JPS58206668A - Asymmetric 1:2 chromium complex dye - Google Patents

Abstract

(57) [Summary] This bulletin contains application data before electronic filing, so abstract data is not recorded.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a chromium complex dye represented by the following formula 1.

In the formula, A-, a residue of hydroxynaphthalene or 2-hydroxynaphthalene, R1 is hydrogen, chlorine or methyl, R2 is hydrogen, nitro or chlorine, Ka means a cation, and the substituent xl, One of x2 and X3 is an SO3 group'z (the other two are hydrogen, but when R1 is a salt and R2 is hydrogen, X3 is a water group.

Ka is an easy ion (for example, of an alkali metal),
There are lithium, potassium or alkali metal ions. Furthermore, Ka
It can be an ammonium ion or an ammonium salt of an organic amine.

Preference is given to dyes of the formula I in which R is chlorine or especially hydrogen.

R2 is preferably hydrogen or nitro.

One of the three characters L Xt + X2 and X3 is an SO3 group and the other two are hydrogen. Preferred dyes are those in which one of X2 and X3 is an S03 group and the other is hydrogen.

In particular, dyes for short hair can be dyed using the following general formula (■).

In the formula, A is a residue of 1-hydroxynaphthalene or 2-hydroxynaphthalene, -R1't: i-core or especially aqueous system, R2 is hydrogen or 2'-Ka (t) means a field ion. , and the direct substituents X2 and X
3 means that one of them is S03 construction and the other is hydrogen, and R
When 1' is a base thread and R2 means hydrogen, X
3 is water-based.

Dyes according to the wood invention can be produced by methods known per se. The analogy is to take a 1=1 chromium complex of a dye of 2 or a 1=1 chromium complex of a dye of 2'c2:s M, and then convert the chromium complex of the formula Manufactured by reacting with dyes. In addition, in the above Niso Omahi h', R1, R2 and A111 have the meanings expressed in formula I, and three direct substituents X1+
One of X2 and X3 means 5O3H and the other two mean hydrogen, but when R1 is a single element and R2 is hydrogen, X3 is water dyed.

The above-mentioned 1:1 chromium complex salt is produced by a method known per se, preferably using a chromium (1) base in melted sand. The compound is reacted with an azo compound of formula 1 or old in a weakly acidic, neutral or slightly alkaline medium.

It is also possible to react mixtures of aso-dyes of the formulas H and ■ with the chromating agent. In this case, in addition to the chromium complex of formula I, there is also a dye of 2-7! 1 containing two symmetrical 1:2 complex salts, each south of
: A two-button salt mixture is produced.

The novel ROM complex dyes of formula 1 obtained by the above method can be used in the form of salts, particularly alkali metal salts, especially sodium gt or lithium salts, or ammonium salts or with a nitrogen atom positively charged. It is isolated in the form of a salt of an organic amine with This new ROM complex dye has the presence of a leveling agent! or various charges for kidnapping on his own behalf,
For dyeing and printing of nitrogen-containing materials, especially of wool or wool, and also of synthetic fibers made from polyamide or polyurethane, and especially of leather, A15.
Suitable for color and printing.

Gray-blue, blue and 1l-1 with excellent fastness, especially excellent needle fastness and resistance to wet processing.
: Obtains dark blue dyeing.

A preferred differentiation of the dyes according to the invention is the dyeing of wool and polyamides and especially fur or leather. The leather is suitable for dyeing, for example, chrome-tanned sheep, cow or pig leather, re-tanned leather or suede leather, all of these types of leather.

The dyes according to the invention are particularly suitable for use in the form of dye mixtures, in particular for use in one or more color combinations.

Which dye mixture is preferably used? I is a mixture containing the following components:

a) a blue 1:2 metal complex of formula I above, b) formula V (wherein m is an integer from 0 to 2, and nitro and is 5);
a red or reddish-brown 1:2-chromium or -cobalt complex of a dye (located in the -ox or 6- position), and C) a dye of the formula ■ (where m has the above zl: taste); dyed book 1 L'
L color 1:2 cobalt complex salt, or Shiba Fu1's yellowish brown 1:2-cobalt or -chromium ", (" temperature) of formula 1 (where m is as described above, taste 2).

French Patent No. 1220529 *++:4)
z h = most g + most similar known dye contained in Example 2 (dye of the 6th α1st column), i.e. sulfo group xl,'
The above French patent 1' containing (containing one sulfo group at the 8-position of χ-naphthol) instead of x2 or X3
Publicly known similar to GaJ manufactured by i-! , 1, the Xz i or X3 sulfo group dyes according to the present invention are characterized by their much superior wet processing properties.
Yrou 1-μ (separated by IC.
+ Kakumei dyeing 4 = 1 is superior to the known JJ dyeing method in terms of its durability at p++ 3K, which is an especially important factor when coloring leather. .

