CS260712B1 - Liquid preparation for dye stuffs fastness increase on fibre and method of its production - Google Patents

Abstract

The solution is liquid formulations for increasing the stability of substantive dyes after wet on the basis of dicyandiamidoformaldehyde condensates containing, based on the composition as a whole, by weight of 1.2 to 4 proceta chloride and / or ammonium sulfate and 35 to 50% of water having a liquid consistency even at low temperatures, high and long term stability at normal and elevated temperatures, easy solubility already in cold water and high cationic activity. They are preparing energy saving and economically efficient reaction of dicyandiamide with ammonium chloride and / or ammonium sulfate, s formaldehyde and ammonia.

Description

BACKGROUND OF THE INVENTION The present invention relates to liquid formulations for enhancing the stability of dyes on a fiber and to a process for their preparation.

Preparations for increasing the stability of substantive dyes in wet are characterized by liquid consistency even at low temperatures, high and long-term stability at normal and elevated temperatures, easy solubility already in cold water and high cationic efficiency.

Water-soluble anionic dyes have a strong affinity for cellulose. Their characteristic feature is to get out of the aqueous solution onto cellulose fibers and to attach to them - nouns. The stabilization of the substan- tive dyes with cationic preparations increases the dye molecule stored in the inter-micellar spaces of the cellulose fiber and furthermore decreases its solubility. Both changes prevent easy release of the dye from the fiber, especially when wet treatment of the textile product. In particular, stabilization will increase wet stability.

At present, a variety of liquid and powder formulations, mostly based on dicyandiamidoformaldehyde condensates, are used to fix anionic, water-soluble azo dyes, which have a number of disadvantages.

Powder fixing compositions are prepared from solutions of dicyandiamidoformaldehyde condensates that are poorly stable in aqueous solution, easily condense to a highly viscous to solid, sparingly water soluble material.

According to known methods, cationic fixing agents are prepared based on dicyandiamidoformaldehyde precondensates in an acidic medium and stabilized by drying.

For example, dicyandiamide is condensed in an aqueous medium in the presence of acids to form a water-insoluble condensate with varying amounts of formaldehyde, usually one to three moles of formaldehyde per mole of dicyandiamide.

The resin composition is as follows:

- ý - C Ξ N!

• · - N - C ~ · · J 12.

The condensation product is neutral, soluble in concentrated acids.

The resin thus prepared is treated in an aqueous medium with acetic acid, formic acid, hydrochloric acid, or sulfuric acid to hydrate the nitrile groups resulting in the basicity of the resin, which simultaneously forms a salt with the acid present.

+ t 2 .H 2 O + n CH 2 OOH

-N-CH a nh-co-nh.

CH 2 COO _u

- N - CH -

The reverse procedure is followed for the next production process. The dicyandiamide is treated with a mineral or organic acid in an aqueous medium to obtain a stable salt of the strong organic base of dicyandiamine.

_χ NH-CO-NHr,

HSO ^

Subsequent condensation with formaldehyde in an aqueous medium yields a cationic resin in the form of a water-soluble and dilute acid-soluble organic base sulfate.

Another industrially utilized process is the process wherein the dicyandiamide is heated with ammonium chloride and converted through a biguanide to guanidine chlorohydrate, which is further condensed with formaldehyde to a cationic resin in the form of an organic base chlorohydrate.

NH-CΞΝ

NH II

NH

N H 1, CT HpN ™ CH 2 - CH 2

N He na

HCt h-, ra.

NH \ e Π, \ '-x O

H / ~, \ ί-Ο · NH- Cip \

CH,

H - NH C ™ NH-C Hp ~ / \ ^i! NH (HCl).

ZoOH / H.

The disadvantage of the known methods is the energy-intensive technology. The prepared cationic resin is unstable in aqueous solutions and is stabilized by addition of salts such as sodium acetate and drying.

Addition of sodium acetate to which 0.9 to 1 wt. part per 1 wt. Due to the acidic nature of the resin, acetic acid is released during production and drying. Before drying, which is usually carried out in spray driers, it is necessary to add a solution of sodium chloride or sulfate in an amount of 2.5 to 3 wt. parts of solutions of these salts per 1 wt. a portion of dicyandiamide to reduce resin sticking to the oven walls.

The dried product contains 40 to 50 wt. salts and is difficult to dissolve in water. Before preparing the application solution, the dried product must be crushed in hot water, i.e., a slurry must first be prepared from the powder and then dissolved in warm water, since by direct dosing of the powdered product into warm water poorly soluble lumps of the preparation are formed. The dried preparation, containing anhydrous sodium acetate, is hydrotropic and readily absorbs air humidity, resulting in sticking of the preparation.

These drawbacks are eliminated by liquid formulations for increasing the stability of substantive wet dyes based on dicyandiamidoformaldehyde condensates of the general formula

NH

H ~ c - N H - · CH $ ~ OH L L

I i · í Ή

I | V - · H H - H N N O i i

NiI where n is 4 to 16 and

X is 2HCl or H. SO2 containing, based on the weight of the composition as a whole, 35-50% water and 1.2-4% ammonium chloride and / or sulfate salts.

