JPS6233355B2 - - Google Patents

Description

[Detailed description of the invention] "Textil praxis international" 1975, No. 313-
Starting on page 324, an organic acid (optionally mixed with hydrochloric acid) is stirred into the acid-stable sizing agent onto a cellulosic material primed with an alkaline processing solution containing a coupling component and sodium nitrite, and then this mixture is It is known to print printing pastes obtained by adding solutions or dispersions of aromatic amines. It is pointed out that in this process nitrogen oxide-containing gases are generated, which on the one hand requires the use of special equipment and on the other hand can give rise to various difficulties. This is because due to the diazotization of the amine a corresponding amount of nitrous acid is lost and the amine that has not been diazotized is therefore printed along with it. This amine can act as a coupling component and can darken the color.

In order to avoid leakage of nitrogen oxide-containing gases, it is proposed in the above-mentioned document to prepare the printing paste using a mixture of two base materials. Sodium nitrite is mixed into the first stock and a base (amine) dissolved in hydrochloric acid is mixed into the second, and then the two stock mixtures are mixed together. The resulting mixture is subsequently buffered with another base mixture containing sodium acetate and acetic acid.

The present inventor has discovered that when producing a color developing dye by printing a diazonium salt on a cellulose material subbed with an alkaline processing liquid containing a coupling component, the printing paste is a first base material containing sodium nitrite. In the method for producing the above-mentioned dye, the second base paste contains an acid, one of the two base pastes is mixed with an amine, and then this dye is mixed with a second base paste. We have discovered a method for producing the above dye, which is characterized by combining two base glues.

In contrast to the known process in which the base (amine) is first dissolved in hydrochloric acid, in the process according to the invention no means for forming the salt of this amine are necessary. Surprisingly, it has been found that in the process according to the invention the acid need not be a mineral acid, but also moderate to weak acids can be used. These moderate to weak acids, especially organic acids, are preferred because they do not require buffering the reaction system and do not pose corrosion problems.

Even if the acid in the process according to the invention is a mineral acid, for example hydrochloric acid, buffering of the reaction system can be avoided. This is because the process can actually be carried out with only stoichiometric amounts or only a slight excess of acid. Furthermore, relatively weak acids offer the advantage that sizing agents that are sensitive to mineral acids can also be used.

The process according to the invention exhibits the additional advantage that it is not limited to amines that are completely soluble in hydrochloric acid. In particular, for example German Patent Specification no.
Finely divided dispersions of solid aromatic amines, such as those described in US Pat. No. 2,346,612, can also be used. This dispersion contains a maximum particle size of less than 0.03mm and a maximum
There is an amine with an average particle size of 0.005 mm.

In addition to the fact that the process according to the invention is no longer subject to any limitations regarding the diazo component, whereas in the known process the diazotization conditions have to be selected in each case for each amine, in the present invention There is also the advantage that all amines can be treated in the same way.

As amines, therefore, basically all amines which are suitable for cold dyeing technology are used. Preferred amines are German Patent Specifications No. 2346612 and No. 2449782
listed in the number. It also describes methods for converting these amines into suitable finely divided dispersions.

For the production of the original glue mixture, modified or degraded locust bean flour or guar products, optionally also cellulose or starch ethers or vegetable mucilage, are used as thickening agents. is preferable.

It is advantageous to use the same sizing agent for each of the two base glue mixtures.

Acids include inorganic and organic acids of moderate to weak strength. In particular, low-molecular-weight aliphatic carboxylic acids such as monochloroacetic acid, glycolic acid, citric acid, tartaric acid, oxalic acid, formic acid, but also, for example, phosphoric acid, are used in amounts of 20 to 80 g per kg of base mixture.