1 shows the embodiment of the present invention. Koha is indomitable 19.”
, vl, is for the purpose of clarifying, and is not intended to limit the scope of this section 5.3. Note that "part" is the subtotal j% and "percentage" is the middle 1□knee percent.

Example 1 1 (chromium atom): 1. (dye molecule) type chromium complex compound (this is chromium 5.2 H'ivz, diazotized 5-nitro-2-amino-1-hydroxybenzene and 1-hydroxynaphthalene-1-sulfonic acid) and·
(contains 38.9 parts of monoazo glaze made from)
, and 43.9 parts of a monoazo saccharide prepared from diisolated 6-nitro-1-amino-2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene.
Heat at 95°C in 00 parts of water. This mixture was adjusted to 1) II 8 and 4) with sodium hydroxide. Stir at 1□A degree and at p+11[rl until no starting mass is dissolved. After the reaction is completed, the dye is spray dried to perform AiY. The resulting dye is in the form of a dark powder, which dissolves in water to give it a blue color. This dye dyes leather in a light-fast dark blue shade.

Example 2 38.9 parts of monoazo dye prepared from diazotized 5-nitro-2-amino-1-hydroxybenzene and 1-hydroxynaphthalene-3-sulfonic acid and chromium 5
．． Add 2 parts of 1:1 chromium candy salt to 500 dilute water and diazotized 6-nitro-1-amino-
Monoazo Toryo 43 containing 2M of 2-hydroxynaphthalene-4-sulfonic acid and 2-hydroxynaphthalene
．． I can write the 9th part. this? Next pli 7~7
．． 5. Asymmetry with 85-90°c vtc 1:
Stir until a dicomplex dye is formed. After the reaction is complete,
The product is dried and the resulting dye Qi is separated. The product obtained is in the form of a dark powder, imparting a color scheme to water, and the product has a leathery 93 color to a dark blue tone with needle base fastness.

48.9 parts of a chromium complex compound of the 1 (chromium atom): 1 (dye molecule) type (this is 5.2 parts of chromium and diazotized 6-nitro-1-amino-2-hydroxynaphthalene) A diazotized 5-nitro-4-chloro-2-amino- Monoazo dye prepared from 1-hydroxybenzene and 1-hydroxynaphthalene-5-sulfonic acid 4
Add 24 capitals. The reaction mixture was heated to 90-95 °C and diluted with sodium hydroxide to give a p) I'Q of 7.5 to U'3.
M. Maintain this temperature and this constant pli (directly) until the disappearance of the starting material. After the end of the reaction 11.
The dye is isolated by concentrating it to dry matter. This product is in the form of a dark powder, dissolves in water to give a blue color, and this product dyes leather in a dark blue shade that is lightfast.

According to the method described in Examples 1 to 3 above, another one:
Other dyes that can be produced using dichromium complexes are shown in the table below. In either case, one of the dyes applied to the I) lock or rt jW of the garment is used as a 1:1 chromium complex, and the other dye opposite in the garment is used as a non-metallic dye. . The dyes obtained dye wool and polyamides in grey-blue, blue or dark background to dark blue tones.

Implementation 1 Criterion 4 Chromium complex compound of type 1 chromium atom: 1 molecule of dye *4
4.4 parts (this includes 5-2 parts of chromium, diisolated 1-amino-2-hydroxynaphthalene-4-sulfone and 2-
Monoaiso dye formed from hydroxynaphthalene 3
and 38.41 parts of a monoisomer formed from diazotized 5-ditro-2-amino-1-hydroxybenzene and 1-hydroxynaphthalene-4-sulfonic acid. Together we will work together on 800 copies of water.

, the reaction mixture was added at 90-95°O, pQ'>C,
The pH was then adjusted to 7.5-8.0 with sodium hydroxide a=
+W<-. This mixture is then stirred until no starting material is detected. After the reaction child, 111
The resulting dye is precipitated by adding sodium chloride,
So I said goodbye and went to bed. The applied dye is in the form of a dark powder, is soluble in water and imparts a CI'j color, and colors leather, polyamide or wool to an f'1 tone with excellent fastness properties.