A method for preparing a stable liquid fixative comprises condensing dicyandiamide with ammonium chloride or sulfate or a mixture thereof with formaldehyde and ammonia by condensing a mixture of 1 mole of dicyandiamide with 2.5 to 3.1 moles of formaldehyde and 1.5 to 2.1 moles. and / or 0.75 to 1.55 moles of ammonium sulfate and 0.1 to 0.33 moles of ammonium hydroxide at 90 to 125 ° C.

It has been found that the addition of ammonia, preferably ammonia water, before or during condensation in an amount of 0.1 to 0.3 moles per mole of dicyandiamide yields a stable, slightly viscous aqueous solution of dicyandiamidoformaldehyde condensate (resin) which dissolves well already in cold water. The fixative prepared in this way achieves a high efficiency, which is not known in the liquid formulations produced so far and is comparable with powder formulations by its high efficiency.

The use of alkaline ammonium salts and other nitrogen bases, for example, ammonium phosphate, ammonium carbonate, hexamethylenetetramine, triethanolamine and pyridine, has also been verified. However, none of these substances achieved results such as ammonia in the form of ammonia water, both in the viability of the process technology and in the quality and efficacy of the formulation.

For example, when using ammonium carbonate, comparable results to ammonia can be achieved, but the reaction process produces a sharp discharge of carbon dioxide, which causes severe foaming even with slow dosing. The resulting foam hardly falls off and therefore this salt is not suitable for industrial production of the formulation.

When hexamethylenetetramine and / or triethanolamine are used, the formulation has a high viscosity, is poorly water soluble and has a lower cationic activity. Salts are excreted from preparations prepared using alkaline phosphates, which also have lower potency. Using pyridine also results in lower efficiency, high viscosity and, moreover, an unpleasant odor of the formulation.

Formulations for enhancing wet stability are equally effective whether the organic base chloride or sulfate, or a mixture thereof.

The preparations according to the invention belong to the group of cationic preparations which substantially increase the stability of substantive dyes and prints on cotton, flax, pulp, viscose, copper and acetate rayon, as well as mixtures of these fibers with webs of animal origin against water, sea water, moisture , sweat, wet ironing, dressing, sizing, wet brushing, coloring, kicking and home washing.

The solutions of the formulation according to the invention are stable to the water hardness of the diluted acids and bases as well as the metal salts, which makes it possible to use it in combination with metal salts, thereby increasing both the wet and light and color fastnesses. salts is not effective. This extends the possibility of using substantive dyes even in cases where universal stability is required.

The formulations according to the invention are highly stable, their fixing efficiency did not change even after 18 months of storage at normal temperatures. The viscosity and color also remain unchanged. When stored at extremely low temperatures, i.e. -15 to 25 degrees Celsius, they solidify, but when heated to -5 to 0 ° C they reversibly into solutions.

Example 1

Cotton fabric "Callot" dyed with Saturn red F 3B (C.I. Direct Red 80) was stained thoroughly with water by dyes adhering to the surface of the fiber. A 1% solution of the preparation was prepared in the fixture of the tub with a sash (so-called long bath).

The cotton fabric was held in this solution for 30 minutes at 27-29 ° C. The fabric was then stripped of the fixing solution, rinsed with water and dried.

The fixation efficiency of the formulation was determined on a companion fabric of the same material and wool. Stability tests were performed on a dyed fabric without stability in the formulation as compared to the fabric established in the formulation by water, sweat and washing tests.

The three figures of stability data express:

Changing shades of orig. an embossing sample on a backing fabric of the same material and a specimen after the embedding test on a wool backing fabric

Color fastness is graded by numbers up to 5, that is from lowest to fastest.

Saturn water red

F3B:

sweat pH 5.5 sweat pH 8 wash 40 ° C

1—2 1—2 1—2 3 unsteady 4—5 3—4 3—4 3—4 3—4 4—5 ' 4 4-5 4-5 4—5 4—5 3—4 settled 4—5 4—5 4—5 4—5 4 4-5 4—5 4—5

Example 2

The cotton-linen composite fabric dyed with Saturn Bord LB (C.I. Direct Red 99) was freed from the dye adhering to the fiber surface by thorough rinsing in water.

A Foulard fixture was prepared with a 1% fixture solution. The blended fabric was fixed in the solution of this formulation for 30 minutes at 25 ° C

Saturn water pot pH 5.5 hordo LB degrees Celsius. The fabric was then drained, rinsed with water and dried.

The fixation efficacy of the preparation was tested on a companion fabric of the same material, i.e. on a cotton-linen and wool blend fabric. Stability tests were performed on a non-stabilized dyed fabric and compared to a fabric stabilized in a 1% solution formulation by water stability tests at 30 ° C of sweat and washing.

sweat pH 8 wash ° C

1 1 1 2 unsteady 4 2—3 4 3—4 3—4 3—4 3 4—5 4—5 4—5 3-4 3—4 settled 4 4—5 3—4 4-5 3—4 4—5 4—5 4-5

Example 3

Linen fabric stained with Saturn Blue LBRR (C.I. Direct Blue 71) was freed from the dye adhering to the fiber surface by thorough rinsing in water.

