JPS6248768A - Fiber reactive triphenodioxazine compound - Google Patents

Abstract

NEW MATERIAL:A compound expressed by formula I [A is formula II (R1 and R2 are H or 1-4C alkyl; X is -SO2CH2CH2Cl, -SO2CH=CH2-, -SO2CH2 CH2OSO3H, etc.; Y is halogen; Z is aliphatic or aromatic crosslinking group which is, as necessary, substituted; ring B is benzene ring or naphthalene ring which may have another substituent group; n is 0 or 1]. EXAMPLE:A compound expressed by formula III. USE:A dye for dyeing fibrous materials containing OH or amino groups, e.g. wool, silk, polyamide, cellulose, cotton, etc., to reddish blue color and having improved reproducibility and uniform dyeing properties since it is scarcely affected by dyeing temperature. PREPARATION:For example, 2mol diamine expressed by formula IV is reacted with 1mol 2,3,5,6-tetrachloro-1, 4-benzoquinone to give a dianilide, which is then cyclized in fuming sulfuric acid while heating. The resultant triphenodioxazine base and an amine expressed by formula V are condensed with a cyanuric halide expressed by formula VI.

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to a fiber-reactive triphetdioxazine compound. n represents 0 or 1.

R,, R, is a hydrogen atom or a C2-4 alkyl group,
is the group -8O□CH2CM, CI, -8O2C) (=C
Toki, -SO, C Toki CPbO803M, -8o! CH,
CH,0PO3R2t-N(R,)80゜cHI
C) represents a group of 0803 H, R represents a hydrogen atom, a methyl atom or an ethyl group; OY represents a halogen group; 2 represents an optionally substituted aliphatic or aromatic bridging group; , Ring B represents a benzene or naphthalene ring which may have other substituents. m represents 0 or 1. ] The present invention relates to a triphetdioxazine compound represented by the following.

General formula (1) NoA substitution a'g R1s R2(1')
The 7/L'ki μ group of C52 includes methyl group, ethyl group, n-propyl group, 186-propyl group, n-butyρ
base, la.

- Spot/L/X, 5ee- Spot I'? fss tar
0-ring B, which can include a t-butyy group, has other substituents other than X, such as a C1-4 alkyl group, a 01-41μ koxy group, a fluorine atom, a chlorine atom, a bromine atom, a nitro group, and a hydroxy group. , a ponic acid group, and a sulfonic acid group. When the crosslinking group 2 is aliphatic, it can be a C2-4 alkylene group, and when it is aromatic, it can be a phenylene group in which 0.1.2 or 8 sulfonic acid groups are disubstituted. Another example is the naphthylene group.

In general formula (1), R1 and R2 are particularly preferably a hydrogen atom or a methyl group or an ethyl/1/ group, R3 is particularly preferably a hydrogen atom, and Y is particularly preferably a chlorine atom or a fluorine atom. The bridging group 2 is particularly an ethylene i% 1 ,
a-t hi I 4-phenylene group, 2-sulfo-1
, 4-phenylene group, 2,5-disμ-1,4-7enylene group, 4-sulfo-1,3-phenylene group, 5-sulfo-1,2-phenylene group, or 4, 8-disulfo-
2,6-naphthylene group is preferred 0 The triphetdioxazine compound represented by the general formula (I) is, for example, a diamine of the general formula (6) [wherein R1, Z, m and h have the above-mentioned meanings] 2 moles of 2,8,5.6-detofukuroρ-
1. The dianilide obtained by reacting with 1 mole of 4-benzoquinone is cyclized by heating in oleum, and in some cases, sulfonation can be simultaneously carried out to introduce a sulfonic acid group. Formula (8) [wherein R2, Z, m and n have the above meanings. ] A trifetdioxazine base represented by the following and the general formula ■R.

In formula c, 8%R1 and X have the above meanings. ] Amines represented by the general formula [wherein, Y
has the above-mentioned meaning 0] It can be produced by condensation with a cyanuric halide represented by 0 The following types of compounds can be mentioned as diamines of the general formula (9) that can be used in the present invention 1.8 -1 or 1,4-diamitbenzene, 2,6-diamitbenzene-1-sulfonic acid, 4,4'-diaminodiphenylamine-2,8-disulfonic acid, 4,4'
-Diaminodiphenylamine-2,2', 5'-
) disulfonic acid, 8', 4-diaminodiphenylamine-2,4'-disulfonic acid, 2', 4-diaminodiphenylamine-2゜6'-disulfonic acid, 4,4'
-diaminodiphenylamine-2-sulfonic acid, 2-amino-6-(4'-aminophenylamino)naphthalene-214,8-)disulfonic acid or 5-amino-2-
<21-Amineethylamino)benzene-1-nulfonic acid The following types of compounds can be mentioned as the amine represented by the general formula 4.

