r

SO2CH2CH2OSO3H (please read the notes on the back and fill in the pages on this page)

Γ • n Hi n 11 —ϋ i^inn ^ · I 1_1 n ϋ_1 ϋ n , T β. F 1-6 12 This paper scale applies to Chinese National Standard (CNS) Α4 specification (210X297 mm) 1301501 A7 B7 , invention description (9) Such dyes can be applied to cellulose fibers such as cotton, rayon, hemp and artificial hemp, as well as dyeing of polyamide fibers and polyester fibers such as wool, silk and nylon. It can also be applied to the dyeing of cellulose fibers or polyamide fibers with polyester fibers, polypropylene fibers and other fibers. It can obtain dyes with good dyeing properties, especially in daylight fastness. Performance. DETAILED DESCRIPTION OF THE INVENTION The preparation of the compound of the formula (I) of the present invention can be carried out by a conventional method, and a monoazo reactive dye of the formula (I) can be produced, for example, by the following synthesis method of the step (a) to the step. In step (a), the azo dye masterbatch of the following (III) and the trihalogen triazine compound of the following formula (IV) are first tested for acidity 3~7.

NH2 +

Hak ^Halτ τ Ν丫 Ν Hal (Please read the notes on the back and fill out the details on this page)

叮 111 I S· (HI) (IV) 13 This paper scale applies to the Chinese National Standard (CNS) Α 4 specification (210X297 mm) ---~

Hal !3〇15〇ι i 'Invention description (10)

Ϊ Temperature (2) Generation The preferred temperature is 2 generations or less, and the compound 'where Hal' is a commercial element such as gas, chlorine or an atom. Step (b), when X is not a _ element, then the compound of the formula (v) is further represented by the following formula (V 〇 compound at a pH of 4 to 12, preferably, a pH of 6 to 10 and a temperature of 20 〜 8 (TC, preferably, the temperature is 4〇~6〇 reaction) (Please read the notes on the back and fill in the fields on this page)

Hal

H—X (VI) 14 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 V. Invention description (11)

(VII)

N

丫 X

VHal N can obtain a compound of the formula (VII) wherein X can be -Nhcn, -OH, -sch2cooh, -nhso2ch3, 3-carboxypyridine, and R1, R2, R3 and η are as defined in the above formula (I) reactive azo The dyes shown by the dye 'H a 1 are halogen, such as fluorine, chlorine or bromine atoms. Step (c), and finally a compound of the formula (VII) and a compound of the following formula (¥111), or when X is a halogen, directly with a compound of the formula (V) and a compound of the following formula (VIII), -nhso2- (please Read the notes on the back and fill in the details on this page. Η Ν D D VIII VIII VIII VIII VIII VIII VIII VIII VIII VIII VIII VIII VIII VIII 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 酸 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳 较佳The reactive azo dye of the formula (I) of the present invention can be obtained by a condensation reaction at 100 ° C, preferably at a temperature of 5 5 to 85. In the above-exemplified processes, the order of reaction between them can be changed arbitrarily, and the reactive azo dye of the formula (I) is obtained in the same manner. For the synthesis method of the compound of the formula (III), reference may be made to the U.S. Patent No. 15 paper scale applicable to the Chinese National Standard (CNS) A4 specification (21〇χ297 mm) 1301501 5. The invention is disclosed in (12) 4,837,310. The synthesis step of the compound of the formula (III) is exemplified as follows. The compound of the following formula (8) is diazotized at a temperature of from 1 to 2 (r, and then with a naphthol compound of the following formula (X:) at a temperature _ 10 to 5 (rc, preferably, at a temperature of 30 C, the acid value is controlled to be i to 7, preferably, at i to $, the coupling reaction is carried out to prepare a compound of the following formula (χπ) And then in the presence of sodium sulfide at a temperature of 40 to 10 (rc can be subjected to a nitro reduction reaction to obtain a compound of formula (III). OH (s〇3H)n h2n

(XI) (Please read the notes on the back and write the details on this page; > (X)

N〇2 The compound of the above formula (X) can be exemplified by the following examples: 2·methoxy-4-nitroaniline, 2-ethoxy-4-stone sulfanilide (2-ethoxy-4- Nitroaniline), 2-propoxy-4-des-aniline (2-^1*〇0〇\}^4-11彳七〇31111丨1^), 2-butoxy-4 -shixylaniline (2 - but ο X y - 4 - nitr 〇ani 1 ine), 4 - Shisuke aniline -2- 16 This paper size applies to Chinese National Standard (CNS) A4 size (210X297 mm)

1301501 A7 B7 V. INSTRUCTIONS (13) 4-nitroaniline-2-sulfonic acid, 2-carboxy-4-nitroaniline, 2-fluoro-4-stone sulfanilide (2-fluoro-4-nitroaniline), 2-chloro-4-nitroaniline, 2-bromo-4-nitroaniline, and the like. The compound of the above formula (XI) can be exemplified by the following examples: ho3s

OH

Nh2

s〇3H

Nhch3 ho3s^^^^^so3h (Please read the notes on the back and fill in the fields on this page)

H03S

Nhc2h5

NHC2H5 ho3s \ s〇3h -------- order ---------I .

OH

NHCH2CH2CH3

OH

NHCH2CH2CH3 so3H 17 This paper size applies to Chinese National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7

V. Description of the invention (14 OH

Nhchch3 ch3

NHCHCH3

HO3S so3h ch3

NHCH2CH2CH2CH3 so3H

OH

.NHCH2CHCH3 CH3

OH

NHCH2CHCH3 so3h I ch3 (Please read the notes on the back and fill in the fields on this page) • 1 ^^1 ^^1 —ϋ ^^1 ·ϋ J 丨, * βϋ i^i ·ί, v

NHCHCH2CH3 ch3

H03S

OH

NHCHCH2CH3 ch3 so3h

OH

NHCH2SO3H

Nhch2so3h \ s〇3h 18 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7

OH

V. Description of the invention (15)

Ho3s The aromatic amine of the above formula (VIII) is obtained by alkylation of an aromatic amine of the following formula (XIII); the alkylating agent used may be an alkylhalide or a dialkyl sulfate. (dialkylsulfate), monosubstituted ethylene, or oxide 〇h2n-dz (XIII) Haloperane may be methylchloride, ethylchloride, n-propyl chloride (n -propylchloride), isopropyl chloride, n-buthylchloride, isobuthylchloride, sec-buthylchloride, methylbromide, ethyl Br (ethylbromide), n-propylbromide, isopropylbromide, n-buthylbromide, isobuthylbromide, or butyl bromide (sec- 19 The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill in the pages on this page)

• ϋ n ϋ I -..... ϋ, 一一^· n ϋ ϋ - -I 1301501 A7 B7 V. INSTRUCTION DESCRIPTION (16) buthylbromide) 〇 Dialkyl sulfate may be dimethyl sulfate ( Dimethylsulfate), diethylsul fate, dipropylsulfate, etc.; single replacement ethylene with acrylonitrile, acrylic acid, methylacrylate, ethyl acrylate (ethylacrylate), acrylamide, vinylsulfonic acid, and the like. The oxides include ethylene oxide, propylene oxide, glycol, trimethylene oxide, β-buthyloxide, 2-methyl-α-butyl oxide. 2-methyl-a-buthyleneoxide, 2-ethyl-3-methyleneoxide, methoxyethylene oxide, or n-butoxyacetate N-buthoxyleneoxide) and the like. The compound of the above formula (XIII) can be exemplified by the following examples: 1-aminophenyl-3-β-sulfatoethylsulfone, 1-aminobenzene-3-p-sulfatoethylsulfone, 1-aminophenyl-2-beta-sulfate-ethyl l-aminobenzene-2-P-sulfatoethylsulfone, 1-aminobenzene-3-phosphatoethylbenzene, 1-amino-4-methylbenzene- 3-β-metiylbenzene-3-P-sulfatoethylsulfone, 1-aminobenzene-3-β-gasified sulphate (1-aminobenzene-3-p-chloroethylsulfone) ), 1-Amino-4- _20_ This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) (Please read the notes on the back and fill in this page) i^i ϋ — i^i Ml I 0 n -1 ϋ in n .1 nose · 1301501 A7 ___B7_ V. Description of invention (17 ) methoxybenzene-3 - β - sulfate complex 醯 (1 - ami η 〇 - 4 -methoxybenzene-3 -p-sulfatoethylsulfone),1·amino-2,5-dimethylphenyl-4_0-sulfatoethylsulfonate (1-&111丨11〇-2,5-dimethylbenzene-4-P-sulfatoethylsulfone) ^ 1-Amino-2-methoxybenzene-4_β-sulfur Ethyl sulfonate (l_amino-2-methoxybenzene-4-p-sulfatoethylsulfone), 1-amino-2-oxobenzene-4-β-sulfate acetoin (1-3111丨11〇-2- Ch 1 〇r 〇benzene - 4 - β - su 1 fat 〇ethy 1 su 1 f ο ne), 1 -amino-4 methoxybenzene · 5-β_sulfate sulphate (1-ami no -4-methoxybebzene-5-p-sulfatoethylsulfone), 2-aminonaphthalene-8-sulfate acid-2-aminonaphthalene-8-p-sulfatoethylsulfone-6-sulfonic acid , 2-Amino-8-β-sulfate sulphate (2 - am inonaphthalene - 8-β_ 8111€&{〇6{]1}^18111€〇116), 1-amino- 2,5-Dimethoxybenzene-4-ethylsulfonate-Si (1-amino-255-dimethoxybenzene-4-vinylsulfone), 1-amino-2-methoxy-5-methylbenzene 4-β -1-amino-2-methoxy-5-methylbenzene-4-p-sulfatoethylsulfone, 2-aminonaphthalene_4,5,6·β-sulfate complex Aminonaphthalene-LSj-p-sulfatoethylsulfone), 2-aminonaphthalene-4?5,7-P-sulfatoethylsulfone, 1-amino-2 Benzene-4- 1-amino-2-bromobenzene-4-vinylsulfone, 2-amino-8-acid ketone-6-β-sulfate ketone orange (2-3) 111丨11〇- 8- 21 This paper size is applicable to China National Standard (CNS) Α4 specification (210X297 mm) (Please read the notes on the back and fill in the fields on this page) « i^i I ϋ · ϋ IH ϋ .n ϋ · 1301501 A7 B7 V. INSTRUCTIONS (18) sulfonaphthalene-6-β-sulfatoethylsulfone), 2-aminonaphthalene-8-β-phosphate ethanoxene-6-protamine (2-aminonaphthalene-8-p-phhosphatoethylsulfone- 6-sulfonic acid), 2-aminonaphthalene-8-ethyl stearidin _6·hemeic acid (2-81^11〇11&0]11:113161^-8-vinylsulfone-6-sulfonic acid) , 1-amino-2-methoxy-5-methylbenzene-4_β-gasification: ^Si(l-amino-2-methoxy-5-methy 1 benzene - 4 _ β - ch 1 〇r 〇ethy 1 su 1 f ο ne), 1-aminobenzene-253-^^^ii(l-aminobenzene-253-vinylsulfone) ^ 1-Aminobenzene- 2,4_ 浠 浠 醯 (laminobenzene_2,4-villylsιιlfone) , 1-Amino-2-methoxy-5-gasbenzene-4-β-gasified ethyl scutellaria (l-amino-2-methoxy-5-ch Lorbenzene-4-p-chloroethylsulfone), 1_Amino-2-methoxy-5-chlorobenzene-4-vinylsulfone, 1-amine 1-Ethyl-2-ethoxy-5-chlorobenzene-4_P-chloroethylsulfone, 1-amino-2-ethoxy-5 - Benzene-4-ethylhydrazine>^Si(l-amino-2-ethoxy-5-chlorobenzene-4-vinylsulfone), 2-aminonaphthalene-8-beta-sulfate 2-aminonaphthalene-8-P-sulfatoethylsulfone-l-sulfonic acid, 5-chloroaniline-2-P-sulfatoethylsulfone, 5-acid acid group Benzene _ 2 - β - sulphate sulfonate (5 - su 1 f 〇ani 1 in e - 2 - β - sulfatoethylsulfone), aniline - 2-β-phosphorus: acid acetyl chloride (aniline-2- P-phosphatoethylsulfone), 5-chloroaniline - 2 - 22 The paper size applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) (please read the notes on the back and fill in the fields on this page)