Compounds capable of coupling in the vicinal position of hydroxyl groups, in particular arylamides of aromatic or heterocyclic o-hydroxycarboxylic acids or acylacetic acids, as coupling components for subscribing cellulosic materials, as well as other aromatic Alkaline solutions of group or heterocyclic hydroxy compounds and compounds having enolizable or enolized ketomethylene groups present in the heterocycle are suitable. Such compounds include, for example, 2-hydroxy-3
-naphthoic acid or its derivatives substituted in the 6-position, 2-hydroxy-anthracene-3-carboxylic acid, cresotic acid, halogensalicylic acid, 4
-Hydroxy-diphenyl-3-carboxylic acid, 2
-hydroxy-carbazole-3-carboxylic acid,
5-hydroxy-1,2,1',2'-benzocarbazole-4-carboxylic acid, 3-hydroxy-diphenylene oxide-2-carboxylic acid, 3-hydroxy-diphenylene sulfide-2-carboxylic acid , arylamides such as acetoacetic acid, benzoylacetic acid or terephthaloyl-bis-acetic acid, hydroxybenzenes substituted in the p-position, such as 4-chloro-1-hydroxybenzene, 4-methyl-1-hydroxybenzene, 4 -isopropyl-1-hydroxybenzene, 4-tert-butyl-1
-Hydroxybenzene, 4-acylamino-1-
hydroxybenzene or 3-amino-4-methyl-1-hydroxybenzene, polyhydroxybenzenes such as 1,3-dihydroxybenzene,
1,3,5-trihydroxybenzene, 2,4-
Dihydroxybenzophenone or 1,4-di-
(2′,4′-dihydroxybenzoyl)-benzene,
Hydroxynaphthalenes, such as 2-hydroxynaphthalene, 6-bromo-2-hydroxynaphthalene, 6-methoxy-2-hydroxynaphthalene, 7-methoxy-2-hydroxynaphthalene,
1-acylamino-7-hydroxynaphthalene,
5-chloro-1-hydroxynaphthalene, 4-chloro-1-hydroxynaphthalene, 5,8-dichloro-1-hydroxynaphthalene, 1-acylamino-7-hydroxynaphthalene, 7-benzoylamino-2-hydroxynaphthalene, 1- Hydroxynaphthalene-5-sulfonic acid amide, 1-
Hydroxy-4-methoxy-naphthalene, 1-hydroxy-4-benzoyl-naphthalene, 2-hydroxynaphthalene-3-carboxylic acid methyl ester, 2-hydroxynaphthalene-6-carboxylic acid arylamide, 2-hydroxynaphthalene-6- Sulfonic acid amides or 2-hydroxynaphthalene-6-alkyl sulfones, dihydroxynaphthalenes, such as 1.3-, 2.6- or 2.
7-dihydroxynaphthalene, pyrazolones such as 1-phenyl-5-pyrazolone-3-carboxylic acid amide, 1-phenyl-3-methyl-5-pyrazolone, 1-(4'-chlorophaer)-3-methyl-5 -pyrazolone, 1-(2'.5'-dichlorophenyl)-3-methylpyrazolone-(5) or 1-(naphthyl-2)-3-methyl-5-pyrazolone, or a barbituric acid derivative.

A particularly preferred embodiment of the printing process according to the invention is detailed below: First, two base mixtures are prepared. In this case, the first mixture (mixture) is, for example, diluted locust bean flour ether in a sizing agent of 10 to 30%
g/Kg of sodium nitrite, preferably 15-20
Contains g/Kg of sodium nitrite. Since sodium nitrite can be used in slight excess of the stoichiometrically required amount, nitrite-base mixtures can be used for various amines without the need for precise quantitative adjustments. can.

For the original glue mixture, add the same glue to e.g.
- Mixing with 100 g, preferably 40-50 g of monochloroacetic acid and subsequently bringing the mixture to 1 Kg.

Before the two base mixtures mentioned above are brought together, the amine prepared in each case is added to the mixture in an amount limited by the fabric underlay.

When the original glue mixture is mixed with the original glue mixture with added amine, it is preferred to charge the mixture first and cover it with the second mixture () under stirring.

The printing pastes can additionally contain customary printing auxiliaries such as glycerin, diglycol and dihydroxydiethyl sulfide.

The following examples illustrate in detail the implementation of the invention, but the invention is not limited thereto. The color index numbers listed for the dyes used in the examples are from the 3rd edition (1971
year). References to percentages of substances used according to the invention mean % by weight, unless stated otherwise.

If aqueous dispersions of amines are mentioned, these have an average particle size equal to or smaller than 0.005 mm (corresponding to German Patent Specification No. 23 46 612).

Example 1 A cotton fabric is subbed with an aqueous solution containing 20 g of 2-hydroxy-3-naphthoylamino-benzene and 25 g of caustic soda solution (32.5%) in
and dry. Printing is then carried out using a printing paste, which is prepared as follows: Original glue mixture: 500 g of a 5% aqueous solution of locust bean flower ether as a sizing agent and 16-18 g of sodium sulfite. Mix in.

