JPH0678554B2 - Detergent for re-washing textile prints or dyeings with reactive dyes - Google Patents

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention is a substantially water-free (excluding water of crystallization) composition that can be used to re-wash a print or dye obtained by printing or dyeing a cellulose-containing fiber material with a reactive dye. , Or an aqueous detergent composition and a washing method using the same. The detergent composition according to the present invention is particularly suitable for rewashing with mineral-rich hard water.

The composition according to the present invention is characterized by containing the following components (A) and (B).

(A) at least one inorganic salt which belongs to a polyphosphate or silicate of an alkali metal such as sodium or potassium and is soluble or dispersible in water; and (B) a salt of a monomeric hydroxycarboxylic acid or a polymer fat. Group carboxylic acid salts.

In addition to the components (A) and (B) mentioned above, the compositions according to the invention can also contain further additives and auxiliaries.

Components (A) and (B) can each be present as a single compound or as a mixture. However, it is preferably used as a single compound.

It is particularly preferred that the composition according to the invention contains the components in the following amounts, based on the total amount of the composition.

Component (A) 40 to 85% by weight, component (B) 3 to 40% by weight, preferably 3 to 30% by weight, and additives and auxiliaries 0 to 30% by weight.

As the component (A), which is a novel active ingredient peculiar to the present composition, which is suitable as a re-washing agent, a water-soluble alkali metal metasilicate is suitable, and a ratio of Na ₂ O: SiO ₂ is preferably
Sodium silicate of 1: 1 to 1: 3.5, especially the alkali metal metasilicates, especially pentametahydrate or decahydrate of meta-potassium or sodium metasilicate. Magnesium silicate is also preferred.

Also very suitable as component (A) are sodium diphosphate, sodium tripolyphosphate and the corresponding potassium salts.

A particularly preferred component (A) is sodium metasilicate nonahydrate.

As component (B), alkali metal salts of aliphatic mono- or polycarboxylic acids containing hydroxyl groups having 3 to 10 carbon atoms, such as sodium, potassium or lithium salts, can be used advantageously. Examples of the above-mentioned carboxylic acids include glycolic acid, lactic acid, hydroxyacrylic acid, hydroxybutyric acid, tartaric acid, citric acid and 2,2 '.
-Dihydroxysuccinic acid, gluconic acid, mannonic acid, glyceric acid, biscarboxymethylglyceric acid, triscarboxymethylglycerol and the like.

Also suitable are polymeric carboxylic acids having a molecular weight of at least 450 in the form of water-soluble sodium, potassium or ammonium salts. Among these polymers, preferred are those obtained by polymerizing ethylenically unsaturated mono- or di-carboxylic acids having 3 to 7 carbon atoms,
For example, polyacrylic acid, or polymers of methacrylic acid, citric acid, α-hydroxyacrylic (methacrylic) acid, maleic acid, itaconic acid, teraconic acid, fumaric acid, citraconic acid or mesaconic acid, and copolymers of these carboxylic acids. Polymers, or copolymers of these carboxylic acids with vinyl compounds, especially C ₂ -C ₄ -olefins such as ethylene, propylene, isoptylene or acrylonitrile, acrylamide, vinyl acetate, vinyl propionate, vinyl alkyl ethers or styrene. is there.

In particular, the following have been found to be useful as component (B).

(A) sodium gluconate or especially trisodium citrate, (b) partially hydrolyzed polymaleic anhydride, which is in principle partly in the form of a water-soluble salt, and preferably has a molecular weight of 500 to 5000. (C) Polyacrylic acid or acrylic acid which is present in the form of a water-soluble sodium salt or potassium salt, preferably has a viscosity of 1000 to 3000 m · Pa · s at 20 ° C., and a molecular weight of 5000 to 100000. Copolymer with acrylonitrile or acrylamide.

In addition to the components (A) and (B) described above, the novel compositions according to the invention can additionally contain, as component (C), a mixture of monomeric and oligomeric phosphorus compounds of the formula:

In the formula, Y represents hydrogen or -CO-T, R, T, and X each represent alkyl having 1 to 4 carbon atoms, and m is a number of 1 to 15.

Examples of the alkyl group represented by R, X, T in the phosphorus compound of the formula (1) are methyl, ethyl, n-propyl, isopropyl,
It is n-butyl, sec-butyl, isobutyl, etc., with methyl being preferred.

When Y means -CO-T, T and R preferably mean the same. However, Y is preferably hydrogen. m is preferably a number from 1 to 12. in this case,
It is preferable that a monomer and an oligomer having an average value of m of 2 to 9 form the main component of the mixture.

These mixtures are known per se and are prepared by known methods. That is, for example, it is produced by reacting phosphorus trichloride with acetic acid and optionally acetic anhydride in an aqueous medium.

