TW201009027A - Novel bis-reactive dye with N, N-dialkylamino bridge group - Google Patents

Abstract

The present invention relates to a novel bis-reactive dye with N, N-dialkylamino bridge group, represented by the following formula (I): wherein E1, E2, R, R1, R2, R3, R4, R5, R6, G, G', B, B', X, m, and n are defined the same as the specification. The bis-reactive dye of the present invention is suitable for exhaust dyeing, cold pad batch, continuous dyeing, printing and digital spray printing materials that contain hydroxyl group or polyamine fibers.

Description

201009027 IX. Description of the invention: [Technical field to which the invention pertains] The present invention relates to a novel reactive dye which is a bridging group of a #-dialkylamino group (A^, iV-dialkylamino), especially one suitable for hydrogen-containing A new reactive dye for the dyeing, cold dyeing, continuous dyeing, printing and digital printing of oxy and polyamine fibers.

10 15 [Prior Art] The azo dye is a pigment precursor composed of a diazo component and an even component. It is widely used because of its wide color gamut and high molecular absorption coefficient. It is used as a dark dyeing agent such as orange, red, navy, and black. The pigment precursor of the reactive dye used. Among the azo dyes, CI Reactive Black 5, which is a naphtha reactive dye developed by Hoechst in Germany in 1957, is the most famous. Its structure is as follows. Formula (A), and such a dye can dye the fabric to a very dark color.

Fiber-reactive dyes have been used in the dyeing and finishing industry for many years. Today, the development of reactive dyes is oriented towards economics with higher fixation and higher dyeing. In order to surpass the high-durability and economical characteristics of CI Reactive Black 5, many teams have been engaged in research and development over the years. For example, Hoyer St. Hoyer et al., 1980, published in US Pat. No. 4,244,258, 5 20 201009027 sulfonyl is a bridge-based Tetraazo structure in which the dye can be as shown in formula (B).

5 1997 CIBA Geigy's Tzikas et al. in the US patent case US

A tetrazo structure having an amine Daichi (311^11〇.&]'1)〇11}4) or an aminesulfonyl group as a bridging group is disclosed in Pat. No. 5,629,410. (C) is shown.

However, the new compounds developed by the above research team are still unable to meet market requirements due to their dyeing depth, hue shift, leveling and washing fastness, so there is an urgent need for improvement. 6 201009027 [Summary of the Invention] 5 Through a multi-party research experiment, it was found that a new compound containing a ruthenium, αΓ-dialkylamino bridge group (shown by the following formula (D)) and a ruthenium, #-dialkylamino bridge group were synthesized. The technology is applied to reactive dyes, and a series of novel structures such as yellow, orange, red, navy, and black can be synthesized to exhibit high color, high fixation, stable fiber and dye bonding, and excellent fastness characteristics. (R2)0*3

(Rl)〇-3

R B—(CH2)m—N—(CH2>n-Β·- -νη2 (9) 10

Accordingly, the present invention provides a novel reactive dye structure having a novel dialkylamine group as a bridging group, and the cellulose dye fiber dyed by the reactive dye can exhibit good fixation rate, excellent dyeing property, and has excellent properties. Wash fastness and wet fastness characteristics. The novel reactive dye having a dialkylamino bridging group of the present invention has the following structural formula: (I):

B—(GH2)m—N- (CH2)n—B*

(^2) 0-3

X (i) where,

Ei and E2 are each independently selected from a substituted or unsubstituted phenyl group structure, a substituted or unsubstituted naphthalene group structure, and a substituted or unsubstituted monoazo Group 201009027 (monoazo group) structure group; R is hydrogen, Ci_4 alkyl, Ci_4 alkylcarbonyl, phenyl, nitroso, or substituted C-4 alkane a group, wherein the substituent is selected from the group consisting of a halogen, a hydroxy group, a carboxyl group, a 5 or a sulfo group; (Ri)o-3 and (R2) 〇_3 is 0 to 3 identical or different substituents, and each is independently selected from the group consisting of hydrogen, halogen, hydroxy, carboxyl, sulfonic acid, nitro (nitr), cyano, Cw alkyl, c 1-4 a group consisting of alkoxy, ureido, and amido; 10 R3 and 4 are each independently hydrogen or Cw alkyl;

Rs and Re are each independently hydrogen, Cl_4 alkyl or benzene ring;

Or a group of unsubstituted C丨.4 alkyl groups; (Do-3 is 0 to 3 identical or different substituents, and each independently selects 15 free hydrogen, halogen, hydroxyl, carboxyl, sulfonic acid Base, nitro, cyano, ei_4 ® alkyl, Ci-4 alkoxy, ureido or amine; B and B' are each independently selected from linear, -S〇2- and -CONH-(CH2)k -S02- group; k is an integer of 1, 2, 3, 4, 5 or 6; C0NH-(CH2)d-S02-U, 0-thiosulfate (β-thiosulfatoethylsulfonyl), _R,- S〇2-U ruler ' is Cm alkyl or phenyl; 20 Q is -S02-U, 〇(CH2)_ thiosulfate sulfonyl L'-S02-U or -R'-U'; 8 201009027 d and r are each independently an integer of 2, 3 or 4; U is -CH2CH2W or -CH=CH2; W is -Cl, -0S03H, -OP03H, quaternary ammonium, ° bite ( Pyridine), carboxypyridinium, methylpyridinium, carboamine ί8