• —^1 1_1 _ιϋ ϋ i^i 1·ϋ ^^1 In 丨,· ^^1 i^ii^i ^^1 , T 1301501 A7 B7 V. Description of invention (19 ) β-dissonate 5-chloroaniline-2-p- phosphatoethylsulfone, 5-chloroaniline-2-vinylsulfone, 5-sodium aniline-ethyl hydrazine (5-sulfoaniline) -2-vinylsulfone), aniline - 2 - β-gasification of ani 醢 醢 (aniline-2-p-chloroethylsulfone), 5-chloroaniline-2-β· gasified acetonite (5-chloroaniline_2-p-chloroethylsulfone ), 5·jic acid aniline·2·β-5-sulfoaniline-2-p-chloroethylsulfone, aniline-2-β-thiosulfate sulfonate (311丨1丨) 11- 2-0-thiosulfatoethylsulfone), 5-chloroaniline-2-β-thiosulfatoethylsulfone, 5-sulfonylaniline 2-β-thiosulfuric acid 5-sulfoaniline-2-p- thiosulfatoethylsulfone, 3-amino-2f-(2-sulfatocholyl)-phenylbenzamine (3-Amino-2'-(2) - sulfatoethylsulfonyl)ethylbenzamide), 4-amino-based coffee 2'- (2-sulfate complex B Acyl) Amides ethylbenzene (4_Amin〇-2, - (2- sulfatoethylsulfonyl) ethylbenzamide) and the like. The dye of the present invention can be produced by the above method, and the reaction conditions are clearly described in the above description. The dye of the present invention can be obtained by spraying, sedimentation or pressure filtration, and the type of the dye is powder, fine powder, granule or liquid, and additives such as retarder, leveling agent, dyeing agent, and interfacial activity. Agent or dispersant, etc. The dye of the present invention contains at least an anionic group such as a sulfonic acid group. For _______ 23 This paper size applies Chinese National Standard (CNS) A4 specification (210X297 GM)~~--------- (Please read the notes on the back and fill in the fields on this page)

• ai^i ai^i i>ni^i —ϋ .1 ϋϋ ^ ^ · m ^^1 «Bn ι_ϋ ·ϋ· Λ· V. Description of invention (20 ) == Ming is expressed in free acid form in the specification Bengbu: The more the 1^ is in the form of water-soluble salts, especially the gold test::: such as sodium salt, chain salt, bell salt or money salt, preferably with sodium salt, the test of metal salt (1) Wood is in accordance with the present invention having fiber reactivity and used in the oxime oxime and amino group-containing materials. ... silk, hair: two (1) dyes are suitable for dyeing a variety of different materials. Such as Xinzhiwei fiber and Juyue urinary burning, especially all those containing fiber such as cotton =: the second type of fiber material is natural cellulose fiber, and the second one is the second kind of fiber or polyamide fiber. a mixture. Forms of J-month wood can be printed in various ways, especially aqueous dye solutions, and fixed to the fibers. It is suitable for dyeing and emulsion dyeing. If it contains a commensurate salt, the dyed article is dyed and dyed in the aqueous dye solution. If it is properly heated, the dye is fixed in the dyed after the treatment or in the presence of the test. On the item. The dyes of the invention are particularly suitable for use in the so-called cold-rolling dyeing process where the dyes are applied to the pad dyeing machine and then stored at room temperature for several hours to fix the color. After fixing, the dye is rinsed with cold water and hot water, and if necessary, the dispersant is added to remove the unfixed portion. The invention also relates to the use of the dyeing (including printing and dyeing) dyeing material of the compound of the formula (I) and relating to dyeing (including printing and dyeing) the printing material by a conventional method, wherein the formula (1) is a coloring agent, which will The material of the compound of formula (I) applied to the aqueous medium is fixed to the dyed material by heat or alkali or both. The dye of formula (I) is characterized by high reactivity, good fixing ability and extreme

1301501

V. Description of the invention (21) Good dyeing. It also has excellent color depth, leveling and detergency, as well as high solubility, high depletion ratio and high fixation ratio. It can therefore be used in dip dyeing processes at low dyeing temperatures and requires only a short steam treatment time in the steaming process. The fixing rate is high and easy to wash unless there is a fixed part, and the difference between the dyeing rate and the fixing rate is extremely small, that is, the soaping loss is extremely low. The dyes of the formula (1) are also particularly suitable for printing and dyeing, especially cotton, and are also suitable for printing dyed nitrogen-containing fibers, such as wool or silk or wool or silk blended fabrics, dyeing and printing of cellulose fiber materials with the dyes of the invention. It has high chroma and high fiber dye combined with stability, in the range of acid and test, and has good sun fastness, sweat fastness and excellent wet fastness, such as water wash and water resistance. It is resistant to sea water, cross-dyeing and fast-resistance, as well as good resistance to renewal, fastness to burn and fastness to rubbing. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT The following examples are illustrative of the invention, and the scope of the invention is not limited thereby. The compounds of the formula are in the dissociated acid form; usually they are isolated in the form of their metal salt and used in dyeing in their salt form. The dissociated acid form starting compound mentioned in the following examples can likewise be used in the synthesis immediately or in the form of its salt type (preferably an alkali metal salt such as a sodium salt or a potassium salt). The following examples are illustrative of the invention, and if not specified, the parts and the percentage of the knives are covered with juice. The relationship between parts by weight and parts by volume is like the relationship between kilograms and liters. (Please read the notes on the back and fill in the fields on this page) 袅.

1301501 V. DESCRIPTION OF THE INVENTION (22 The maximum absorbance in the visible range of the compound of the invention is determined by means of its alkali metal salt in an aqueous solution. Example 1 21.8 parts of 4-nitroaniline_2-sulfonic acid and 21.7 parts of a 35°/〇 sodium nitrite solution was dissolved and dispersed in 150 parts of water, and then added to ice acid water containing 300 parts of ice water and 35.5 parts of concentrated hydrochloric acid, and then continuously stirred until diazotization was completed. Add 31.9 parts of 2-amino-8-pyridinyl-3,6-dihydro acid to it, and stir the mixture at room temperature to complete the coupling reaction. Then, adjust the pH value of the reaction mixture to 8 1〇, then mix 1〇·7 parts of sodium sulfide, heat the mixture to 6 (rc and keep the temperature until the reduction is completed. Then add 4 parts of sodium chloride to the reaction mixture, then filter and rinse. The above filtrate was dispersed in 4 parts of ice water, and 16.7 parts of cyanuric chloride was added thereto, and the mixture was stirred at 0 to 1 (rc while maintaining a pH of 4 to 5 with an aqueous solution of sodium carbonate). Inside, a mixture containing the compound of the formula (1) (A) NH~f can be obtained. γΝ

Cl (please read the notes on the back and fill in the fields on this page), one point β. 26 (1) 1301501 A7 _B7 V. Invention description (23) ^~' --- Example 2 In this mouth (A Adding 27·8 parts of N-ethylamino benzene-sulfate group B and heating to 55 χ: and maintaining the pH value of 4 to $, after the reaction is completed, salting out to obtain the formula (2) compound, (λ_Χ 525 nm),