The amount of component (C) in the composition is 0 to 15% by weight,
If present, it is preferably based on the total amount of the composition.
0.1 to 12% by weight.

As another additional component [component (D)] in the composition, the formulation of the present invention comprises aldose and ketose type monosaccharides or hydrogenated products thereof (having 4 to 7 carbon atoms in the molecule). Can be included. For example,
It may contain fructose, maltose, sorbose or especially glucose, sorbitol or mannitol.

The suitable amount of monosaccharide added to the composition to achieve rapid dispersibility in a short time is in the range of 5 to 10% by weight, based on the total amount of the composition according to the invention.

A sometimes preferred composition according to the invention comprises at least the following components:

(Aa) sodium metasilicate, (Bb ₁ ) trisodium citrate or (Bb ₂ ) aqueous solution of a polymer of ethylenically unsaturated monocarboxylic acid or dicarboxylic acid having 3 to 5 carbon atoms or (Bb ₃ ) glucone Combination of sodium acid with an aqueous solution of a mixture of monomers and oligomers of phosphorus compounds of the formula: (Where m ₁ is a number from 1 to 12).

The compositions (Aa) + (Bb ₂ ) and (Aa) + (Bb ₃ ) preferably additionally contain a monosaccharide.

The re-washing agent according to the present invention can be produced by simply stirring and mixing the components (A) and (B), and optionally (C) and / or (D) in water or without water. The resulting mixture is homogeneous and, when it is an aqueous composition, has good storage stability at room temperature and does not precipitate.

The water-free detergent according to the invention has the following composition as basic constituent (amount based on total composition):

Ingredient (A), especially sodium metasilicate 65-85% by weight
And component (B), especially 15 to 35% by weight of trisodium citrate.

The aqueous composition preferably has the following composition (amount based on total composition):

Component (A), especially sodium metasilicate 40 to 60% by weight, component (B) 5 to 35% by weight, component (C) 5 to 15% by weight, component (D) 0 to 15% by weight, preferably 3 to 12 %, And at least 25% water.

If desired, the composition according to the invention can also contain substances such as: Acetic acid ester, malonic acid diester, succinic acid diester, adipic acid diester, 2-ethylhexanol, neopentyl glycol, benzyl alcohol, furfuryl alcohol, alkylbenzene, tetralin, decalin, paraffin oil or silicone oil, or ethylene bis fatty acid amide. No addition of fatty alcohol polyglycol ether is necessary.

The composition according to the invention is particularly preferably used for rewashing dyeings or prints of cellulosic fiber materials or of mixed fabrics of cellulose with synthetic organic materials such as linear polyesters or modified celluloses (cellulose esters). As the cellulose, both natural cellulose and regenerated cellulose are considered. It can be, for example, hemp, flax, jute, viscose rayon, staple rayon or especially cotton. In the case of mixed fibrous materials, the polyester part can also be dyed before or after cellulose dyeing. In addition, the dyeing or printing of the cellulose-containing fiber material referred to in the present specification is understood as a dyeing or printing obtained by dyeing or printing a cellulose-containing fiber material by any method using a reactive dye. I want to be done. in this case,
The composition according to the invention is used for post-treatment.

The material to be dyed can be in any processed form. For example, it may be in the form of flocs, twisted and pre-stretched staple fiber bundles, filaments, yarns, especially woven or knitted fabrics. Reactive dyes are the usual anionic dyes that chemically bond with cellulose, such as Color Index 3rd Edition (1971), Volume 3, pages 3391-3562, "Reac.
Refers to dyes described as "tive Dyes".

The composition according to the invention makes it possible to wash the dyeings or prints made with the above-mentioned reactive dyes directly with hard water (miscellaneous water) such as tap water. With the composition according to the invention, the hardness of water can be eliminated without the addition of electrolytes, ion exchangers and / or complexing agents as is conventional. Of particular note is that water hardness can be eliminated without the use of phosphate containing compounds such as phosphonic acids and inorganic phosphates. This means that the use of phosphate-containing compounds has recently become increasingly restricted from an ecological standpoint and legislative measures requiring the use of non-phosphate-containing products have been strengthened. This is an important advantage if you consider it.

The invention therefore also relates to a process for printing or dyeing cellulose-containing fiber materials with reactive dyes and washing the dyeings or dyeings with the detergents according to the invention. A feature of the method of the present invention is that the print or dye is preferably 60
The composition according to the invention at a temperature of from 100 to 100 ° C.
The treatment is carried out in an aqueous laundry bath containing an amount of 10 to 10 g /. After treatment, the textile material is removed from the wash bath and washed with fresh water until the wash bath components are completely removed. As a result, a printed material in which the white background portion is not contaminated can be obtained. Further, a dyed product having desired wet fastness, particularly washing fastness can be obtained by the exhaust method.