—N-C2H4SO3H I base 0 is more than carbonamidopyridinium, or ~;

Rs and R9 are each independently hydrogen or C!_4 alkyl;

10 15 ❷ U' is α,; ί3·α,β-halopropionyl, α-haloacryloyl, β-halopropionyl, or α- Alpha-haloacryloyl; X is a function, and m and η are each independently an integer of 2, 3 or 4. In the reactive dye of the formula (I) of the present invention, wherein Ε! and Ε2 may each independently be a substituted or unsubstituted phenyl group structure, preferably a structure of the following formula (* indicates a coupling position): s 〇3h

(1-1) wherein * is a coupling position, R10 is hydrogen, a Ci_4 alkyl group, a C2_4 alkanoic acid group, or a Cm alkyl group substituted with a substituent, and the substituent is a hydroxyl group, a 20 gas group, a mercapto group , acid group, methoxycarbonyl, ethoxycarbonyl, or acetoxy. 201009027 In the reactive dye of the formula (I) of the present invention, wherein Ei*E2 may each independently be a substituted or unsubstituted naphthyl group structure, preferably a structure of the following formula (* represents a coupling position):

OH

5

In the reactive dye of the formula (I) of the present invention, wherein Ei* E2 may each independently be a substituted or unsubstituted monoazo group structure, preferably a structure of the following formula (* indicates a coupling position):

10

201009027

(1-5). For the convenience of description, in the specification, the compounds are all expressed in the form of free acid, but the dye in the present invention is often used in the form of a water-soluble salt when it is manufactured or used, and the suitable salt may be an alkali metal or an alkaline earth. A metal, ammonium salt or organic amine salt, preferably a sodium salt, a potassium salt, a lithium salt, a money salt or a triethanolamine salt. The dye of the present invention can be prepared by a known method, and the reaction sequence of the preparation thereof is not strictly limited, and the chromophore can be prepared first, and then the dye required for the synthesis can be synthesized; or the dye preparation process can be carried out. In the middle, the chromophore is synthesized. The dyes of the present invention are suitable for use in the dyeing or printing of fibrous materials, especially cellulosic fibrous materials, and fibrous materials comprising cellulosic fibers. The fiber material is not particularly limited, and may be natural or regenerated cellulose fibers, such as cotton, hemp, linen, hemp, sesame, mucus snails, or fiber materials containing cellulose fibers. The dyes of the invention are also suitable for dyeing and printing of fiber blended fabrics containing hydroxyl fibers. The dyes of the present invention can be fixed to the fibers in a variety of ways, particularly in the form of aqueous dye solutions and printing pastes. Dyeing and printing are carried out by means of dip dyeing, continuous dyeing, cold pressing, 20 printing and digital printing. The dyeing or printing of the present invention can be carried out according to a conventionally known and conventional method, wherein the exhaust dyeing method is a well-known inorganic neutral 11 201009027 salt (such as anhydrous sodium sulfate and sodium carbonate) and a well-known acid binder. (such as sodium carbonate, sodium hydroxide) used alone or in combination. The amount of inorganic neutral salts and bases is not critical, and inorganic neutral salts and bases can be added to the dye bath once or in divided portions by conventional methods. In addition, it is also possible to add a dyeing aid (such as a leveling agent, a 5 retarder, etc.) according to a conventional method, and the dyeing temperature is usually 4 (rc_9 (rc, preferably 50 〇C-70 〇C. The dyeing method is to dye the substance to be dyed, using well-known inorganic neutral salts (such as anhydrous sodium sulfate and sodium hydride) and well-known acid binders (such as (four) sodium, nitrogen 10 15 20 sodium oxide), and then The resulting material is dyed in a coil form at room temperature. The continuous dyeing method is to mix a well-known acid binder (such as sodium carbonate or sodium carbonate) with a padding solution, and the dye to be dyed is carried out according to a usual method. The dyeing process makes the obtained material dry or steam-solidified. The grain-pressing method is carried out by padding with _=color material and then treated with a well-known inorganic neutral salt (such as sodium sulphate). The method of drying or steaming solid fabric printing of the treated material, for example: ih ^ ^ ^ ^ deuteration method, which is a printing paste containing a well-known acid such as money, printed on the (4) (four), dry or K Steam-solid color; the two-phase printing method contains a substance, and the obtained substance is immersed in a colloidalized material (such as a gasified sodium) and a well-known acid. ^ ^ Fixation in neutral salt solution. The method according to the invention, such as gas oxidation or carbonation, is not limited to the dyeing or printing method of the preceding column. [Embodiment] 12 201009027 For the convenience of further explanation, The following examples are given to illustrate the invention in more detail. The following examples illustrate the invention, and the scope of the invention is not limited thereby, wherein the compound is expressed in the form of a free acid, but the actual form may be metal. The salt, more likely an alkali metal salt, 5 especially a sodium salt, unless otherwise stated, the parts or percentages used in the examples are in units of weight and the temperature is in degrees Celsius, C. Example 1 14.05 parts of p-aminostyrene sulfone dissolved in 50 parts of water, temperature control 10 in 0~5 °c, after adding 45% NaOH aqueous solution, stirring for a while and then adding 2 parts of 40% methylamine (methylamine), in the room The reaction was carried out for 4 hours under temperature, and the precipitate was filtered and dried to obtain a product structure of the formula (1).