1-aminobenzene-2-1-8- or -4-β-sphatoethyl/l/nurphone, 1-aminobenzene-8
-#-)N suphatoethyl sulfone, 1-amino-4
-Methylbenzene-8-β-sulfatoethylsulfone, 1-aminobenzene-8-β-chloroethylsulfone, 1-amino-4-methoxybenzene-8-β-sulfatoethylsulfone! Resulfone, 1-aminobenzene-4-β-
Sulfatoethylsulfone-2-sulfonic acid, 1-aminobenzene-5-β-sulfatoethylsulfone-2-
Nurphonic acid, 1-7t nobenzene-5-β-sulfatoethyl sulfone/L/dinon-24-disulfonic acid, 1-aminonaphthalene-4-β-sulfatoethylsulfone, 1
-amino-2,5-dimethoxybenzene-4-β-sulfatoethylsulfone, 1-aminebenzene-4-β-
Sulfatoethylsulfone-2-carboxylic acid, 1-aminobenzene-5-β-sulfatoethylsulfone-2-
force ~ ponic acid 11-amino-2-methoxybenzene-4-
β-sulfatoethylsulfone, l-amino-2-chlorobenzene-4-8-nulfatoethylsulfone, 1-
Amino-2-methoxybenzene-5-β-sulfatoethylsulfone, 2-aminenaphthalene-8-β-sulfatoethylsulfone, 2-aminonaphthalene-8-β-
Sulf-1-ethyl A/Sulfur-6-sulfonic acid, l-amino-2,5-dimethoxybenzene-4-vinylsulfone, 1-amino-2-methoxy-5-methylbenzene-
4-β-nulfatoenals ρphone, 1-amino-2,
6-jethoxybenzene-4-β-sulfatoethylsulfone, 1-amino-2-bromobenzene-4-β-sulfatoethylsulfone, l-amino-2-bromobenzene-4-vinysulfone, 1-7 minobenzene-5-
Vinylsulfone-2,4-disulfonic acid, 1-aminobenzene-5-β-phosphatoethylsulfone-2,4-
Disulfonic acid 11-aminobenzene-5-β-chloroethyl ρphone-2,4-disulfonic acid, 2-7minonaphthalene-8-β-phosphatoethylsulfone-6-su
Fonic acid, 2-aminonaphthalene-8-pini #7-1L/
Phone-6-sulfonic acid, 1-amino-2-methoxy-5
-Methylbenzene-4-β-chloroethylspone, 2
-7 minopheno/L/-4-β-sulfatoethylsulfone, 1-aminobenzene-8- or -4-vinylsulfone, 1-amino-2-hydroxybenzene-4-
β-sulfatoethylsulfone, 1-aminobenzene-
6-Pynylsulfone-2-sulfonic acid, 8-(N-methyl-β-nuphatoethylsuhonylamino)-1-aminobenzene, 8-(N-ethyl-β-,7=/L/phatoethylsuhonylamino)-1 -7 minobenzene,
8-β-sulfatoethyl/1/nulfonylamino-1-
Aminobenzene 0 The compounds of the invention can be used to water-soluble a wide range of substances having hydroxy/' groups or amino groups, in particular textile materials such as wool, silk, synthetic polyamides and natural or regenerated cellulose, @Llf wood tablets or viscose rayon materials. It can be dyed according to the usual methods carried out using reactive dyes.

For example, in the case of cellulosic fibers, dyeing is carried out using the compound of the invention and an acid binder such as caustic soda, sodium carbonate, phosphate, silicate or sodium bicarbonate. The dyeing method can be selected depending on the properties and physical shape of the fiber, and for example, an exhaustion method, a printing method, a cold-bud patch-up method, etc. can be adopted.

In the case of the exhaust method, in the case of the 0 printing method, which is carried out at a relatively low temperature in a dye bath containing mirabilite or common salt in the presence of an acid binder such as IJ carbonate, sodium phosphate, or caustic soda,
Thickening or emulsifying thickening agents such as sodium alginate or starch ether and alkaline or BIIVC is applied to the fiber together with an alkali-releasing agent, optionally with the addition of customary printing aids or dispersants, such as urea, dried and heat-treated, especially in the presence of water vapor.
In the case of cold-pad-batch-up dyeing, which can be dyed easily when applied, caustic soda alone as an acid binder,
Alternatively, sodium silicate, sodium carbonate, or trisodium phosphate may be used in combination, and in some cases, mirabilite or common salt may be added. Pad and low/
It can be dyed by rolling it up to 1/4 inch, leaving it for 8 hours or overnight, washing with water, and drying.

The compound according to the present invention can particularly dye cellulose fibers at relatively low temperatures with a good fixation rate, and the dyed products obtained have excellent fastness to light, sweat, sunlight, chlorine, etc., and also have good fastness to washing, etc. It shows good fastness to wet processing and
In particular, it is excellent against acid bleed 1 and can eliminate the drawbacks of reactive dyes having monochlorotriazinyl groups.Furthermore, in the cheese dyeing method, which is a type of exhaust dyeing method,
Differences in dyeing degree and hue between the inner and outer layers of cheese tend to occur, which is a big problem in dyeing factories, but since the compound of the present invention has very good suitability for dyeing cheese, these interpolation points can be resolved. Advantages Also, since the compound of the present invention is not easily affected by dyeing temperature, it has excellent reproducibility and also has excellent level dyeing properties.