A 2% fixative solution was prepared in a continuous short pass fixture.

The linen fabric was fixed in the solution of this preparation for 8 minutes at 60 ° C. The fabric was then stripped of the fixing solution, rinsed with water and dried. The fixation efficacy of the formulation was tested on an accompanying fabric of the same material, i.e., flax, and then on wool. The stability tests were carried out on the dyed non-stabilized fabric and compared to the fabric stabilized in the formulation by the water, sweat and wash stability tests.

Saturns blue LBRR water sweat pH 5.5 1 1 unsteady 3—4 3-4 3—4 3—4 4—5 4-5 settled 4-5 4 4-5 4—5 Example 4 Fabric of acetate silk-

LG Saturn Turquoise Blue (C.I. Direct Blue 86) was rinsed thoroughly in water and stripped of dye adhering to the fiber. In a Foulard fixture, a 1% fixture solution was stored at room temperature for 18 months prior to use. The dyed fabric was fixed in this solution at 45 ° C for 30 minutes. After settling, it was rinsed with water and dried. Light stability was determined by xenotest on a steady and unsteady sample of acetate silk fabric.

The light fastness has 8 degrees of fastness. 1 - (very low) to 8 - (excellent).

Measurement result:

sweat pH 8 wash ° C

1 2 3—4 3—4 3—4 4—5 4—5 3—4 4—5 4—5 4—5 4-5 Stability in the light nonwoven fabrics 4 to 5. Stability in the light steady fabrics 6 to 7.

Example 1 a d 5

In a 3.5-meter cubic enamelled reactor equipped with a stirrer and a duplicator for heating and cooling, 1000 kg of 37% w / w foirmaldehyde was added to which 600 kg of dicyandiamide and 580 kg of ammonium chloride were added with stirring. 80 kg of ammonia water containing 25 wt. ammonia. The reaction heat was heated to 85 ° C and then heated to boiling, i.e. 118 ° C. After 20 minutes, when the boiling was complete, an additional 460 kg of mild formaldehyde was added to the reaction mixture for 30 minutes. After impregnation of this amount of formaldehyde, the boiling point dropped to 108 ° C. The reaction mixture was maintained at this temperature for 45 minutes and then cooled to 60 degrees Celsius and discharged. A clear, slightly viscous formulation with high cationic activity was obtained.

Example 6

900 kg of 37% by weight of formaldehyde were charged to the enamelled reactor, and 950 kg of ammonium sulfate and 600 kg of dicyandiamide were added with stirring. The reaction mixture was heated to boiling point 120 ^DEG C., 150 g of ammonia water containing 25% ammonia were allowed. After. the boiling, which lasted 20 minutes, was. 850 kg of formaldehyde was added to the reaction mixture over 30 minutes. During the addition of formaldehyde, the reaction mixture was maintained at a gentle boiling, which was reduced to 105 ° C after addition of all formaldehyde. The reaction mixture was then held at 95-105 ° C for a further 90 minutes, then cooled to 60 ° C, 300 L of water was added and discharged from the reactor. A clear, slightly viscous liquid fixative with high cationic efficiency was obtained.

Example 1 a d 7

400 kg of formaldehyde at a concentration of 37 percent by weight were charged to the enamelled reactor. and 400 kg of water and added with stirring. 410 kg of ammonium sulfate, 340 kg of ammonium chloride and 600 kg of dicyandiamide. The reaction mixture was heated to boiling, i.e. to 120 ° C, and at this temperature 120 kg of ammonia water containing 25 wt. ammonia. Then it was until. 1220 kg of 37 wt.% formaldehyde were added to the reaction mixture under gentle boiling. and the reaction mixture was maintained at 105 ° C for 45 minutes. The reactor contents were then cooled to 60 ° C and drained. A clear, slightly viscous liquid fixative with high cationic efficiency was obtained.

Claims (2)

Liquid preparation for enhancing the stability of dyes on the fiber based on dicyandiamidoformaldehyde condensates of the general formula I nh / II - M · C · N HCH / · On / On V-N-C-NH ....... CH 2 - / OH In H NH where n is 4 to 16 and X is 2 HCl or. H2SO4, characterized in that it contains from 35 to 50% by weight of the composition as a whole. % water and 1.2 to 1.4 wt. chloride and / or. ammonium sulfate. Process for the preparation of a liquid preparation of the formula I according to claim 1, characterized in that a mixture of 1 mole of dicyandiamide with 2.5 to 3.1 mole of formaldehyde in the presence of 1.5 to 2.1 mole of ammonium chloride and / or 0 is condensed. 75 to 1.55 moles of ammonium sulfate and 0.1 to 0.3 moles of ammonium hydroxide at 90 to 120 ° C for 60 to 120 minutes.