So2ch2ch2— N-H2 ch3 ch2co2s

Nh2 (l) 15 Example 2 Dilute 16 parts of o-aminophenyl sulfonyl vinyl sulfone (OAVS) dissolved in 60 parts of water, the temperature is controlled at 0~5 ° C, add 45% NaOH aqueous solution, stir for a while Further, 2 parts of 40% methylamine was added, and the mixture was reacted at room temperature for 4 hours to obtain a product structure of the formula (2). 20 CH30- h2n '\—so2ch2ch2—n-ch2ch2o2s ^ CH3

Och3 nh2 (2) 13 201009027 Example 3 Take 28.1 parts of p-aminostyrene sulfone dissolved in 100 parts of water, the temperature is controlled at 0~5 ° C, add 45% NaOH aqueous solution, stir for a while and then add 3 parts of ethanolamine (ethanolamine), the reaction is carried out at room temperature, and after the completion of the reaction, it is precipitated and dried to give a product structure of the formula (3).

So2ch2ch2—n-ch2ch2o2s ch2ch2oh

Nh2 (3)

10 Example 4 Take 14.05 parts of p-aminostyrene sulfone dissolved in 50 parts of water, the temperature is controlled at 0~5 ° C, add 45% NaOH aqueous solution, stir for a while and then add 4 parts of 40% guanamine, in the room After reacting for 4 hours at a temperature, an aqueous solution of 16 parts of anthranilyl vinyl hydrazine which was vinylated at a low temperature was further added thereto, and the temperature was controlled at room temperature, and stirred for a while to obtain a product structure of the formula (4).

(4) Example 5 (a) First, 9.4 parts of 1,3-phenyl-p-phenylenediamine-4-sulfonic acid (M4 acid) was dissolved, and then dripped 9 to 5 parts of a cyanuric chloride ice dispersion was added, the temperature was controlled at 0 to 5 ° C, and the reaction was carried out for 1 hour. After filtration, the filtrate was taken. The pH was adjusted to neutrality, and 3.59 parts of sodium nitrite water-soluble 14 20 201009027 solution and 19 parts of 32% hydrochloric acid aqueous solution were added, and the diazotization was controlled at 0 to 5 ° C, and the reaction was completed in about 2 hours. (b) Dissolve 16 parts of 1-Chaoling-8-amino-3,6-disulfonic acid (H-acid) with liquid test 5 Thereafter, the solution was added dropwise to the aqueous solution obtained in the above (a), and after reacting for a while, 14 parts of 4-(P-sulfatoethylsulfone) aniline (PASE) was added, and the pH was adjusted to 3 with a 15% aqueous sodium carbonate solution. ~5, react 2 hours standby. (c) Add 30 parts of water to 2 parts of the compound of formula (1) and 3 parts of 32% hydrochloric acid water 10 and stir well, then add 0.76 parts of sodium nitrite solution dropwise, and control to carry out weight at 0~5 °C. Nitriding, the reaction is completed in about 1 hour. (d) The aqueous solution obtained by betting (b) is added to the solution (c) for coupling reaction, and the pH is adjusted to 5~7 with 15% sodium carbonate aqueous solution. After 4 hours of reaction, it is taken out by a salting-out method to obtain blue. The product is structured as follows:

SO2CH2CH2——nch3 (5) Example 6 20 (a) After dissolving 9.4 parts of M4 acid, add 9.5 parts of trimeric cyanide ice dispersion, the temperature is controlled at 0~5 °C, reaction 1 After the hour, the filtrate was taken after filtration. The pH was adjusted to neutrality, and 3.59 parts of an aqueous solution of sodium nitrite and 19 parts of a 32% aqueous solution of hydrochloric acid were added to control diazotization at 0 to 5 ° C, and the reaction was completed in about 2 hours. 15 201009027 (b) After diluting 16 parts of H acid with liquid alkali, it is added dropwise to the aqueous solution obtained in the above (a), and after reacting for a while, 14 parts of p-aminostyrene oxime (PASE) is added to 15% carbonic acid. The sodium aqueous solution was adjusted to pH = 3 to 5, and the reaction was allowed to stand for 2 hours. 5 (c) Take 30 parts of water, add 14 parts of the compound of formula (2) and 8 parts of 32% aqueous hydrochloric acid, stir well, then add 0.7 parts of sodium nitrite solution dropwise, and control the diazonium at 5~10 °C. The reaction was completed in about 1 hour. (d) The aqueous solution obtained in (b) is added to the solution (c) for coupling reaction, and the pH is adjusted to 5 to 7 with 10 15% aqueous sodium carbonate solution. After 4 hours of reaction, it is taken out by general salting out to obtain a blue product. The structure is as follows:

(6) Example 7 15 (a) First, 1.73 parts of m-aminobenzenesulfonic acid (capric acid) was dissolved in 15% aqueous sodium carbonate solution, and added dropwise to 1.86 parts of cyanuric acid cyanide dispersion to 15 % sodium carbonate aqueous solution was adjusted to ρ Η = 3.5 to 4, the temperature was controlled at 5 to 10 ° C, and the reaction was carried out for 2 hours. After filtration, the filtrate was taken for use. (b) After dissolving 3.19 parts of citric acid with a liquid alkali, adding the 20 aqueous solution obtained in the above (a) dropwise, adjusting the pH of the reaction liquid to 3 to 4 with sodium argon carbonate powder, and controlling the temperature at 15 to 20 At °C, an aqueous solution was obtained after 4 hours of reaction. (c) Take 20 parts of water and add 2.14 parts of the compound of formula (3) and 2.5 parts of 32% of salt 16 201009027 acid aqueous solution, stir well, then quickly add 76·76 parts of sodium nitrite aqueous solution, control at 〇~5°c Diazotization is carried out, the reaction is completed in about 5 hours, and the aqueous solution obtained in the above (b) is added, and the pH of the reaction is adjusted to 6 to 7 with sodium hydrogencarbonate powder. After 3 hours of reaction, it is taken out by general salting out to obtain red. The product is structured as follows:

Ίο

(a) First, 3.19 parts of citric acid is dissolved in liquid alkali by adding 'drops to l86 parts of trimeric cyanide ice dispersion'. The pH is adjusted with sodium bicarbonate powder, and the temperature is controlled at 8~1 (TC, reaction 2 After the filtration, the filtrate was taken for use after the filtration. (b) 20 parts of water was added to add 2.14 parts of the compound of the formula (3) and 2.5 parts of a 32% aqueous solution of hydrochloric acid to fully mix and disperse ', and then rapidly add Ο.% of the aqueous solution of sodium nitrite to control Diazotization is carried out at 0 to 5 ° C, and the reaction is completed in about 5 hours. The filtrate obtained in the above (a) is added, and the pH of the reaction is slowly adjusted to 5 to 7 with sodium hydrogencarbonate powder. After 3 hours of reaction, a red product is obtained. (c) After 1.41, the amino acid is diluted with 5% (MASE) and dissolved in 5% aqueous solution of sodium carbonate, and then quickly added to the aqueous solution obtained in (b) above, sodium bicarbonate at 35~40 °C. The powder adjusts the pH of the reaction solution to between 5 and 7 'after 4 hours of reaction, a red product is obtained, and the structure is as follows: 17 20 201009027

h〇3S〇h4c2〇2S

P_NH

Cl HO3S

-NH OH

N=N—SO2C2H4-

-NCH2CH2OH

SO3H (8) Example 9 (a) First, 2.6 parts of N-(5-amino-2-sulfonic acid phenyl)-/9-alanine (CEM4) 5 acid was dissolved in a 15% aqueous sodium carbonate solution. 1.86 parts of the trimeric cyanide ice dispersion was added, the temperature was controlled at 5 to 10 ° C, and the reaction was carried out for 2 hours, and φ was obtained as an aqueous solution.

(b) After dissolving 2.81 parts of p-aminostyrene sulfone with a liquid base, it is quickly added to the aqueous solution obtained in the above (a), and the pH value is adjusted to 3 to 5 with sodium hydrogencarbonate powder, and the temperature is controlled at 30~ Between 35 ° C, an aqueous solution was obtained after the reaction overnight. (c) Take 20 parts of water and add 2.14 parts of the compound of formula (3) and 2.5 parts of 32% aqueous hydrochloric acid to fully disperse and disperse, then quickly add 0.76 parts of sodium sulfoxide aqueous solution, and control the weight at 0~5 °C. Nitriding, the reaction is completed in about 1.5 15 hours, added to the aqueous solution obtained in the above (b), and the pH of the reaction solution is adjusted to 5 to 7 with sodium hydrogencarbonate powder. After 4 hours of reaction, a yellow product can be obtained, and the structure is as follows:

N=N-h^ ^―: S〇2C2H4-

-NC2H4OH (9) 20 Example 10 18 201009027 (a) First, 2.39 parts of 2-Amino-5-naphthol-7-sulfonic acid (J acid) The solution was dissolved, and 1.9 parts of the trimeric cyanide ice dispersion was added dropwise, and the pH was adjusted to 1 to 3 with a 15% sodium carbonate aqueous solution, the temperature was controlled at 5 to 10 ° C, and the reverse 5 was 1.5 hours. The filtrate is ready for use. (b) After dissolving 2.8 parts of p-aminostyrene sulfone (PASE) with a liquid base, it is quickly added to the aqueous solution obtained in the above (a), and the pH is adjusted to 3 to 5 with a 15% aqueous sodium carbonate solution, and the temperature is controlled. Between 30 and 35 ° C, an aqueous solution was obtained after the reaction overnight. 10 (c) Take 30 parts of water, add 2 parts of the compound of formula (2) and 3 parts of 32% aqueous hydrochloric acid, stir well, then add 0.7 parts of sodium nitrite solution dropwise, and control the diazonium at 5~10 °C. The reaction was completed in about 1 hour. (d) The aqueous solution obtained in (b) is added to the solution (c) for coupling reaction, and the pH is adjusted to 5 to 7 with 15 15% aqueous sodium carbonate solution. After 4 hours of reaction, it is taken out by general salting out to obtain a yellow product. The structure is as follows:

Examples 11 to 44 (10) Referring to the synthesis of Examples 5 to 10, the reactive dyes of the formulae (11) to (44) in Table 1 using a dialkylamine as a bridging group were obtained. Table 1 19 20 201009027 Example Dye structure type Hue 11 12 HO3SH4C2HN-γ-ΗΝ ν^ν h〇3S'hC5_

OH

^-N=N SO3H Ο SO2C2H4 -nch3 Orange

Cl

COOH (ii)

SO2C2H4-ch3

-NCH2CH2OH red 13

Cl

1 3 N yhn Wch3 NYN

SO2C2H4- •NCH3 Orange 14 15 H2N-|^NvfpHN—(v y)—N=N—^ y-N=N_C λ>—SO2C2H4- ΝγΝ -ci

H03S H03S

(14) •nch3 brown C2H5

-NH OH T.J00C-0 SO2C2H4- -NCH3 Red

H03S' v v, s〇3H(15) OH ch3 Ν'

I HO3SOH4C2O2SH4C2 — N v,j|~ N,N 丫SO3H SO3H Cl N=N— SO2C2H4- -nch3 Scarlet 20 (16) 16 201009027 17 18 HO3SOH4C2O2SH4C2- OH^VHNrx^rc γ T03H , Cl SO3H SO2C2H4- -nch3 Scarlet (17) 92HS· so3h HO3SOH4C2O2S—^ ''jj-HN—^ N=N nyn Cl ^n^t_n=n_{3_s〇2C2H4' (18) Red

-NC2H4OH

19 20 21

* HN—HN—^ ^—N=N NYN HsN

N=N—f SO2C2H4 OH (19)

-NC2H4OH Red OCH3

0^hn-0-hN^ H〇3SOH4C2〇2S T

S03H

N=N H2N

SO3H N=N—f x)-S〇2〇2H4 (20)

SO3H

-NC2H4OH red

22 H03S0H1C202S^ NYN 〇H H3CO’

HO3SOH4C2O2S

SO2C2H4-

-NC2H4OH Red (21) S03H -HN-^Nv|pHN <]T- Y H2M Cl

N=N -^^YS〇3H 1^\^-Ν=Ν_ OH SO2C2H4-

-NC2H4OH Red 21 (22) 201009027 23 24 HO3SOH4C2O2SH4C2 OH ".&νΗΝ^ϋ li, III sc^h SO2C2H4- ci (23) HOs^ v v, S〇3H(24)

-NCH2CH2OH Scarlet -nch2ch2〇h Red

25

H2N—^HN—^ N=N-Y p H03s H03S

n=n—SO2C2H4- -nch2ch2oh Color (25) 26 丫 Cl

HO3SOH4C2O2S—HN—^Nvjp HN

H03S H03S

S02C2H4-

-NCH2CH20H Brown (26)

SO3H HO3SOH4C2O2S—^ HN—^N^|pHN 27 丫 Cl

H03S H03s

S02C2H4-

-NCH2CH20H plucking color (27)

28 29 HO3SOH4C2O2S- /SOaH Bu hnW ΝγΝ

HO3S HO3S

SO2C2H4- color (28)

HO3SOH4C2O2S

H03S H03s

S02C2H4- -nch3 brown (29) 22 201009027 30

HO3SOH4C2O2S

Sweeping color HO3SOH2CH2C1 31 32

Il SO3H nh2 oh

-N=N- HO3S (31) nh2 oh H〇3SOH2CH2〇〇2S~~HN—N=N—S〇2CH2CH2- S〇2CH2CH2--nch3 -nch3 blue blue

(32)

H03SOH2CH2CI 33 35

HO3SOH2CH2D

SCbH:0^HNtVHN'Crl Cl s<^ (33) X s〇3H (34)'"ζνχτ1 SO3H (35) HO3SOH2CH2CO2S-d /-HN- nh2 oh