Next, in the following description of the present invention by way of examples, parts represent parts by weight.

Example 1 7.2 parts of 4.41-diaminodiphenylamine-2,8-disulfonic acid and 2,8,5.6-tetofuclo/l
A neutral solution of 2.5 parts of '-1,4-benzoquinone dissolved in 50 parts of water is stirred at 50 DEG C. for 6 hours by adding a sodium hydroxide solution to adjust the pH to 6 to 7 KmN.

The solution is then cooled and salted out by adding 15 parts of sodium chloride, filtered, washed with 25 g of brine and dried at 80°C. 10 parts of this product are added to 10 parts of oleum 2096;
Stir at 20°C for 2 hours, then add 100 parts of ice water.

The precipitate is separated by F and washed with saturated brine. After adding a small amount of nonionic surfactant to a neutral solution of 8.9 parts of the obtained trifetdioxazine base dissolved in 150 parts of water, 4.0 parts of cyanuric chloride was added to O-? The mixture was adjusted to pH 6-6 by adding sodium hydroxide solution.
7 and stir at 0 to 5°C for 4 hours. Next, add 1-aminobenzene-3-β-spharateethyl sulfone 6.
．． Add 1 part and leave at pH 4.5-5.5 for 5 hours,
After stirring at 20℃, raise the temperature to 55-60℃ and reduce the liquid volume to 259℃.
Salting out by adding 6 equivalent amount of sodium chloride, filtering,
Wash with 096 salt water and dry. 15.2 parts of a compound represented by the following formula (1) was obtained.

Used: 4.4'-diaminodiphenylamine-2,8
'-Dinulfonic acid is obtained by condensing 4-nitrochlorobenzene-2-sulfonic acid with 1,4-furylenediamine-2-sulfonic acid and reducing the obtained nitro compound [Reference Example 1 Formula Dissolve 0.8 parts of the compound represented by (1) in 200 parts of water, add 20 parts of Glauber's salt, add 10 parts of cotton, and raise the temperature to 60°C.

Then, after 80 minutes, add 4 parts of soda carbonate and boil at the same temperature.
After the time-dyed O dyeing was completed, washing with water and soaping were performed to obtain a bright reddish-blue dyed product with high density and excellent fastness to chlorine, light, sweat, and sunlight.

Examples 2-7 1-aminobenzene-3-β used in Example 1
The corresponding compounds were obtained in exactly the same manner as in Example 1, except that the following amines were used in place of sulfatoethylnurphone. Using the compounds thus obtained, Reference Example 1 and When dyed in the same manner, a bright reddish-blue dyed product with high concentration and excellent chlorine, light, sweat and sunlight fastness was obtained in both cases. Nurphone (8) 1-aminobenzene-8-β-phosphate ethyl-spone (4) 1-aminobenzene-3-β-chloroethylsulfone +5) 1-amino-4-methoxybenzene-8-β
-Sulfatoethylsulfone (6) 1-Amino-2-methoxybenzene-5-β-sulfatoethylsulfone (7) 2-Aminenaphthalene-8-β-nuphatoethylsulfone-6-sulfonic acid implementation Examples 8 to 19 The following triphenodioxazine bene [compound of the above general formula (B)] Column 2A, halogenated cyanide p [compound between the above general formulas]: Bm, amine [compound of the above general formula 4]
:Using CM, the color tone on cellulose was obtained by the same method as in Example 1: A compound characterized by column D was obtained.0 Procedural amendment (method) September 72, 1985 l Incident display Showa 1961 Patent Application No. 180586 2 Name of the invention Fiber-reactive triphueddioxazine compound 3 Relationship to the case of the person making the amendment Patent applicant address 5-15 Kitahama, Higashi-ku, Osaka Name (20
9) Sumitomo Chemical Co., Ltd. Representative Mori
Hideo 4 Agent Address: 5-15 Kitahama, Higashi-ku, Osaka 8, 1986
June 25th, 6, Description subject to amendment 7, Contents of amendment A copy of the specification originally attached to the application, Attached sheet (no change in content) 0 or more

Claims (1)

[Claims] In the form of a free acid, the following general formula ▲ has a mathematical formula, chemical formula, table, etc. ▼ [In the formula, A represents a group ▲ has a mathematical formula, a chemical formula, a table, etc. ▼, and n is 0 or 1 represents. R_1 and R_2 are hydrogen atoms or C_1_ to_4 alkyl groups, X is a group -
SO_2CH_2CH_2Cl, -SO_2CH=CH
_2, -SO_2CH_2CH_2OSO_3H, -S
O_2CH_2CH_2OPO_3H_2 or group -N
(R_3) represents a group of SO_2CH_2CH_2OSO_3H, and R_3 represents a hydrogen atom, a methyl group or an ethyl group. Y represents a halogen atom, Z represents an optionally substituted aliphatic or aromatic bridging group, and ring B represents a benzene ring or naphthalene ring which may have other substituents. m represents 0 or 1. ] A triphenodioxazine compound represented by