Examples 3 to 33 The procedure of Example 2 was repeated, but the reaction was carried out by substituting the substituted compound shown below for 1-N-ethylaminophenyl-3-β-sulfate sulfonate, respectively; 2 nm blue red mono azo dye. EXAMPLES ALTERNATIVE COMPOUNDS EXAMPLE 3 1-Ν-Ethylaminobenzene- 4-β-sulfate complexes Example 4 1 - Ν-ethylaminobenzene-2 _β-sulfate lycopene Astragalus membranaceus Example 5 1-Ν-Ethylamine-4-decyloxybenzene-3-β-sulfate sulfonate Example 6 1 -Ν-decylaminophenyl-3-β-sulfate Ethylene sulfonate Example 7 1-Ν-Methylaminophenyl-4-β-sulfate ethanesulfonate Example 8 Ν Ν -Methylaminophenyl-2-β-sulfate sulfonate 27 The paper scale applies to the Chinese National Standard (CNS) Α4 specification (210X297 mm) (please read the notes on the back and fill in the pages on this page)

--------- order-------- β. A7 ______B7 Example 9 1_N-methylamine_4_methoxybenzene-3-β-sulfate sulfonate Example 1 0 1 - Ν - β -Aminomethylaminoethyl benzene _ 3 _ β _ sulphate ethane sulfonate Example 1 1 l-Ν-β-amine methyl hydrazide ethyl phenyl sulfate ethane sulfonate Example 12 l-Ν-β-Aminomethylaminoethylbenzene-2_β_sulfate sulfonate Example 13 l-Ν-β-amine meglumine 4-amine methoxy _ 3邛-sulfate ethanesulfonate Example 14 Ν Ν - n-propylamino benzene _ 3 _ β _ sulfate ethanesulfonate Example 15 1 - Ν - n-propylamino benzene _ 4 _ β · Sulfate sulfonate Example 16 1 - Ν-n-propylaminobenzene-2 - β-sulfate ethanesulfonate Example 17 1-Ν-n-propylamine-4-methoxybenzene-3 -β-sulfate ethanesulfonate Example 18 l-Ν-β-cyanoethylaminobenzene _3邛_sulfate sulfonate Example 19 Cyanoethylaminobenzene _4·β-sulfate Ethyl sulfonate Example 20 Di-β-cyanoethylamino benzene·2-β-sulfate ethanesulfonate Example 2 1 1-Ν_β-cyanoethylamine-4-decyloxybenzene-3 -β-sulfate ethanesulfonate Example 22 l-Ν-β- Hydroxyethylamino benzene 3-3-β-sulfate ethanesulfonate Example 23 1-Ν_β-hydroxyethylamino benzene·4-β-sulfate sulfonate Example 24 l-Ν-β- Hydroxyethylaminobenzene 2-1-β-sulfate sulfonate 1301501 V. Inventive Note (24) (Please read the notes on the back and fill in the fields on this page) __28 This paper scale applies to Chinese national standards (CNS) A4 size (210X297 GM) 1301501 A7 B7 V. Description of the invention (25) Example 25 l-Ν-β-hydroxyethylamine-4-methoxybenzene-3-β-sulfate sulfonate Example 26 1 · Ν - β - Rhein Ethylaminobenzene - 3 - β - sulphate Ethyl sulphate Example 2 7 l-Ν-β-methoxycarbonylethylaminophenyl-3-β - Sulfate complexation Example 2 8 1-Ν-ethylamine-2-methoxybenzene·5·β-sulfate ethanesulfonate Example 2 9 Τ"-Ν-ethylamine-2 , 4-Dimethylbenzene-5-β-sulfate ethanesulfonate Example 30 1-Ν-Ethylamine-2-methoxy-5-methylphenyl-3-β-sulfate醯Example 3 1 1-Ν-Ethylamino Qin-6-β-sulfate ethoxylate Yellow Brewing Example 3 2 1-Ν·ethylamine-8-sulfonate naphthalene-6-β-sulfate Ethylene sulfonate Example 3 3 1-Ν-Methylaminonaphthalene-8·β-sulfate ethanesulfonate (please read the notes on the back and then fill in the pages of this page), tr Example 34 in the mixture ( A) adding 3.78 parts of an aqueous solution of cyanamine dissolved in 1 part of water, and heating to 40 to 60 ° C, while controlling the pH value in the range of 8 to 10 with sodium carbonate aqueous solution, until the reaction is completed. The mixture (B) is further subjected to salting out filtration to obtain a monochlorinated three well compound of the formula (34). ^ , ____29 This paper scale applies to China National Standard (CNS) A4 specification (210X297 public slowdown) — Dance 1301501 A7 B7 V. Description of invention (26)

NHCN (34) Example 3 5 Add 25.3 parts of 1-aminophenyl-3-β-sulfate ethanesulfonate to the mixture (B) and heat to 55 ° C and maintain a pH of 4 to 6 After the reaction is completed, it is filtered through salting out to obtain a compound of the formula (35), (Xmax = 525 nm).

SO2CH2CH2OSO3H (35) (Please read the notes on the back and fill in the fields on this page)

.^^1 ϋ i^i in m · ϋ-i ϋ ^^1 ϋ I -- I a. Example 3 6 to 7 6 The procedure of Example 3 5 was repeated except that the substitution compounds shown below were substituted The reaction was carried out with 1 -aminophenyl-3 -β-sulfate group; a blue red monoazo dye at 5 25 ± 2 nm was obtained. EXAMPLES ALTERNATIVE COMPOUNDS - EXAMPLE 3 6 1 - N · Ethylaminophenyl-4 - β - sulphate Ethyl sulphate 30 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1301501 V. INSTRUCTIONS (27) A7 B7 Example 37 1-Ν-Ethylaminophenyl-2-β·sulfate sulfonate Example 38 1 - Ν-ethylamine-4 -methyllactylbenzene- 3 - β - sulphate ethoxylate yellow brewing Example 39 1-Ν -Methylaminophenyl-3-β-sulfate ethanesulfonate Example 40 1 - Ν-mercaptoaminobenzene-4 - β - sulphate ethoxylate yellow brewing Example 4 1 1-Ν -Methylaminophenyl-2-β-sulfate ethanesulfonate Example 42 1 · Ν-Methylamine-4 -methyllactylbenzene- 3 - β - sulphate sulphate yellow brewing Example 4 3 1-Ν-β_amine-branched ethylamino benzene - 3-β-sulfate acetylacetonate Example 44 1 - Ν - β - Amine oxime ethylamine basic -4 - β -sulfate complex 醯 Example 45 1 - Ν - β - amine methyl ethyl phenyl 2- 2 - β - sulfate complex 醢 Example 4 6 l-Ν-β-amine meglumine ethylamine 4-methoxybenzene_3_β-sulfate ethanesulfonate Example 4 7 1 - Ν - positive Aminoaminobenzene-3 - β - sulphate ethoxylate yellow brewing Example 4 8 1-indole-n-propylaminobenzene-4-β-sulfate sulfonate Example 4 9 1 - Ν - positive Propylaminophenyl-2-beta-beta-sulfate complex B's brewing Example 5 0 1 - Ν-n-propylamine-4 -methoxybenzene-3 - β-sulfate sulphate 5 1 l-Ν-β-gas ethylamino benzene-3 - β - sulphate ethoxylate yellow brewing Example 5 2 l-Ν-β-gas ethylamino phenyl-4 - β - sulphate B. Brewing Example 5 3 l-Ν-β·gas ethylaminobenzene-2 - β-sulfate root ethyl iron yellow brewing 31 ---------, can be ------- - (Please read the notes on the back and fill in the fields on this page.) The paper size is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) β 1301501 A7 B7 V. Invention Description (28) Example 54 l-Ν -β-cyanoethylamine-4 -decyloxybenzene-3·β-sulfate ethanesulfonate Example 5 5 l-Ν-β-hydroxyethylaminophenyl-3-β-sulfate complex B Sulfonium sulfonium Example 5 6 l-Ν-β-hydroxyethylaminophenyl-4_β-sulfate sulfonate Example 57 Ι-Ν-β-turned ethylamino benzene 2- 2-sulfate络 黄 黄 实施 实施 实施 5 5 l-Ν-β-hydroxyethylamine-4-methoxybenzene-3-β-sulfate acetylacetonate Example 5 9 1 - Ν-β-sulfonic acid ethylaminobenzene-3 - β - Sulfate ethanesulfonate Example 60 l-Ν-β-methoxycarbonylethylaminophenyl-3-β-sulfate sulfonate Example 6 1 1-Ν-ethylamine-2-methyl Oxybenzene-5-β-acidate ethyl ether continued to brew Example 62 1-Ν-ethylamine-2,4-dimethylbenzene-5·β-sulfate ethanesulfonate Example 63 1-Ν -ethylamine-2-methoxy-5-methylbenzene-3-β-sulfate ethanesulfonate Example 64 1-Ν-Ethylaminonaphthalene-6-β-sulfate sulfonate Example 65 1-Ν-ethylamine-8-sulfonate naphthalene-6-β-sulfate sulfonate Example 66 1-Ν-Methylaminonaphthalene-8-β-sulfate sulfonate Example 67 1-Aminobenzene-4-β-sulfate ethanesulfonate Example 68 1 ·Aminobenzene-2-β-sulfate ethanesulfonate Example 69 1-Ν-Ethylaminobenzene -3-β-sulfate ethanesulfonate Example 70 1_Amino-4-methoxybenzene-3-β-sulfate ethanesulfonate Example 7 1 1-Amino-2-methoxy Benzene-5_β-sulfate ethanesulfonate 32 (please read the precautions on the back and fill in Put each page)

-i^i ^1· ·ϋ 1-^ Hi n- - I n I 参. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 V. Invention description (29) Example 72 1-Amino-2-methoxy-5-mercaptobenzene-4-β-sulfate sulfonate Example 73 1 - fe-based-2,4-methyl-benzene-5-β Sulfate Roots Brewing Example 74 1-Amino-n-n-β-beta-sulfate-branched-branched Example 75 1 -Amino-8-pro-naphthalene-6-β-sulfate complex Example 76 1-Aminonaphthalene-8-β-sulfate ethanesulfonate Example 77

Add 25.3 parts of 1-aminobenzene-3-h sulfate ethanesulfonate to the mixture (A), and heat to 55 ° C and maintain a pH of 4 to 5, and then add 18.5 parts after the reaction is completed. The 3-mercapto-β is more than a bite and heated to 85 to 90 ° C and maintains a pH of 4 to 5, and after salting out by reaction, the compound of the formula (77) (Xmax = 528 nm) is obtained.