Hereinafter, the present invention will be further described with reference to examples. Parts in the examples are parts by weight and percentages are percentages by weight.

Production Example Example 1 800 g of sodium metasilicate nonahydrate and 200 g of trisodium citrate are mixed in a ball mill to homogenize.

Aqueous formulations can be made from this powdery mixture before use. However, it is also possible to add the powder mixture directly to the bath at the time of use.

Example 2 A stirring vessel is charged with the following ingredients and continuously stirred and mixed at room temperature.

Sodium metasilicate nonahydrate 500 g, hydrolyzed polymaleic anhydride (50%) (sodium salt) 400 g, sugar 100 g.

This gives a storage-stable, homogeneous, low-viscosity solution.

Example 3 A stirring vessel is charged with the following ingredients and continuously stirred at room temperature to mix.

Sodium metasilicate nonahydrate 500 g, polyacrylic acid (viscosity at 23 ° C 1600 mPas) 300 g, water 200 g.

This gives a storage-stable homogeneous solution.

Example 4 The following ingredients are charged in a stirring container and continuously stirred and mixed at room temperature.

Sodium metasilicate nonahydrate 500 g, sodium gluconate 45 g, mixture of monomer and oligomer of phosphate ester of the following formula 116 g, 100g sugar, 309g water.

This gives a storage-stable solution.

Example of use Example 5 A) Bleached and mercerized cotton knitted fabric (195 g / m
² ) 10 kg was immersed in a closed Wins dyeing machine and immersed in 400 water containing the following substances.

400g dye of the following formula, Sodium chloride 32Kg, m-nitrobenzenesulfonic acid sodium salt) 800g.

The dyebath is then heated to a temperature of 95 ° C and then 85 ° C.
The temperature was held for 30 minutes.

After this, 8 kg of sodium carbonate and 1.2% of sodium hydroxide solution (30%) were added to the dyebath and the fabric was dyed at 85 ° C. for a further 60 minutes. The bath was allowed to cool, the dyeings were rinsed and dried.

B) Three sample pieces of the cotton knitted fabric dyed in the above (A) were respectively subjected to the following three types of washing baths in Ahiba-
Using a dyeing machine, a bath ratio of 1:50 was applied for 20 minutes under boiling.

1. Deionized water.

2. Water with a hardness of 20 ° dH (German hardness).

3. Water with a hardness of 20 ° dH + 4 g of the composition produced in Production Example 1
.

Then, combine each sample piece together with Permutit:
It was washed with cold water treated with an ion exchange resin (trade name).

These dyed and treated specimens were spun down to 100% squeeze and tested for wet iron fastness according to Swiss Standard SNV-Norm19832. That is, a white cotton cloth is put in distilled water to be moistened and centrifugally dehydrated to a squeezing ratio of 100%. A piece of dyed moist knitted fabric is placed on a dry cotton white cloth, and the above-mentioned moistened white cotton cloth (adjoining cloth) is placed thereon. The dyed sample pieces are ironed together with the iron set at a temperature of 180 ° C. on the cloths thus laminated. Iron for 2 minutes. After that, color transfer (contamination) to the white cotton accompanying cloth that had been pre-moistened.
The iron fastness of the dyed sample piece is determined by checking the presence or absence of the above.

As a result of this test, the dyed sample pieces obtained in the selective bath 3 did not contaminate the white cotton companion cloth at all. On the other hand, the dyed sample pieces washed in the washing baths 1 and 2 strongly contaminated the white cotton accompanying cloth.

Example 6 A) Bleached and mercerized cotton satin (120 g / m
² ) was applied to a Rolex-type printing machine to print 1 kg of the printing paste having the following composition.

Original paste consisting of the following ingredients 900g: 5% algin paste ・ ・ 550 parts urea ・ ・ ・ 150 parts sodium m-nitrobenzenesulfonate ・ ・ ・ 10 parts 30% sodium carbonate solution ・ ・ 60 parts water ・ ・ ・ 230 parts 50g dye of the following formula, 50 g of water.

After printing, the fabric was steamed at 101 ° C. for 8 minutes and then rinsed with cold water for 5 minutes.

B) The following three types of washing baths were prepared and heated to the boiling temperature (98 ° C).

1. Deionized water.

2. Water with a hardness of 20 ° dH.

3. Water with a hardness of 20 ° dH + 4 g of the composition produced in Production Example 1
.

Each of the three sample pieces printed in (A) was placed in the washing bath, and treated at a bath ratio of 1:60 under boiling for 5 minutes. After treatment, it was rinsed with cold water and air dried.