HQaS nh2 oh

H03S nh2 oh h3oc, n=n-r^Sr^t-N^N-

^ SO3H H〇aS S〇2CH2CH2--NCH2CH2OH a 2 Blue S02CH2CH2- S02CH2CH2-

-NCH2CH20H

-NCH2CH20H Blue Blue 36 37 HO3SOH2CH2CO2S—(vy)-HN-^Nv^-HN-r^[-N=N- Ν·νΝ kJj Heart SO3H HO3S (36) nh2 9H H3OC, -N=N- , So3h S02CH2CH2*· -nch3 blue (5-

S02C2H4- __3 Orange 23 201009027

Red (38) 39

SO2Q2H4- -nch3 Yellow (39)

40 41

SO3H

N=N_^~~y, SO2C2H4 -NCH3 yellow

(40) SO3H HOOCH4C2HN ΊΤ ) ! N=N—~\—SO2C2H4- -NH—^\Tm r N^N HO3SOH4C2O2S T Cl (41)

OH H3CO

-NCH2CH2OH yellow

42 43 , jC6:

HO3SOH4C2O2S—^ HN—ΗΝ, \^\^, 3〇3Η 'SO2C2H4- V ci(42)

-NCH2CH2OH orange

Orange 24 (43) 201009027 OH H3C〇 —

SO2C2H4——NCH2CH3 ^ Orange-2 (44) Example 45 (a) First, 3.19 parts of H acid was dissolved in liquid alkali, and 1.86 parts of trimeric cyanide ice dispersion was added dropwise to sodium hydrogencarbonate powder. Adjust ρΗ=1~3, control the temperature at 8~10 °C, react for 2 hours, filter and take the filtrate for later use. 5 (b) After dissolving 2.8 parts of PASE with liquid alkali, quickly add to the aqueous solution obtained in the above (a), adjust the pH to 3~5 with 15% sodium carbonate aqueous solution, and control the temperature at 30~35 °C. Between the two, an aqueous solution was obtained after the reaction overnight. (c) Take 20 parts of water, add 2.14 parts of the compound of formula (4) and 2.5 parts of 32% hydrochloric acid 10 aqueous solution, stir well, then quickly add 0.76 parts of sodium nitrite aqueous solution to control diazo in 0~5 °C. The reaction was completed in about 1.5 hours. The filtrate obtained in the above (b) was added, and the pH of the reaction was slowly adjusted to 5 to 7 with sodium hydrogencarbonate powder. After 3 hours, a red dye was obtained.

(45) 15 Example 46 25 201009027 5 e 10 15 Reference 20 (a) First, 3.19 parts of H acid was dissolved in liquid alkali, and added dropwise to 186 parts of cyanide ice dispersion to sodium bismuth carbonate powder. The pH was adjusted to 1 to 3, the temperature was controlled at 8 to 10 ° C, and the reaction was carried out for 2 hours. After filtration, the filtrate was taken for use. (b) After dissolving 2.8 parts of p-aminostyrene oxime with a liquid base, it is quickly added to the aqueous solution obtained in the above (a), adjusted to a value of 3 to 5 with a 15% aqueous sodium carbonate solution, and the temperature is controlled at 30 to 35 t. Between: After the reaction overnight, an aqueous solution was obtained. (c) First, 2.39 parts of J acid is dissolved in liquid alkali, added dropwise to 19 parts of melamine ice dispersion, adjusted to pH=i~3 with 15% sodium carbonate aqueous solution, and the temperature is controlled at 5~10. . (:, the reaction was carried out for 1.5 hours, and the filtrate was taken up after filtration. (d) After dissolving 2.8 parts of p-aminostyrenesulfone with a liquid base, it was quickly added to the aqueous solution obtained in the above (a) 'with 15 〇/〇 carbonic acid The sodium solution is adjusted to a pjj value of 3 to 5'. The temperature is controlled between 30 and 35 ° C, and an aqueous solution is obtained after the reaction overnight. (e) 20 parts of water is added to add 2.14 parts of the compound of the formula (4) and 2.5 parts of 32%. The aqueous hydrochloric acid solution is stirred and dispersed well, and then 76 parts of sodium nitrite aqueous solution is quickly added, and the control is carried out at 〇~5. (: Diazotization is carried out, the reaction is completed in about 1.5 hours, and the solution obtained in the above (b) and (d) is added. Slowly adjust the pH of the reaction to 5~7 with sodium bicarbonate powder. After 3 hours of reaction, a dark blue dye is obtained. 26 201009027 —HN<r poor