The procedure of Example 77 was repeated, except that the following ten alternatives were substituted for the reaction of the 1-aminobenzene _3-β·furnace μ Ρ sulfate sulfonate in Example 77; Blue red single gas dye at 528 ± 2 nm. ____33 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 Gong Du Ding (please read the notes on the back and fill in the fields on this page)

• HI i^in - - - - n I , ^- HI i^i ^^1 in .^1 I *. 1301501 A7 B7 V. Inventive Note (30) Example No. Substituting Compound Example 78 1·Ν - Ethylaminobenzene _4·β·sulfate sulfonate Example 79 1 - Ν -ethylamino benzene -2- 2 - thiosulfate sulfonate Example 8 0 1-indole -ethylamine _4_Methoxybenzene-3-β-sulfate ethanesulfonate Example 8 1 1-Ν-decylamino benzene _3-β-sulfate ethanesulfonate Example 82 1-Ν -曱Aminophenyl benzene 4-β-sulfate ethanesulfonate Example 83 1 - Ν -Methylaminophenyl -2- 2 -β-sulfate ethanesulfonate Example 8 4 1-Ν-decylamine- 4- methoxybenzene-3-β-sulfate ethanesulfonate Example 8 5 l-Ν-β-amine methyl hydrazide ethyl phenyl sulfate ethanesulfonate Example 8 6 l-Ν-β -Aminoguanidinium ethylaminobenzene-4-4-[beta]sulfate ethanesulfonate Example 87 Example of l-Ν-β-aminoformamidoethylaminobenzene-2-β-sulfate sulfonate 88 l-Ν-β-amine meglumine ethylamine·4·decyloxy-3-β-sulfate sulfonate Example 89 1-Ν-n-propylaminobenzene_3_β-sulfate Ethyl sulfonate Example 90 1 - Ν - n-propylamine Benzene 4 - β - sulphate sulphate sulphate Example 9 1 1-Ν·n-propylamino benzene 2 _β-sulfate ethanesulfonate Example 92 1-Ν-n-propylamine _4· Methoxybenzene-3-β-sulfate ethanesulfonate Example 93 Cyanoethylaminobenzene _3_β_sulfate sulfonate Example 94 1βΝ·β-cyanoethylaminobenzene _4-β - Sulfate ethanesulfonate ____ 34 This paper scale applies to China National Standard (CNS) A4 specification (21〇χ297 mm) (Please read the notes on the back and fill in the fields on this page) Install I ^1 ϋ ϋ -1"J- ϋ 1 ii ϋ β 1301501 V. INSTRUCTION DESCRIPTION (31) A7 B7 Example 95 Example of l-Ν-β-cyanoethylaminobenzene-2-β-sulfate sulfonate 9 6 1·Ν-β-cyanoethylamine_4_methoxybenzene-3-β-sulfate-ethyl sulphate oxime ^Package 9 7 1_Ν-β-ethylaminobenzene-sulfate Continuation of Example 9 8 l-Ν-β-Hydroxyethylaminophenylsulfate sulfonate Example 9 9 l-Ν-β-hydroxyethylaminophenyl-2-β-sulfate Ethylene sulfonate Example 1 〇〇l-Ν-β-hydroxyethylamine-4-methoxybenzene-3-β-sulfate sulfonate Example 1 0 1 1->^邛-sulfonic acid Aminophenylbenzene-3邛-sulfate ethanesulfonate Example 102 l-Ν-β·methoxycarbonylethylaminophenyl-3-β-sulfate complex 醯 Example 1 0 3 t-N _ethylamine-2-methoxybenzene-5-β-sulfate ethanesulfonate Example 1 0 4 1_Ν_ethylamine-2,4-dimercaptobenzene-5-β-sulfate complex B Sulfonium Example 105 1-Ν-Ethylamine-2·decyloxy-5-methylbenzene-3-β-sulfate complex B. Example 106 1 - Ν-ethylaminoQin-6 β _ sulphate ether continued to brew Example 107 1-oxime -ethylamine-8 -sulfonate naphthalene-6 - β -sulfate ethanesulfonate Example 108 1-Ν -Methylaminonaphthalene-8- --sulfate ethanesulfonate Example 109 1 -Amino phenyl-4 - β _ sulphate sulfonate Example 1 1 〇 1 -Aminobenzene-2 - β - sulphate ethyl ether continued brewing Example 1 1 1 1-Ν-Ethylaminophenyl-3-β-sulfate ethanesulfonate Example 1 1 2 1-Amino-4-mercaptobenzene-3-β-sulfate sulfonate 35 (Please read the notes on the back and fill in the fields on this page)

• ϋ ϋ n ϋ ϋ ϋ, one $"J- -_ϋ H •纛. This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 ___B7 V. Description of invention (32) Example 1 1 3 1 —Amino-2-methoxybenzene-5 -β-sulfate ethanesulfonate Example 1 1 4 1-Amino-2·methoxy-5-methylbenzene·4_β_sulfate Ethyl sulfonate Example 1 1 5 1-Amino-2,4-dimethylbenzene_5-β-sulfate sulfonate Example 1 1 6 1 -Amino-n--6-β-sulfate Ethyl sulfonate Example 1 1 7 1 -Amino-8-sulfonate naphthalene _ 6 _ β _ sulphate ethanesulfonate Example 1 1 8 1 -Aminonaphthalene-8 - β -sulfate ethanesulfonate醯Example 1 1 9 21.8 parts of 4-nitroaniline 2 -sulfonic acid and 21.7 parts of 35% sodium nitrite solution were dissolved and dispersed in 15 parts of water, and then added to contain 300 parts Ice water and 3 5 · 5 parts of concentrated hydrochloric acid in ice acid water, and then continue to disturb to complete the diazotization. Next, 33.3 parts of 2-indolyl-methylamino-8-hydroxynaphthalene-3,6-disulfonic acid was added thereto, and the mixture was stirred at room temperature until the coupling reaction was completed. Then, the acid mixture of the reaction mixture was adjusted to 8 to 1 Torr, and then mixed with 1 Torr. 7 parts of sodium sulfide' The mixture was heated to 6 ° C and the temperature was maintained until the reduction was completed. Then, 40 parts of sodium sulfide was added to the reaction mixture, which was then filtered and washed. The above filtrate and product were dispersed in 400 parts of ice water, and then 16.7 parts of cyanuric chloride was added thereto, and the mixture was stirred at 0 to 1 ° C while maintaining the pH value in an aqueous solution of sodium carbonate. The first condensation reaction can be completed within the range of 4 to 5 until the end of the reaction. Add 3 · 7 8 parts of cyanamide dissolved in 1 part of water to the reaction mixture, and heat the mixture to 4 〇 to ___ 36 This paper scale is suitable for Zhongguanjia Xian (CNS) from secret (21GX297 public)繁)—(Please read the notes on the back and then fill in the pages of this page) Pack---------Book-------- #. !3〇1501 V. Description of invention (33) The second condensation reaction is completed at 60 ° C while controlling the acid value in the range of 8 to iO with the aqueous sodium carbonate solution until the end of the reaction. Further, 2 5 · 3 & 1 -aminobenzene _ 3 _ sulphate was added to the above reaction mixture. The mixture was heated to 55. . And maintaining the pH value of 4 to 6, and after the completion of the reaction, salting out to obtain a compound of the formula (丨丨9), 〇max = 530 nm),

Ho3s nhch3 (Please read the notes on the back and fill in the fields on this page) "Y^NHCN ΝΗ·

SO2C2H4OSO3H (1 1 9) Example 1 2 0 to 1 9 3 Example 119 was repeated to replace the 2-N-methylamino-8-hydroxynaphthalene compound of the formula (乂1} naphthol compound listed in the second block of the following table. -3,6-disulfonic acid, the compound of formula (X) listed in the third block replaces 4-nitroaniline_2-sulfonic acid, the cyanamide listed in the fourth block, and the formula listed in the fifth block ( VIII) The aromatic amine compound is substituted for the 1-amino stupid-3 - β-sulfate group to obtain the desired monoazo compound. Example No. Molecular Formula (X) Compound

Ate formula (VIII) compound leg ^ Hue • ^^1 ϋ i^i 1^1 ^^1 I Iϋ ϋ_ι n Λ 37 1301501 A7 B7 V. Description of invention (34)

NH2CN h2n-{^ S02C2H40S03H nh2cn t NH2CN h^Q

S02C2H40S03H

S02C2H40SQ3H nh2cn nh2cn nh2cn ?H2C: HN~~(; NH2CN JH2, nh2cn nh2cn nh2cn nh2cn nh2cn ^ c2h5x nh2cn t NH.CN ,

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

-S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

Blu-ray red blue red red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red (please read the back of the note before filling each column) T • ^^1 11 nm ^^1 ·ϋ Hi an ^ - ·1-1 ·1_· n in 11 .—ϋ I , vu

S02C2H40S03H 38 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 V. Invention description (35) 134

H03S, V V , S03H ►H H03! , /NHCH2CH2CH3

N〇2 nh2cn Γ

Blu-ray red

SO2C2H4OSO3H 135 136

H〇3s, nh2cn iH2< HN—

Blu-ray red

Va N-V-NO,

NH.CN

SO2C2H4OSO3H

Blu-ray red

SO2C2H4OSO3H 137 138 139

H03S, so3h nh2cn

NH.CN

NH2CN

Blu-ray red

SO2C2H4OSO3H

-SO2C2H4OSO3H Blu-ray Red (Please read the notes on the back and fill in the fields on this page)

Blu-ray red

S02C2H40S03H 140 OH HO3S, ,nhc2h5 ho3s-

NH.CN h2n- c2h5

S02C2H40S03H Blu-ray red 141 H〇3:

So3h NHC2H5 so3H h3co. -N〇2

NH.CN

Blu-ray red

S02C2H40S03H 142 ho3s-

H03S. VNHC2H5 H2N-

NH2CN 143 ho3!