Example 5 1 chromium atom: 1 dye molecule type chromium compound 4g 47
．． 4 parts (this is 5.2 parts of chromium, 42.4 parts of a monoazo dye produced from diisolated 5-nitro-4-chloro-2-amino-1-hydroxybenzene, 1-hydroxynaphthalene-4-sulfonic acid, and 1) ),
and 139.4 parts of monoazole produced from diazotized 1-amino-2-hydroxynaphthalene-4-sulphos and 2-hydroxynaphthalene were introduced into 800 parts of water and heated to 95°. 1 with sodium hydroxide
) II fy) Continue stirring at this temperature until no more Yamamoto 1 residue is removed. Reaction brother finished,
The L formula is precipitated by cooling with sodium chloride, filtered and dried. The resulting product is in the form of a dark powder, dissolves in water to give a blue color, and gives excellent fastness to wool, polyamide and leather in a blue shade K.
>3. color.

Example 6 Diasolated 1-amino-2-hydroxynaphthalene-4~
394 parts of the monoazo compound obtained from sulfonate and 2-hydroxynaphthalene and diazotized 5-ditro-2-
Monoazo dye obtained from amino-1-hydroxybenzene and 1-hydroxynaphthalene-4-sulfonate 3
8.9 parts of water were added to 800 parts of water and the mixture was heated to 80°C-4. Add 1j5 of water (sodium chloride to 75 to 1'8), and chromium 5.7 to 3'4J of the sodium salt of chromium salicylic acid. Target 1 Father Keka, Eru.

The metallization of this reaction liquid is completed by 1 flow force (1,
qlH, do it. Hammer inside or spray dry "corpse (・Remove trapped water. (Used product?), lfi'
, :Color V and shape at the end? It dissolves in water and turns blue.1. This product is a mixture of leather, wool and polyamide in a uniform color tone with excellent waxing properties (J, L: colored 1, non-dyed +- [is a mixture of 1: 1; .

Chromium salicylic acid, instead of chlorium salt;
If the acid-resistant cobalt or acid-resistant cobalt of i or 1 is added and the same procedure as described in 2 is carried out, a mixture of cobalt 1,1 salts corresponding to the above formula is obtained.

This polyester, polyamide, or wool is dyed to a reddish dark blue color with excellent waxiness.

Other 1=2 according to the method described in Examples 4 and 5 of L-
Chromium lead salts can further be prepared starting from the dyes shown below. In each case, one of the dyes in the I column or the ■ column of the garment is used as a 1=1 chromium complex, and the other dye shown in the opposite position on the table is used as a non-metallic complex! ■It is used for one history. The obtained 'n-1:2 complex salt material is a highly durable material for leather, wool and polyamides.
A: Dye to the same color tone with one strand of yarn. .

Example 1 Tariff I (chromium atom): 1 (dye molecule) type chromium complex 44.4 parts of 1 size product (this consists of 5.2 parts of chromium and 1-diazotized
(containing 39.4 parts of a monoazo dye produced from amino-2-hydroxynaphthalene-4-sulfonic acid and 1-troxynaphthalene) was added to diisolated 5-nitro-2-amino-1-hydroxybenzene. and 38.9 parts of a monoazo group produced from 1-hydroxynaphthalene-3-sulfonate and 1-hydroxynaphthalene-3-sulfonate.

The reaction mixture was heated to 85-90°C, the pH was adjusted to 7.5-8 with sodium hydride, and the Idemitsu powder quality was obtained while maintaining the crystallinity and pH. Continue stirring until no more chiya comes out. Once the reaction is complete, the dye produced is isolated by evaporation and evaporation to a dry form. stomach? The absorbed dye takes the form of a dark powder and dissolves in water.
imparts color and dyes the leather to a dark blue tone.

Example 8 Chromium atom 1: Dye molecule 10 types of chromium ■, 1 compound 44.4 parts (this consists of 5.2 parts of chromium and diazotized 1-
39.4 parts of a monoazo dye obtained from amino-2-hydroxynaphthalene-4-sulfonic acid and 1-hydroxynaphthalene) and diisolated 5-nitro-1-\chloro-2-amino- 14-star monoazo dye 42.4196 from 1-hydroxybenzene and 1-hydroxynaphthalene-4-sulfonic acid was added to 750 μm of water and heated to 80-85°C. 7~-7.5 and pll
Stirring is continued at this temperature while keeping the temperature constant until the starting material J1 disappears.

After the reaction is completed, the product is qi
g = do. The raw bx product obtained was in the form of a dark powder,
Does it dissolve in water and turn blue? give. This product dyes the leather in a dark blue shade with excellent needle fastness.

'Example 9 Diasolated 1-amino-2-hydroxynaphthalene-4-
Monoazo dye produced from sulfonic acid and 1-hydroxynaphthalene: 1:1 chromium complex compound containing 39.4 parts of chromium and 5.2 parts of chromium & 500 parts of water, then diisolated 5- Add 38.9 parts of a monoazo dye prepared from nitro-2-amino-1-hydrocybenzene and 1-hydroxynaphthalene-5-sulfonic acid. This mixture was heated to a temperature of 80-85°C and a pll of 7-7.5
Stir until no redundant T4 comes out.