SO2CH2CH2——nch3 S03H HO3SOH2CH2CO2S- S03H H03S H03SOH2CH2C02S·

So2ch2ch2 (46) Test Example 1 Reference 3 parts of the dye prepared in Example 5 was dissolved in 100 ml of water, and 5 was made into 30 parts/boost dye solution; 25 ml of alkali solution was used (using caustic soda 15 ml/liter and Glauber's salt 30 parts / liter) was added to the dyeing solution and uniformly stirred. The resulting mixture was poured into a Roller dye press, and then the cotton fabric was subjected to roller dyeing and then rolled into a shaft shape. This form of cotton fabric was stored at room temperature for 4 hours. Then, the obtained blue dye is first washed with cold water, then washed with boiling hot water for 10 minutes and 10 minutes, then soaped with boiling non-ionic detergent for 10 minutes, and finally washed again with cold water, and dried to obtain blue. The dye has excellent dyeing and coloring rate. ❹ Test Example 2 15 Three parts of the dye prepared in Example 10 were dissolved in 100 ml of water to prepare 30 parts/boost dye solution; 25 ml of alkali solution was used (using caustic soda 15 ml/liter and Glauber's salt 30 parts/升) is added to the dyeing solution and uniformly stirred, and the resulting mixture is poured into a Roller dyeing machine, and then the cotton fabric is subjected to roller dyeing and then wound into a shaft shape. This form of cotton fabric was stored at room temperature for 4 hours. After 20, the yellow dye obtained is first washed with cold water, then washed with boiling hot water for 10 minutes 27 201009027 hours, then soaped with boiling non-ionic detergent for 1 minute, and finally washed again with cold water, after drying The yellow dye has excellent dyeing and coloring rate. 5 ❹ 10 15 m 20 Test Example 3 Take 100 parts of urea, 10 parts of sodium m-s-benzenesulfonate, 20 parts of baking soda, 55 parts of sodium alginate, and 815 parts of warm water, 1000 parts in total. Additive paste. Three parts of the dye prepared in Example 7 were sprinkled on the above-mentioned auxiliaries paste and quickly scrambled. The 45-degree twill plate printing screen of 1 〇〇 mesh is covered on a suitable size of mercerized cotton twill, and the color paste is placed on the screen and scraped. Place the scraped cloth at 65. (: Dry in the oven for 5 minutes; put the dried cloth into the steamer and steam for 10 minutes at atmospheric pressure saturated steam 1〇2~1〇5°C. Then the red dye is washed first by cold water, then Wash with boiling hot water for 10 minutes, then soap with boiling non-ionic detergent for 1 minute, and then rinse again with cold water. After drying, the red dye can be obtained with excellent dyeing and coloring rate. The invention can indeed achieve the object of the invention by the disclosed technical idea, which is novel, progressive and industrially applicable, and is in conformity with the invention patent requirement. However, the above disclosure is a preferred embodiment, Partial changes or modifications resulting from the technical idea of the case are easily inferred by those familiar with the technology, and the patent rights of the case are not excluded. 28 201009027 <φ The above embodiments are merely examples for convenience of explanation. The scope of the claims should be based on the scope of the patent application, and is not limited to the above embodiments. 5 [Simple description of the diagram] None. [Main component symbol description] 10 None.

Claims (1)