As a result, no contamination was found in the non-printed white background portion of the printed sample piece obtained by using the washing bath 3. On the other hand, the white background portions of the printed sample pieces treated with the washing baths 1 and 2 were strongly contaminated.

Example 7 A) Mixed woven fabric of polyester 67% and cotton 33% (208 g /
m ² ) was applied to a Schablone type printing machine and printed using a printing paste having the following composition.

Original paste consisting of the following ingredients 93g: Algin paste ・ ・ 500 parts Urea ・ ・ ・ 50 parts Atrium carbonate ・ ・ ・ 8 parts Water ・ ・ ・ 442 parts Dye of the following formula 30g, 32g of dye of the following formula.

After printing, the woven fabric was placed in a high temperature (HT) steamer at 180 ° C for steaming for 8 minutes and then rinsed with cold water for 5 minutes.

B) The following three types of washing baths were prepared and heated to the boiling temperature (98 ° C).

1. Deionized water.

2. Water with a hardness of 20 ° dH.

3. Water with a hardness of 20 ° dH + 4 g of the composition produced in Production Example 1
.

Three pieces of the mixed woven cloth printed in the above (A) were put in the washing bath one by one, and treated at a bath ratio of 1:60 for 5 minutes under boiling. After treatment, it was rinsed with cold water and air dried.

As a result, no contamination was found in the non-printed white background portion of the printed sample piece obtained by using the washing bath 3. On the other hand, the white background portions of the printed sample pieces treated with the washing baths 1 and 2 were strongly contaminated.

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Claims (18)

[Claims] 1. At least one inorganic salt which belongs to (A) an alkali metal polyphosphate or silicate and is soluble or dispersible in water, and (B) a salt of a monomeric hydroxycarboxylic acid or a polymer fat. A water-free or aqueous detergent, characterized in that it contains a salt with a group carboxylic acid. 2. The detergent according to claim 1, wherein the component (A) is an alkali metal metasilicate. 3. The component (A) has a Na ₂ O: SiO ₂ ratio of 1: 1 to 1: 3.
The detergent of claim 1 which is sodium silicate which is 5. 4. The detergent according to claim 1, wherein the component (A) is sodium metasilicate nonahydrate. 5. The detergent according to claim 1, wherein component (B) is an alkali metal salt of an aliphatic mono- or poly-carboxylic acid containing 3 to 10 carbon atoms and a hydroxyl group. 6. The detergent according to claim 5, wherein the hydroxycarboxylic acid is citric acid. 7. The detergent according to claim 5, wherein the hydroxycarboxylic acid is gluconic acid. 8. A detergent according to claim 1, wherein component (B) is a polymeric aliphatic carboxylic acid in the form of a sodium salt, potassium salt or ammonium salt having a molecular weight of at least 450. 9. A detergent according to claim 8 wherein the polymeric carboxylic acid is an incompletely hydrolyzed polymaleic anhydride having a molecular weight of 500 to 5000. 10. The polymer carboxylic acid is a polyacrylic acid having a viscosity at 20 ° C. of 1000 to 3000 m · Pa · s.
Detergent described. 11. Detergent according to claim 1, which additionally contains, as component (C), a mixture of monomeric and oligomeric phosphorus compounds of the formula: (In the formula, Y represents hydrogen or -CO-T, R, T, and X each represent alkyl having 1 to 4 carbon atoms, and m is a number of 1 to 15). 12. The detergent according to claim 1, which comprises sodium metasilicate (A) and trisodium citrate (B). 13. Detergent according to claim 1, containing sodium metasilicate (A) and an aqueous solution (B) of polymerized ethylenically unsaturated mono- or dicarboxylic acid having 3 to 5 carbon atoms. 14. A formula of sodium metasilicate (A) and sodium gluconate (B) The detergent according to claim 11, which contains an aqueous solution (C) of a mixture of monomers and oligomers, wherein m ₁ is a number from 1 to 12. 15. Detergent according to claim 1, containing 65 to 85% by weight, based on the total mixture, of sodium metasilicate and 15 to 35% by weight of trisodium citrate. 16. 40 to 60% by weight of sodium silicate, 5 to 35% by weight of component (B) and additionally 5 to 15% by weight of component (C), based on the total mixture.
The detergent according to claim 11, which comprises: 17. The detergent according to claim 16, which contains 3 to 12% by weight of a monosaccharide as an additional component (D). 18. A method of washing a printed material or a dyed material obtained by printing or dyeing a cellulose-containing fiber material with a reactive dye, the method comprising the step of washing the printed material or the dyed material with an aqueous washing bath containing the detergent according to claim 1. A method of processing.