144

HO

So3h NHC2H5 so3H NHC2H5 so3H H03!

H03S,

Blu-ray red • i^i i^i ·ϋι 1.^1 m ϋ— ^^1 In I— m I— I—in ·ϋ nh2cn Π

NH2CN

S02C2H40S03H

Blu-ray red ginseng

S02C2H40S03H :ch2oh

Blu-ray red

S02C2H40S03H 145 ho3s-

,^NHC2H5 h2n a ^ 'Bu n〇2 nh2cn

Blu-ray red so3h

S02C2H40S03H 146 pH H〇3Sv <,nhch2ch2ch2ch3

Nh2cn

Blu-ray red

S02C2H40S03H 39 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 V. Description of invention (36)

151 H03SV

Nhch2ch2ch2ch3 152 153

Nhch2ch2ch2ch3 H〇3:

Nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn T27

-S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

OH

S02C2H40S03H 154

NH2CN

S02C2H40S03H 155

H〇3; 156

157

H〇3: 158

H〇3! 159

160 H〇3!

NHCH2SO3H S03H NHCH2SO3H so3h NHCH2S03H so3H NHCH2S03H so3h NHCH2S03H so3H NHCH2S03H so3h

HaN-T V-N〇2

N02 h3co. -N〇2 H2N-f V-NO, HO3S. nh2cn h2 NH2CN h2n-Qk-: nh2cn h2 nh2cn ^

S02C2H40S03H

S02C2H40S03H

C2H5 This paper size is applicable to China National Standard (CNS) Α4 specification (210X297 mm)

S02C2H40S03H

S02C2H40S03H

NH.CN

S02C2H40S03H nh2cn

Blu-ray red blue red red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red (please read the back of the note before filling each column) ϋ —ϋ ^^1 ϋ — —ϋ i^i ^ · m 11 —ϋ —-ϋ ^^1 , τ .β.

S02C2H40S03H 1301501 A7 B7 V. Description of invention (37 ) 161

Nhch2s〇3h H03S, v v , so3h HO3!

H2N-e 7-N〇2 nh2cn

S02C2H40S03H 162

NHCH2S03H ho3s' , so3h H03S. -N〇2 nh2cn

S02C2H40S03H 163

NHCH2S03H u ” -/ V ho3s^ v v so3h CV. nh2cn h2n—r V-no2

S02C2H40S03H 164

H03S. 165

HOOC, H2N- -N02 166

-N〇2 167

H2n—f ,) a no2 168 169 170 171 172 173

H2N—7—N〇2 HOOC, h2n- H03S, HOOC, h2n- -N〇2 -N〇2 HOOC H2N—r x)—N〇2

N〇2 -N02 nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red (Please read the notes on the back and fill in the columns on this page) β.

S02C2H40S03H 41 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 V. Invention description (38) 174 h〇3s

NHCH3 )H HOOC, .NHCH3 t h〇3s 175

-N02 176 OH HOsS, ,nhc2h5

HO3S

177 OH HOOQ , NHC2H5 , h〇3s-

-N02 178 OH H〇3Sv , NHC2H5 HO3S·

179 OH HOOQ /NHC2H5

HO3S

H2N—(/ ,) a no2 ho3s* 180

NHCH2CH2CH3 H03S, ho3s 181

NHCH2CH2CH3 -N〇2 ho3s· 182

NHCH2CH2CH3 H03S, ho3s· 183

NHCH2CH2CH3 -N〇2 184

NHCH2S03H H03S. h2n— 185

H03S, 186

H〇3:

N02 nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn nh2cn

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

S02C2H40S03H

—— 02 III , f J- -ϋ I ϋ ϋ 42 This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 V. Invention description (39) 187 188 189 190 191

H03S. h2n- H03S, -N〇2 nh2cn

S02C2H40S03H nh2cn C2H5

S02C2H40S03H -N〇2 nh2cn

H03!

S02C2H40S03H

Nh2cn ϊ 192

_, h2n-

H2CH20H

S02C2H40S03H 193

H2n-^ no2 nh2cn

Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red (Please read the notes on the back and fill in the fields on this page)

S02C2H40S03H Example 194 21 - 8 parts of 4-nitroaniline-2-sulfonic acid and 2 1.7 parts of a 35% sodium nitrite solution were dissolved and dispersed in 150 parts of water, and then added to contain 300 parts of ice water and 3 5.5 parts of concentrated hydrochloric acid in ice acid water, and then continue to stir until diazotization is completed. The carrier was added 3 3 · 3 parts of 2-N-methylamino-8- via ketone-3,6-dibasic acid, and the mixture was stirred at room temperature until the coupling reaction was completed. Then, the pH of the reaction mixture was adjusted to 8 to 10, and then mixed with 1 0.7 parts of sodium sulfide, and the mixture was heated to 60 ° C and maintained at a temperature until the reduction was completed. Then, 40 parts of sodium chloride was added to the reaction mixture, and then filtered and washed. 43.n 1 ϋ i^i - -1; n an , Yi Fen, · ϋ ϋ-· ^^1 ϋ ϋ_ι ^^1 枭· This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm) 1301501

V. INSTRUCTIONS INSTRUCTIONS (40) Washing 2 stipulates that the fermented material is dispersed in the ice water, and then 16.7 parts of dimerized hydrazine is added thereto, and the mixture is enthalpy to 1 Torr. The first condensation reaction is completed by stirring the mixture under the agitation while maintaining the acid value in the range of 4 to 5 with an aqueous solution of sodium carbonate until the end of the reaction. Add 25.3 parts of amphetylbenzene_3_β·sulfur I, ', σ Biao into the reaction mixture, heat the mixture to 5 5 ° C and keep the acid value 4 to 6 until the end of the reaction. The second condensation reaction is completed. In addition, 'J8.5 parts of 3-carboxypyridine is added to the above reaction mixture, and this & is heated to 85 to 90 ° C and the acid value is maintained at 4 to 5, and after salting out, the solution is filtered. A compound of formula (194) can be obtained, 〇max = 5 3 5 nm) 〇

(194) Example 1 9 5 to 2 6 8 Example 194 was repeated to give the formula of the second block of the following table (:? (1) naphthol compound instead of 2-N-decylamino-8-hydroxynaphthalene- 3,6-disulfonic acid, the compound of formula (X) listed in the third block replaces 4-nitroaniline_2-sulfonic acid, the 3-carboxy bite listed in the fourth column, and the column 5 (yin) aromatic amine compound 44 This paper scale applies to China National Standard (CNS) A4 specification (210X297 public) (Please read the notes on the back and fill in the fields on this page) ·I—i^i ^^1 —ϋ ^ · ϋ· 1>1 i^i *1·— ^^1 a· 1301501 A7B7 V. Description of invention (41) instead of 1-aminobenzene-3 - β _ sulfate ethanesulfonate, ie Each desired monoazo compound can be obtained. Example No. Molecular Formula (XI) Formula (X) Compound of 3-carboxyl compound Pyridine Molecular Formula (VIII) Compound Hue 195 ho3s

Nhch3 H03!

H2N-r v>-N〇2 so3h

-S02C2H40S03H

COOH 196 ho3s

Nhch3 so3h

HOOC -N〇2

COOH

S02C2H40S03H 197 ho3s

Nhch3 H03S, H2N-<; 7-N〇2 so3h

C2H5

S02C2H40S03H

COOH 198 ho3s

H3co. h2n—N〇2 so3h

199 ho3s

H03S, H2N-V 7-N〇2 so3h 200 ho3s

So3h H〇3:

N〇2

COOH S02C2H40S03H

(j:H2CH2OH 201 ho3s

Nhch3 so3h H03S, -N〇2

HN-

COOH

S02C2H40S03H 202 ho3s

Nhch3 so3h

N〇2

COOH

S02C2H40S03H 203 ho3s

NHCH2CH2CH3

N〇2

so3H

Blu-ray red blue red red blue red blue red blue red blue red blue red blue red blue red red (please read the back of the note before filling out the columns on this page) _ 1 I l^ii^i I 1 — t^i, one by one "J· ϋ ϋ i^i ϋ -ϋ _

COOH

S02C2H40S03H 45 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 V. Invention description (42) 204205 206 207

HOOC, h2n-HQ3S, h2n-h3co, h2n- H〇3: h2n-

NO,

COOH

COOH

H2N(x ')-SO2C2H4OSO3H

S02C2H40S03H -N〇2 -N02

COOH

208 ho3s*

209 ho3s one

210 H〇3:

211 ho3s*

212 ho3s

213

OH

Nhch2ch2ch3 so3h NHCH2CH2CH3 so3H NHCH2CH2CH3 so3H NHCH2CH2CH3 so3H nhc2h5 so3h NHC2H5 so3H HOaS, h2n- -N〇2

S02C2H40S03H COOH COOH

Ho3!