201009027 X. Application for Patent Park: 1. A reactive dye with dialkylamino bridging group of formula (I): G— R3 (Rik3y Β—(CH^m_N—(CH^n— B* (R2)〇<3 X 5 (i) wherein # & and E 2 are each independently selected from a substituted or unsubstituted phenyl group structure, a substituted or unsubstituted naphthyl group structure, and a substituted or unsubstituted monoazo a group consisting of a group structure; 10 R is hydrogen, a Cl 4 alkyl group, a Cl. 4 alkyl group, a phenyl group, a sub-cup group, or a Cw alkyl group substituted with a substituent, wherein the substituent is selected from the group consisting of a pixel a group consisting of a hydroxyl group, a carboxyl group, or a sulfonic acid group; (Ri)o-3 and (R2)0_3 are 〇 to 3 identical or different substituents, and each is independently selected from hydrogen, argin, and a group consisting of a base, a slow base, an acid group, a nitro group, an aryl group, a ft15 Cl.4 alkyl group, a Cl_4 alkoxy group, a urea group, and an amine group; and the rulers 3 and R4 are each independently hydrogen or a Ci4 alkane. Base; RS and R·6 are each independently hydrogen, Cl_4 alkyl or a stupid ring; (R7) 〇-3, Q, and substituted G and G' are each independently selected from the group consisting of hydrogen, wpr or unsubstituted C1_4 alkyl; (R7) 0-3 is 0 to 3 phase solids忐, 自由... The same substituents, and each independently selected from the group consisting of 虱'halogen, hydroxy, carboxy, which avoids a decanoic acid group, a nitro group, a cyano group '^1-4 30 20 201009027 alkyl group, cN4 alkoxylate a group, a ureido group or an amine group; B and B' are each independently selected from the group consisting of a linear chain, -S02- and -CONH-(CH2)k-S02-; k is 1, 2, 3, 4, 5 Or an integer of 6; 5 Q is -S02-U, -C0NH-(CH2)d-S02-U, -0-(CH2)r-C0NH-(CH2)d-S02-U, thiosulfate thiosulfate (β-thiosulfatoethylsulfonyl), -R, -S02-U or -R, -U,; R' is 〇ι·4 alkyl or phenyl; 丨d and r are each independently an integer of 2, 3 or 4; 10 U is -CH2CH2W or -CH=CH2; W is -Cl, -〇so3h, -opo3h, quaternary ammonium salt, pyridine, carboxypyridine-N-C2H4SO3H group, fluorenyl π ratio bite group, carbon amine group π ratio The occluded group, or R8 and R9 are each independently hydrogen or d-4 alkyl; 15 U is -halopropyl, alpha-halopropyl, cold-halopropyl, or alpha Halopropenyl fluorenyl; | X is a halogen; and m and η are each independently an integer of 2, 3 or 4. 2. The reactive dye having a dialkylamino bridging group as claimed in claim 1, wherein R is hydrogen, Cw alkyl, Cw alkylcarbonyl, 20 phenyl, arylene, or hydroxy or A sulfonic acid group substituted CV4 alkyl group. 3. A reactive dye having an AT, iV-dialkylamino bridging group as described in claim 1 wherein (ROo·3 and (R2)o·3 are 0 to 3 identical or not 31 201009027 The same substituents, each independently selected from the group consisting of hydrogen, a reductive group, a decyl group, and a Cw alkoxy group. 4. A decylalkylamine bridge as described in the scope of claim a reactive dye of the group, wherein t ' G and G are each independently selected from the group consisting of hydrogen, (〇) (Γ2 - 0^(Rr)c3 5 and Q. 5. As claimed in claim 1 a reactive dye having a dialkylamino bridging group, wherein (1) 〇_3 is 〇 to 3 identical or different oxime substituents selected from hydrogen, sulfonic acid groups, Cw alkyl groups and a group consisting of Cl_4 alkoxy groups. 10 6. The reactive dye having a dialkylamino bridging group as described in claim 1, wherein B and B are each independently -s〇2- or -C0NH-(CH2)k-S02-. 7. A reactive dye having a dialkylamino bridging group as described in claim i, wherein 'Q is selected from, 15 C〇NH-(CH2)d -S02-U, -R'-S02-U a group consisting of -R'-U', wherein φ8 is a reactive dye having a dialkylamino bridging group as described in claim 1, wherein E1*E2 are each independently substituted or unsubstituted. The phenyl group structure is of the formula: S03H J\^NHR10 *human γ 20 wherein '* is the coupling position, R1() is hydrogen, Cw alkyl, C2_4 alkanoic acid group, or substituted with a substituent Ci 4 alkyl, and the substituent is a hydroxyl group, a cyanide 32 201009027 base, a carboxyl group, a sulfonic acid group, a methoxymethyl sulfonyl group, a fluorene. A soil, a hexylene phenyl phenyl group or a y. The reactive dye of the group according to the above item, wherein each of & and £2 is a naphthyl group structure of the dialkylamino bridge 5 is a structure of the formula: substituted or unsubstituted 10 ❹ OH H03s^ where '* is the coupling position. 10. A reactive dye as described in claim 1 of the patent application, wherein & and £2 are each independently. The monoazo group structure is as follows: Substituted or unsubstituted (so3h) 0~1 a burnt amine bridge 33 201009027 Where * is the coupling position. 11. A reactive dye having an AT, #-dialkylamino bridging group as described in claim 1 wherein X is a gas. 12. The reactive dye having a dialkylamino-5 bridging group according to claim 1, wherein the compound of the formula (I) is a compound of the following formula (II): (〇) (Γ2 (R7XT3 10 (II). 13. The reactive dye having a dialkylamino bridging group according to claim 12, wherein the formula (II) is a structure of the following formula (5): HO3S0H2CH2CO2S--hn-tVhn-Q| ΝγΝ Cl S03H H03S Nh2 oh -N=N S02CH2CH2- -nch3 Equation (5). 14. The reactive dye having a dialkylamino bridging group according to claim 12, wherein the formula (II) is a structure of the following formula (6): 15 Formula (8). 15. The reactive dye having #,iV-dialkylamino bridging group according to claim 12, wherein the formula (II) is a structure of the following formula (7): 34 201009027 SQ2C2H4--NCH2CH2OH 16. The reactive dye having a dialkylamino bridging group according to claim 12, wherein the formula (Π) is a structure of the following formula (8): S〇2C2H4--NCH2CH20H 17. The reactive dye having a dialkylamino bridging group according to claim 12, wherein the formula (II) is a structure of the following formula (9): S03H hooch4c2hn. N=N—SO2C2H4--NC2H4OH HO3SOH4C2O2S—NH—^N,^jp Cl ©10 (9). 18. The reactive dye having a dialkylamino bridging group according to claim 12, wherein the formula (II) is a structure of the following formula (10): HO3SOH4C2O2S-HN ^Γ-Ν=Ν SO3H SO2C2H4- -NCH3 Formula (10) 35 201009027 ml 7. Designation of representative drawings: (1) The representative representative of the case is: None. (2) A brief description of the symbol of the representative figure: None. 8. If there is a chemical formula in this case, please reveal the chemical formula that best shows the characteristics of the invention: B— — (CH2)n— (^2)〇3 -n=n-e2- S-α X, m and n are as defined in the specification. 4