After the reaction is completed, the live J proboscis is isolated by spraying. The product takes the form of a dark powder and dissolves in water to give a 15' color. This raw material is dyed with leather to the color tone of needle moto kataro 1 falcon.

According to the method described in Examples 7 to 9 above, other 1:2 chromium coti' salts were prepared from the preparations shown in Section 3. In either case, one of the dyes shown in column I or H of the table was used as a 1:1 chromium complex salt,
Then, use the other dye shown in the opposite position on the table as a dyed dye. The 1:2118 salt dye dyes leather, wool, and polyamide in shades of grey, g, or dark blue to navy blue.

Example of dyeing leather, << 100 parts of suede leather for 41 (as dry heavy electric) 'a = '2 parts of 4% ammonia and 1000 v of water'I
Place in a solution with part Jk and soak at 50 °C for 2 hours, and then add 1000 parts of water, 2 parts of ammonia and 6 parts of ammonia in Example 2. In the bath with P and B, it is colored for 1 hour at the consistency of F and Q. Then, add 6 liquids of Mizube O Tanibe and 85 Kaya Ti 7.1 part and further 30 Dye for a minute. Then, leave the leather' (
! Rinse thoroughly and treat the 19-inch platform further with 2 parts of the dicyandiamide/formaldehyde condensation product for 30 minutes at 50' (!).

1 m 4', l+1 suede leather and glove leather can be color-treated to ≦ in the same way.

The dark background dyeings produced in this way are characterized by excellent fastness and good dyeing power.

100 pieces of polyamide yarn for rolling motion are placed in a dyeing bath at 50°C. The Sung color bath is a ridge containing 12 parts of the powder of Example 1, 4 parts of ammonium chain acid, 2 parts of a leveling agent, and a total of 4000 parts of water. Heat this solution for 45 minutes, 2.I, 1 color point, and then
Hold for an additional 45 seconds and dye. Raise the dyed product, rinse thoroughly with cold water, and transfer.

This dyeing process gave the polyamide a -i'j' color of 62 colors and excellent fastness properties.

Add 100 parts of knitting yarn to a dyeing bath of +, f, 7 people. The dyeing bath was a mixture of 2 parts of the 9 vinyl material of Example 8, 4 parts of 80'Z acetic acid, 2 parts of the leveling agent and 4000 parts of water in total. The staining solution was allowed to reach a warm temperature for 45 minutes, and then kept at a low temperature and humidity for an additional 45 minutes. Pick up the dyed material and rinse it well with cold water for proper etiquette. The yarn is dyed in a greenish-white color and has excellent fastness properties.

Claims (1)

[Claims] 1. Formula I (wherein, A+11-hydroxynaphthalene or 2-hydroxynaphthalene residual water, R1 & yo-aqueous system, moonlight or methyl, 1't2I yo-aqueous system, nitro oxdaha J□" crystal system , set K
ali means a cation, and one of the direct substituents Xl, X2 and X3 tastes the S03 group, and the other two taste hydrogen, ]E1 is chlorine and Iri2 is hydrogen.Is X3 hydrogen? , I-1, taste) metal 3
14 salt dyeing. 2, R, is Satoshi and t (1,!H means hydrogen, and t1Xl allows 1 to mean hydrogen.
1L) Dye according to note 1 in the 1st month. 3 One of the direct substitution groups X2 and
if'F +il'l's cry of desire', part 1' shell V1 listed dye No. 1゜71 (wherein A is a residue of 1-hydroxynaphthalene or 2-hydroxynaphthalene, R, / is chlorine or especially aqueous, R2 means hydrogen or nido9, Ka■ means a cation, and substituents X2 and X3, one is 803 and the other is hydrogen, but R1' is chlorine and J: 1. The dye according to claim 1, wherein when R2 is hydrogen, X3 is aqueous. 5.% In the method for producing a dyenate of formula I as claimed in claim 1, a mixture of a dye of formula (1) and a dye of formula (1) is treated with a chromium-releasing compound; 1:1 chromium complex salt or formula of dye H
A process characterized in that, if a 1:1 chromium complex of the dye is formed, it is then reacted with unmetallized dyes of the formulas IV and II, respectively (in each of the above formulas, RIXR2 and A has the meaning defined in formula I and 1
．． - one of the substituents Xl, X2 and X3 is 803
H group and the other two mean hydrogen; however, if R1 is a salt and R2 is hydrogen, then X3° is hydrogen). 6. Use of the dyes of the formula I'&lff1 according to claim 1 for dyeing wool, polyamides and in particular leather or fur. .