N〇2

COOH

CH?CH2〇H

S02C2H40S03H H03S, h2n- -N〇2

COOH

S02C2H40S03H

H2n—r 7—no2 H2N—)—N〇2 H03! h2n_

N〇2

COOH

COOH

COOH

S02C2H40S03H

S02C2H40S03H

-S02C2H40S03H 214 215 216 ho3s

h3C0, h2n- H2N-7-NO2 HOOC, h2n- -N02 -N02

COOH

COOH

COOH

S02C2H40S03H L2H5

S02C2H40S03H

Blu-ray red blue red red blue red blue red blue red blue red blue red red blue red blue red blue red blue red blue red blue red (please read the back of the note before you fill in the columns) .Is --- t^i · n I — i^i

S02C2H40S03H 46 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1301501 Α7 Β7 V. Invention description (43) 217 Γ

Ho3s,,so3h 218

OH

Ho3s,\^^03Η OH ,^nhc2h5 219 220

Η2Ν—^ y~NQ2

COOH

CH2CH2CN

S02C2H40S03H

COOH SO2C2H4OSO3H

COOH

COOH €Η2ΟΗ

S02C2H40S03H

S02C2H40S03H 221 ΗΟ3!

Nhch2ch2ch2ch3 SO3H

Ν〇2

COOH

S02C2H40S03H 222 Η〇3:

Nhch2ch2ch2ch3 S03H Η03!

Ν〇2

-S02C2H40S03H

COOH 223 Η〇3:

Nhch2ch2ch2ch3 η2ν-r >-νο2

SOjH

COOH

S02C2H40S03H 224 HO3S-

Nhch2ch2ch2ch3 SOjH H03S, -Ν〇2

COOH 225 ΗΟ3:

Nhch2ch2ch2ch3 H3CO. Η2Ν—(/ ,) a νο2 226 Η〇3:

227 HQj:

228 Η〇3:

229 HOa!

soaH nhch2ch2ch2ch3 S03H NHCH2CH2CH2CH3 S03H nhch2ch2ch2ch3 SO;,Η nhch2ch2ch2ch3 S03H

H03S, -N〇2

S〇2C2H4〇S〇3H COOH COOH

CH2CH2CN H〇3:

N〇2

COOH SO2C2H4OSO3H H03S. H2N—^ '尸尸 N〇2

N〇2

COOH

COOH

CH2CH2OH

S02C2H40S03H

Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red Blu-ray Red (Please read the notes on the back and fill in the fields on this page)

S02C2H40S03H 47

This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 V. Description of invention (44) 230 231 232

Hobs, h2n- nhch2so3h -Ν〇2

Ho3! η2ν·

Ν〇2

COOH C00H

SO2C2H4OSO3H

C00H 233 Η〇3:

-Ν〇2

234 Η〇3:

So3h NHCH2S03H so3h

COOH h3co, -Ν02

235 Η03ί

〇Η Η ( ^nhch2so3h

Ν〇2

So3h

S〇2C2H4〇S〇3H COOH COOH

CH2CH2CN 236

ΗΟβ ν v, S03H ζ)Η Η〇3: ^nhch2so3h

Ν〇2

COOH

S02C2H40S03H 237 238 J^^^NHCH2S〇3H H03S/^s^Sv;:;^S〇3H ζ)Η V prison Η Ν2Ν·

Ν〇2

COOH

H03S, ν V so3h Ν〇 2

239

HCbS, η2ν- -Ν〇2

240

HOOC, η2ν-

241

Ν〇2

242

-Ν02

CH2CH20H ηΪ-Ο S02C2H40S03H COOH COOH COOH COOH COOH

Blu-ray red blue red red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red (please read the back of the note before filling each column) -^1 ϋ ϋ II 1 ϋ, 1"J* nn —1 I n I . 48 This paper scale applies to Chinese National Standard (CNS) Α4 specification (210X297 mm) 1301501 A7B7 V. Description of invention (45) 243 ^ HO}:

HO3S. 244 H〇5:

245

246 HO,!

Ύ)- Ύ)-Ύ). Ύ)-

.SO3H H2N—7—N〇2

COOH

,s〇3H h2n—(’ , ) a no2

, SC^H

,SQ,H HOOC, -N〇2 -N〇2

COOH

SO2C2H4OSO3H COOH COOH

SO2C2H4OSO3H 247

HO3S

NHCH3 -N〇2

COOH

SO2C2H4OSO3H 248 )H HOOQ /NHCH3

H〇3S

H2n—7—no2

249

HO3S

NHCH3

N〇2

COOH COOH

250 HOOC, /NHCH3

HO3S

H2n-r 7-no2

COOH

SO2C2H4OSO3H 251 HO3S·

NHC2H5

N〇2

COOH

SO2C2H4OSO3H 252 OH HOOC, ,NHC2H5

HO3S

Η2ν^ n>—no2

253 OH HOaS, /NHC2H5 H03S·

-N〇2

COOH COOH

254 ho3s-

OH

NHC2H5

N02

COOH

SO2C2H4OSO3H 255 QH HO3S, /NHCH2CH2CH3 HOf

H2N-r 7-N〇2

Blu-ray red blue red red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red blue red (please read the back of the note before filling each column) • ϋ· n B_^i 1Β_ϋ ^ ^ · mn —ϋ ϋ ϋ n ϋ — , \Η 口枭·

COOH

SO2C2H4OSO3H 49 This paper size is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 V. Invention description (46 256 257 258 259 260 261 262 263 264 265 266 267 268

HOOC, H2N-HOOC, h2n-H03S, H2N^h3co, h2n-H03S. H03S, H2N^:/ >-N02 H03S, h2n-7-n〇2 -N02 -N〇2 -N〇2 H〇3 !

N02 -N〇2 -N02 -N〇2 H03!

N〇2 -N〇2

COOH

COOH

COOH

COOH

COOH

COOH

COOH

COOH

COOH

COOH

COOH This paper scale applies to China National Standard (CNS) A4 specification (210X297 mm)

SO2C2H4OSO3H COOH COOH

SO2C2H4OSO3H

SO2C2H4OSO3H

H2N—C ,)—SO2C2H4OSO3H

SO2C2H4OSO3H

SO2C2H4OSO3H

SO2C2H4OSO3H

CH2CH£N

SO2C2H4OSO3H

S02C2H40S03H

yH2CH2〇H

S02C2H40S03H

S02C2H40S03H Blu-ray red blue red red blue red blue red blue red blue red blue red red blue red blue red blue red blue red blue red blue red (please read the back of the note before you fill in the columns) ϋ I n ϋ I n ϋ n, 一一"J· ϋ— -- - - - n ϋ · 50 1301501 A7 B7 V. Description of the invention (47) Example 269 21.8 parts of 4-nitroaniline_2-sulfonic acid and 21.7 parts A 35 % sodium nitrite solution was dissolved and dispersed in 15 parts of water, and then added to ice acid water containing 300 parts of ice water and 3 5 5 parts of concentrated hydrochloric acid, and stirring was continued until heavy gasification was completed. Next, 23.8 parts of 2-amino-8-pyridin-6-acid was added thereto, and the mixture was stirred at room temperature until the coupling reaction was completed. Then, the pH of the reaction mixture was adjusted to 8 to 丨〇, and then mixed with 7 parts of sodium sulfide, the mixture was heated to 60 and maintained at a temperature until the reduction was completed. Then 4 parts of sodium chloride was added to the reaction mixture, which was then filtered and washed. The above filtrate was dispersed in 4 parts of ice water, and 16.7 parts of cyanuric chloride was added thereto, and the mixture was stirred at 〇 to 1 Torr while maintaining a pH of 4 to 5 with an aqueous solution of sodium carbonate. The first condensation reaction can be completed within the range until the end of the reaction. Add 27.8 parts of 1-N-ethylamino stupid 3-β-sulfate ethyl sulfonate to the above reaction mixture, and heat to 5 5 ° C and maintain a pH of 4 to 5 until the reaction is completed. After salting out, it can be passed to the compound of formula (269), (λ max = 5 18 nm). (Please read the notes on the back and fill in the pages on this page)

Table paper scale applies to China National Standard (CNS) A4 specification (210X297 mm)

1301501 V. INSTRUCTIONS (48) Example 2 7 0 to 2 9 5 Repeat Example 2 6 9 to replace the 2-amino-8-radio-based _6_continued acid: =(XI)Caidu compound instead of 4-nitroaniline-2-acid, listed in the formula (X) + one of the cyanuric chloride or dihydrate listed in the fourth column The gasified mice are individually represented by C1 #F for cyanuric chloride and trimeric gasification cyanide, and the aromatic amine compound of formula (VIII) listed in the fifth block instead of ^N·ethylaminobenzene_3_β_sulfuric acid. After the roots are confirmed, each desired monoazo compound can be obtained. _ Trimer gas Molecular formula (XI) Molecular formula (X) Cyanide compound (VIII) compound or trimerized compound Hue gasification vibration 4 (Please read the back of the note and fill in the fields on this page)

271 HOOC Cl Blu-ray Red Blu-ray Red 272 273 274 275

HN C2H5

SO2C2H4OSO3H H〇3!