Add 484-482g of water Make it 1000g.

Original glue mixture: Disperse 50 g of monochloroacetic acid in 500 g of the same sizing agent as for the original glue mixture.

Add 450g of water Make it 1000g.

To produce the printing paste, 300 g of the original paste mixture were first charged, 15 g of a 60% aqueous dispersion of the fast dyeing base CI No. 37085 and 600 g of the original paste mixture were mixed in under stirring, and 85 g of the original paste mixture were mixed in with stirring. Add water to make 1000g.

After printing, dry, rinse, soap under heat,
And swish again.

A deep red print with good fastness properties is obtained.

Example 2 A staple fiber fabric is laid down as in Example 1 and dried. It is then printed with a printing paste of the following composition: 300 g of the original paste mixture from Example 1 22 g of about 45% of the fast dyeing base CI No. 37135
Add to the aqueous dispersion and 600 g of the original paste mixture of Example 1.

Add 78g of water Make it 1000g.

The print is then further processed as in Example 1.
A burgundy print with good fastness properties is obtained.

Example 3 A blended fabric consisting of 50% cotton and 50% staple fiber is laid down as in Example 1 and dried. Thereafter, printing is carried out using a printing paste having the following composition.

600 g of the original paste mixture of Example 1 but containing glycolic acid instead of monochloroacetic acid are charged first. To this are added 25 g of a 30% aqueous dispersion of fast dyeing base CI No. 37235 and 300 g of the original glue mixture from Example 1.

Add 75g of water Make it 1000g.

The print is further processed as in Example 1. A deep blue print with good fastness properties is obtained.

Example 4 A cotton fabric is primed as in Example 1, dried and then printed using a printing paste of the following composition: 300 g of the original paste mixture of Example 1 are charged first.
Add to this the 30g formula A 45% aqueous dispersion of the compound shown below and 600 g of the original paste mixture of Example 1 are mixed.

Add 70g of water Make it 1000g.

The print is post-treated as in Example 1. A black print with good fastness is obtained.

Example 5 Staple fibers are padded with an aqueous solution containing 20 g of 3,3'-dimethyl-4,4'-bisacetoacetylamino-diphenyl in 1 and 15 g of caustic soda solution (32.5%) and dried.
A printing paste of the following composition is then used to print: 300 g of the original paste mixture from Example 1, 12 g of a 50% aqueous solution of the fast dyeing base CI No. 37000, 600 g of Example 1, but instead of monochloroacetic acid. Make up 1000 g with original glue mixture containing citric acid and 88 g water.

The print is further processed as in Example 1. A yellow print with good fastness properties is obtained.

Example 6 Cotton fabric was mixed with 20 g of 5-chloro-2-acetoacetylamino-1,4-dimethoxy-benzene (CI No. 37613), 32 g of ethanol, and 40 g of water.
and padding with an aqueous solution containing 20 g of caustic soda solution (32.5%). The dried fabric is printed with a printing paste of the following composition: 300 g of the original paste mixture from Example 1 with 20 g of a 45% aqueous dispersion of fast dyeing base CI No. 37130 and 600 g of the original paste mixture from Example 1. Mix.

Add 80g of water Make it 1000g.

Post-printing treatment is carried out as in Example 1.

A yellow print with good fastness properties is obtained.

Claims (1)

[Claims] 1. When producing a color developing dye by printing a diazonium salt onto a cellulose material subbed with an alkaline processing solution containing a coupling component, the printing paste is prepared by using a first source containing sodium nitrite. In the method for producing the above-mentioned dye, which is obtained by mixing a glue with a second base glue, the second base glue contains an acid, and an amine is mixed with one of the two base glues, Next, the method for manufacturing the above-mentioned dye is characterized by combining these two base glues. 2. The manufacturing method according to claim 1, wherein the acid is a moderately strong acid to a weak acid. 3. The manufacturing method according to claim 1 or 2, wherein the acid is an organic acid. 4. The production method according to any one of claims 1 to 3, wherein the amine is used as a fine dispersion. 5. The manufacturing method according to any one of claims 1 to 4, wherein the two base glues contain the same sizing agent.