N〇2

Cl

HN· CH

SO2C2H4OSO3H h3co,

Cl -N〇2 HN· c2h5

SO2C2H4OSO3H H03!

N02 H〇3!

N〇2

Cl

Cl C2H5 SO2C2H4OSO3H HN, 乂

CH2CH2CN, so3h blue red red blue red blue red blue red 52 This paper scale is applicable to China National Standard (CNS) A4 specification (210X297 mm) 1301501 A7 B7 V. Invention description (49) 276 ^ 277 278 279 280 281 282 283 284 285 286 287

Nh2 S03H H03: η2ν·

V\ h2n—/ \-no2 ho3! h2n

N02 H〇3: h2n-

N02 HOOC, h2n- H〇3: h2n-

N02 h3co, h2n- H〇3:

H〇3; h2n

N02 ho3! h2n·

N02

Q J (j:H2CH2QH

Cl HN C2H5

F

F

F

F

F

F

F

F

F HN C2H5

HN C2H5

S02C2H40S03H ) , S02C2H4〇S03H S02C2H40S03H S02C2H40S03H c2h5'

S02C2H40S03H

S02C2H40S03H HN- c2h5^= ~so2c2h4oso3h C2H5 S02C2H40S03H Vr ^^so3h

S02C2H40S03H ch?ch2oh

S02C2H40S03H

288

Ho3! h2n- ho3! h2n. h2n-^ no2

N〇2

N02

F

F

HN-C2H5 S02C2H40S03H

Blu-ray red blue red red blue red blue red blue red blue red blue red red blue red blue red blue red blue red blue red red blue red (please read the back of the note before filling out this page)

I— I -- 1 1 I, 一一"J. I II ϋ I β. 53 This paper scale applies to the Chinese National Standard (CNS) A4 specification (210X297 mm)

1301501 V. Description of invention (5〇) 289

F

C2H5 290

S02C2H40S03H

s〇3H η2ν·

F 291

H3co,

S02C2H40S03H

s〇3H -N02

F HN· C2H5

292

s〇3H

NOj

F 293

S02C2H40S03H

so3H 9H2CH2CN

N〇2

F Blu-ray red Blu-ray red Blu-ray red Blu-ray red Blu-ray red

s〇3H S02C2H40S03H

Example 296 (Please read the notes on the back and fill in the fields on this page) = 1 part of urea, 1 part of reducing agent, 2 parts of baking soda, 5 parts of sodium soda and 815 parts of warm water (10) A portion of the auxiliary paste was obtained by the application of the aid; 3 parts of the dye of the formula (2) prepared in Example 2 was sprinkled on the above-mentioned 100 parts of the auxiliary paste, and quickly mixed.卩 1 () () 811's 45 degree twill print screen is covered on the - size of the mercerized cotton twill, the color paste is scraped 'to put the scraped cloth into the 65t flood box for 5 minutes to dry The dried cloth was placed in a steamer at a constant pressure saturated steam of 102 to 105 < t for 10 minutes. After that, the obtained blue dye is first washed with cold water, washed with boiling hot water for 10 minutes, and soaped with boiling non-ionic detergent for 1 〇 minutes. 54 paper scales are applicable to China National Standard (CNS) A4 specification (210X297 mm). 1301501 A red-blue dye can be obtained with A7 V. Inventive Note (51). It is then washed once with cold water and has excellent drying characteristics. Example 29 7 3 parts of the dye of the formula (7) prepared in Example 2 was dissolved in 100 ml of water to prepare a 30 part/boost dye solution; an alkali agent was used (using caustic soda 38°~'15 ml/liter and awning) Shixiao 3G parts / liter) added to the dyeing solution (the amount of the test agent is a quarter of the dyeing solution) is evenly stirred, the resulting mixture is poured into a Roller dye press, and then the cotton fabric is passed After the roller is dyed, it is rolled into a shaft shape. This form of cotton fabric was stored at room temperature for 4 hours. After that, the obtained blue dye is first washed with cold water, washed with boiling hot water for 1 minute, and then soaped with boiling non-ionic detergent for 10 minutes, then washed once with cold water, and dried. The blue-red dye has excellent properties. Example 2 9 8 Take 0.25 parts of the dye of the formula (2) prepared in Example 2 dissolved in 25 ml of water, referred to as mother liquor (0.1%), and take 4 ml of 〇·1% mother liquor in a dyeing bottle. 2 cotton fabrics, then add 2 · 4 parts of thenardite, then add 2 2 5 ml of soda ash solution; put the dyeing bottle into a 6 〇t horizontal shake dyeing machine, and keep it for 60 minutes. After that, the obtained blue dye is first washed with cold water, washed with boiling hot water for 1 minute, and then boiled with boiling non-ionic detergent for 1 minute, then washed once with cold water and dried. The resulting blue-red dye has excellent properties. 55 The paper size is applicable to China National Standard (CNS) Α4 specification (210X297 mm), can be-------- (please read the notes on the back and fill in the fields on this page) A7 B7 1301501 V. Invention Description (52) Example 299 Take 0.25 parts of the dye of the formula (3 5) prepared in Example 35 dissolved in 250 ml of water, referred to as mother liquor (0 · 1 %) 'take 〇 · 1 % mother liquor 4 〇 ml in a dyeing bottle Put 2 parts of cotton fabric, then add 2 · 4 parts of thenardite, then add 2.5 ml of 32% pure test solution; put the dyeing bottle into 60 ° C horizontal shock dyeing machine, keep warm for 60 minutes. Thereafter, the obtained blue dye was first washed with cold water, washed by boiling hot water for 10 minutes, and then boiled with a boiling nonionic detergent for 10 minutes, washed again with cold water, and dried. The resulting blue-red dye has excellent properties. Example 300 0.25 parts of the dye of the formula (77) prepared in Example 77 was dissolved in 25 ml of water, referred to as mother liquor (0.1%), and 4 ml of H% mother liquor was placed in a dyeing bottle, and 2 parts of cotton fabric was placed. Then add 2·4 parts of thenardite, then add 2·5 ml of 3 2% soda ash solution; put the dyeing bottle into 6 (rc horizontal shake dyeing machine, keep it for 60 minutes. After that, get blue dye first After washing in cold water, it is washed with boiling hot water for 10 minutes, soaped with boiling non-ionic detergent for 1 minute, then washed once with cold water, and dried. The obtained blue red dye has excellent characteristics. 1 Take 25 parts of the dye of formula (119) prepared in Example U9 dissolved in 25 liters of water, called mother liquor (0.1%), take 〇·1% mother liquor 40 ml in dyed dad bottle, put Add 2 copies of cotton fabric, then add 24 4 thenardite, then (please read the notes on the back and fill in the fields on this page) • m ^^1 _^ϋ ^^1 mmmat —ϋ ^^1 ϋ— J ··· ι_1 *1 ^^1 ϋ« 11 ^^1 , ν 一口 · 56 1301501 A7 B7 V. Description of invention (53 ) 32 ml of 32% soda solution; put the dye bottle into 6〇χ: the horizontal shock steam In the machine, keep warm for 60 minutes. After that, 'the blue dye obtained is first cooled: washed' by boiling hot water for 1 minute, washed by Fo Teng's non-ionic detergent for 1 minute' and then washed once with cold water. The obtained blue red dye has excellent characteristics. 'Example 3 02 0.25 parts of the dye of the formula (194) prepared in the example 194 is dissolved in 25 ml of water, referred to as mother liquor (0% by weight), 1 1% mother liquor 4 () ml in a Bi-color bottle, put 2 cotton fabrics, then add 24 4 Glauber's salt, then: into the 32% pure test solution 2.5 ml; put the dye bottle into the human (four) horizontal earthquake In the μ color machine, 'insulate for 60 minutes. After that, the blue dye obtained is washed with cold water, washed with hot water for 1 minute, and boiled with non-ionic detergent: wash for 1 minute, then rinse with cold water - times The dried blue red dye has excellent properties. Example 303 0.25 parts of the dye of the formula (269) prepared in Example 269 is dissolved in 25 ml of water, which is called mother liquor (0.1%), and is taken as 0. 〇/〇 mother liquor, pen 邛, night 4 〇耄 染色 in dyed open tile, put 2 pieces of cotton fabric, then put 2 4 w dead Then add 2·5 ml of 32% soda solution; put the dyeing bottle and DUC level to shake the dyeing machine, and keep it for 60 minutes. After that, the obtained e ώ will be washed with cold water and then boiled. After washing for 10 minutes, it is boiled by non-1Λ ν _ non-ionic detergent soap and washed with cold water. The prepared blue-red paper size is applicable to China National Standard (CNS) Α4 specification (210X297 mm). C Please read the precautions on the back and fill in the details on this page. 叮, 叮β 1301501 5. Inventions (54) The dyes have excellent characteristics and are considered to be 疋' The above are only examples, not limited. example. For example, if you are away from the basics of the invention, j, Ge claims the scope of rights, and should be based on the scope of the patent application... This paper is applicable to the Chinese National Standard (CNS) A4 specification (210X297 mm) for this paper size. -------· (Please read the notes on the back and fill in the fields on this page)

Claims (1)

1301501 No. 91124096 'April 1997 Amendment Page Less A8 Sixth, the scope of application for patents Single azo anti-13⁄4 red dye II of the following formula (I) NH—r^Nvs>—NDZ ά. Γκ'3 Ύ X where X is -NHCN, _〇Η, _SCH2C00H, _NHS02CH3, 3-carboxy σ ratio (3-carb〇xypyriciinium), one ship 02—(3 Or halogen; D is a benzene ring or a naphthalene ring having up to 3 substituents selected from the group consisting of _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ _ , hydroxy, carboxyl, phosphoric acid and sulfonic acid groups; ζ is -S〇rCH = CH2 or -S02-CH2-CH2-U; U is -oso3h, ci or Br ...op〇3H2, H 〇. ^ ^^ COOH R2 is a acid group or a carboxyl group; η is 0 or 1; when X is a halogen atom, then R1 is a hydrogen atom and R3 is a Ci-4 alkyl group or a cle4 alkyl group having at least one substituent; Is -NHCN, _〇H, -SCH2C〇〇H, -NHS02CH3, 3-Weicarb bite (3-Carb〇xypyridinium) or ------------Φ-I Pack--- ------Set ------"β® line · Please read the back note first and then fill in the columns on this page 59 1301501 A8 B8 C8 D8 VI. Patent application scope - nhso2—^ y — And Ri and R3 are independently selected from the group consisting of hydrogenogen so3h, C!-4 alkyl, phenyl, or have 1 Or a plurality of substituents of a mountain alkyl group, the substituents are respectively selected from the group consisting of: a hydroxyl group, a carboxyl group, a sulfonate group, an carbamoyl group or a methoxy group. Carbonyl (meth〇xy carb〇nyl). 2. Single-azo reactive red dyeing according to the scope of the patent application, where X is -NHCN, 3-carboxypyridine, chlorine atom or fluorine raw material. The single-reactive red dye of the patent is deleted, wherein D is a benzene ring having up to 3 substituents. 4. The single azo coating reactive red dyeing according to item i of the patent application range wherein the Z system is - S02-CH = CH2 or -S02_CH2-CH2-0S03H 〇5 · as claimed in the patent item range i, wherein the η system is the early gas reactive red dye 6 • as claimed in the patent range... When X is a chlorine atom or a fluorine atom, R2 is a Cl.4 alkyl group. The shell k is a hydrogen atom and 7 · as claimed in the first item of the patent scope, the towel is XS-NHCN, ^ ^Reactive red dyeing, -SCH2C00H, -NHS〇2CH3, 3_carboxypyridine or -, then the Ri and r3 inter-materials are applicable to the Chinese national standard. (CNS) A4 specification (210x297 public sauce, please read the back of the note first and then fill in the columns of this page « I ϋ-i I · Memmt n ϋ - n ϋ · 3⁄43⁄4r mouth 1301501 VI. Shen Yu patent scope is independent It is selected from a hydrogen atom or a phenotypic group. n=n (HO3S)/ NHR1 material, 1·::^:; the single azo reactive red dyeing of the first item H03S is a reactive dye of the following formula (Ia), so3h ΝΗ~^ΝΎΎ A D-Z R3 X where (la) x is -NHCN, 〇H, -SCH2C〇〇H, 丽S02CH3, 3-carboxypyridine (3 ( rb〇xypyridinium), —NHS〇2 y ^^ Or halogen; D is a fluorene or naphthalene ring having from o to 3 substituents selected from the group consisting of: halooctyl, Γ ^ ^ ̄ ̄® normal alkyl, Cl 4 alkoxy, nitrate a group of an amino group, an amino group, a hydroxyl group, a carboxyl group, a phosphoric acid group and a sulfonic acid group; z is -S〇2_ch=CH2 4_s〇2_CH2_ch2 u ; u is -0S03H, Cl or Br, ·ΟΡ〇3Η2, _Ss〇3 ςΝ]; ^^COOH η is 0 or 1; when field X is a halogen atom, then R1 is a hydrogen atom and R3 is a C^4 alkyl group or a Ci "alkyl group" having at least i substituents, and field X is _NHCN , -OH, _SCH2C〇〇ii, 61 1301501 A8 B8 C8 D8 VI. Patent application scope - nhso2ch3 - NHS〇2 - ^ ^ 3_ carboxypyridine (3_carb〇xypy]ridinium) or R, R3 and R3 are independent of each other It is selected from the group consisting of a hydrogen atom so3h, a Cb4 alkyl group, a phenyl group, or a C^4 alkyl group having one or more substituents selected from the group consisting of: a hydroxyl group, Carboxy, sulfonate 'carbamoyl or meth〇Xy carbonyl. 9 · Single azo reactive red dyeing according to item 8 of the patent application X is -NHCN, 3-carboxyacridine, chlorine atom or fluorine raw material. 10. Single-azo reactive red dyeing according to item 8 of the patent application, wherein D is a benzene ring having 〇 to 3 substituents. 11. The single azo reactive red dyeing according to item 8 of the patent application scope, wherein the Z system is _s〇2-CH = CH2 or -S〇2-CH2-CH2_〇s〇3H. 12·If the patent application scope The monoazo reactive red material of item 8, wherein the II system is 1. ', 13. The monoazo reactive red dye according to item 8 of the patent application, wherein when X is a chlorine atom or a fluorine atom, Ri is hydrogen: R3 is c1-4 alkyl. 14. The monoazo reactive red material of claim 8 wherein X is _NHCN, _〇H, -SCH2C〇〇H, -NHSO2CH3 > 3 ^ ^ _ras〇2^T^ ^ 3-carboxypyridine or ^^, then 1 and the core material 0- I 衣衣 Please read the notes on the back and then fill in the fields on this page - * —I—一^------- #口 . ,d 1301501 A8 B8 C8 D8 6. The scope of application for patents is independently selected from a hydrogen atom or a c i _4 alkyl group. 15. If you apply for a patent (four)! The monoazo reactive red dye of the formula wherein the formula (I) is a reactive dye of the following formula (Ib), ~Γ\ Ζ X is _NHCN, _〇H, -SCH2CO〇H, _NHS02CH3, 3- Carboxypyridine (3-carboxypyridinium), —NHS〇2—(( \ or halogen; Ζ is -S〇2_CH = CH2 or _S02-CH2-CH2-U; U is -OSO3H, C1 or Br; η is 〇 or 1 ; When X is a halogen atom, then R i is a hydrogen atom and r 3 is a C ^ 4 alkyl group; when X is -NHCN, -OH, -SCH2COOH, -NHS02CH3, 3-carboxypyridinium Or -NHS〇2—(!\w, then R! and R3 are independently selected from the group consisting of a hydrogen atom, a Ci-4 alkyl group or a Ci 4 alkyl group having one or more substituents, 63 I The paper scale exceeds the Chinese National Standard (CNS) A4 specification (210><297 metric tons)---β-I loading---------booking ------ line! Please read the back first Note: Please fill in the columns of this page '1/ • k \,- 1301501 B8 C8 D8 J\ Patent Application Scope The substituents are selected from the group consisting of: hydroxy (hydr〇xyl), carboxyl (carboxyl), sulfonic acid groups. (sulf〇), carbam〇yl or A methoxy carbonyl. 16. A monoazo reactive red dye according to claim 15 wherein X is _NHCN, 3-carboxypyridine, chlorine or a fluorine atom. The monoazo reactive red dye of claim 15 wherein Z is -S02-CH2-CH2-0!SC)3H. 18. The monoazo reactive red dye of claim 15 The η system is 1. 19. The mono-radical reactive red dye as described in claim 15 wherein when X is a gas atom or a fluorine atom, then Ri is a gas atom and R3 is a sulfhydryl group or an ethyl group. 20. The monoazo reactive red material according to item 15 of the patent application, wherein X is -nhcn, -_0H, _scH2eQQH, -NHS02CH3, 3-carboxypyridine or -3 is independently selected from the group consisting of hydrogen atoms and cesium, respectively. Base or ethyl • such as f, please patent _ Item 15 of the single-element reactive material' (Formula (10) is a reactive dye of the following formula (M). Please read the back of the note first and then fill in the pages of each page « i^i · *ι_ϋ ϋ—i^ii^i —.1 Hi 1_1 I r · 11 —.1 n_i Hi na 3⁄43⁄4r port, then Ri and r3 ^ 64 Paper scale applicable Chinese National Standard (CNS) MW ^ j2m29T ^ • h 1301501 A8 B8 C8 D8 six patented range NH- VY 丫 n c2h; So2ch2ch2oso3h Cl I]) 22 · As described in the patent application No. 5, wherein the formula (lb) is a reactive dye of the following argon-reactive red dyeing type 2). Please read the notes on the back and fill in the fields on this page. NH- \ Ν Η γ η ^^ S02CH2CH20S03H COCT i strong clothing --------- set------- 1-2 23. Such as the two patents Fan Park No. 15 material, which (lb) is a reactive α of the formula (I-3), such as γ φ , azo-reactive red, dye-line! The Chinese National Standard (CNS) is applicable to the scale of the 纰 Α 4 "-One 1 So2ch2ch2oso3h 1301501 VI. Application for patent scope (1-3) 24 · For example, the first azo-reactive red dye of the first aspect of the patent, the formula (lb) is a reactive dye of the following formula 「 "eight (1-4). Please read the notes on the back and fill in the fields on this page. So2ch2ch2oso3h 1-4 25· As claimed in the patent application, i.e., the formula (lb) is a reactive dye of the following mono-azo reactive red dyeing formula U·5). CNS ) A4; 66 (21〇><2974 1301501 A8 B8 C8 D8 VIII. Patent application scope So2ch2ch2oso3h (1-5) 26. As claimed in claim 15, wherein the formula UbMM is a reactive dye of the formula (1-6). Color dyeing So2ch2ch2oso3h (1-6), -9, 胄A 3 a fibrous material having a hydroxyl group or an amino compound group = 3 printing method, which comprises using an aqueous solution of an early azo-reactive red dye as in the first aspect of the patent application Fiber material. 28. The method of claim 27 is cotton. Among them, fiber material---------#丨壮衣---------订-------Φ00! Read the back of the note and fill out this page g Τ^)Α4^ Τ(Τΐ〇><297^ Ja.