JPH02245096A - Detergent for rewashing material printed or dyed with fiber-reactive dye - Google Patents

Abstract

PURPOSE: To obtain a detergent desirable for use in re-washing with hard water by mixing a water-soluble to water-dispersible alkali metal polyphosphate or silicate with a monomer hydroxycarboxylate or a polymer aliphatic carboxylate.

CONSTITUTION: At least one water-soluble or water-dispersible inorganic salt belonging to an alkali metal polyphosphate or silicate (e.g. sodium metasilicate nonahydrate) is mixed with a monomer hydroxycarboxylate (e.g. sodium gluconate) or a polymer aliphatic carboxylate (e.g. imperfectly hydrolyzed polymaleic anhydride having a molecular weight of 500-5,000). The obtained mixture can give a water-free or aqueous detergent composition which can be used to re-washing a printed or dyed piece prepared by printing or dyeing a fibrous cellulosic material with a reactive dye. This composition is particularly desirable in re-washing with mineral-rich hard water.

COPYRIGHT: (C)1990,JPO

Description

DETAILED DESCRIPTION OF THE INVENTION The present invention provides a material which is substantially water-free (excluding water of crystallization) and which is used for rewashing printed or dyed products of cellulose-containing textile materials printed or dyed with reactive dyes. , or relates to an aqueous detergent composition and a washing method using the same. The detergent composition according to the present invention is particularly suitable for rewashing using hard water with a high mineral content.

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

(A) at least one inorganic salt belonging to the polyphosphates or silicates of alkali metals such as sodium or potassium and soluble or dispersible in water; (B) salts of monomeric hydroxycarboxylic acids or polymeric fats; Salts of group carboxylic acids.

In addition to the aforementioned components (A) and (B), the compositions according to the invention may also contain additional additives and auxiliaries.

Components (A) and (B) can each be present as a single compound or as a mixture.

However, it is preferable to use it as a single compound.

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

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

Component (A), which is the unique active substance of the new composition suitable as a rewashing agent, is suitably a water-soluble alkali metal metasilicate, preferably Na2O: 5i
Sodium silicates with an Oz ratio of I to 1:3.5, in particular alkali metal metasilicates, especially penta- to mesohydrates of 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.

Component (B) has 3 to iog4 carbon atoms. Alkali metal salts of aliphatic mono- or polycarboxylic acids containing hydroxyl groups, such as the sodium, potassium or lithium salts, are preferably used. Examples of the above-mentioned carboxylic acids include glycolic acid, lactic acid, hydroxyacrylic acid, hydroxybutyric acid, tartaric acid, citric acid,
, 2'-dihydroxysuccinic acid, gluconic acid, mannonic acid, glycerin, carboxymethylglycerin, tricarboxymethylglycerol, etc.

Furthermore, polymeric carboxylic acids having a molecular weight of at least 450 in the form of water-soluble sodium, potassium or ammonium salts are also suitable. Preferred among these polymers are polymerized ethylenically unsaturated mono- or dicarboxylic acids having 3 to 7 carbon atoms, such as polyacrylic acid, or methacrylic acid, citric acid, alpha-hydroxy Polymers of acrylic (methacrylic) acid, maleic acid, itaconic acid, terraconic acid, fumaric acid, citraconic acid or mesaconic acid, and copolymers of these carboxylic acids, or vinyl compounds with these carboxylic acids, especially C2C4- Olefins such as ethylene, propylene, isobutylene or copolymers with acrylonitrile, acrylamide, vinyl acetate, vinyl propionate, vinyl alkyl ethers or styrene.

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 as a rule is partially in water-soluble salt form and preferably has a molecular weight between 500 and 5000; (c) present in the form of a water-soluble sodium or potassium salt, preferably having a viscosity of 1000 to 3000 I at 20°C;
-Pa-5 and a molecular weight of 5000 to touoo, a polyacrylic acid or a copolymer of acrylic acid and acrylonitrile or acrylamide.

In addition to the components (A) and (B), the novel composition according to the invention additionally comprises a component (C).
contains a mixture of monomers and oligomer phosphorus compounds of the following formula: where Y is hydrogen or -Co-T
, R, T, and X each represent alkyl having 1 to 44 vJ of carbon atoms, and m is a number of 1 to 15.

Examples of the alkyl group represented by R, .

When Y or -CO-T is meant, T and R preferably mean the same thing. However, Y is preferably hydrogen. Preferably, m is a number from 1 to 12. In this case, it is preferable that monomers and oligomers in which the average value of m is 2 to 9 constitute the main components of the mixture.

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

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

As other additional ingredients in the composition [component (D)], the formulations according to the invention contain monosaccharides of the aldose and ketose type or their hydrogenation products (having 4 to 7 carbon atoms in the molecule). can contain. for example,
It may contain fructose, maltose, sorbose or especially glucose, sorbitol or mannitol.

A suitable amount of monosaccharide added to the composition necessary to achieve rapid dispersibility in a short time ranges from 5 to 10% by weight, based on the total weight of the composition according to the invention.

Particularly preferred compositions according to the invention contain at least the following components:

(Aa) sodium metasilicate, (Bb+) trisodium citrate, or (Bb2) an aqueous solution of a polymer of ethylenically unsaturated monocarboxylic or dicarboxylic acid having 3 to 5 carbon atoms, or (Bb+) sodium gluconate; A combination of a mixture of monomers and oligomers of a phosphorus compound of the following formula with an aqueous solution: (wherein ffi is a number from 1 to 12).

Compositions (A a) + (B b2)S and (A a
) + (B b3) preferably additionally contains a monosaccharide.

The rewashing agent according to the invention can be prepared simply by 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, if an aqueous composition, has good storage stability at room temperature and does not form a precipitate.

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

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

The aqueous composition preferably has the following composition (amounts are based on the total composition).

Component (A), in particular 40-60% by weight of sodium metasilicate; Component (B) 5-35% by weight; Component (C) 5-15% by weight.

Component (D) from 0 to 15% by weight, preferably from 3 to 12% by weight, and at least 25% by weight of water.

If desired, the composition according to the invention can also contain the following substances: Acetate 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. Addition of fatty alcohol polyglycol ethers is not necessary.

The compositions according to the invention are particularly preferably used for rewashing dyeings or prints of cellulose fiber materials or fabrics of mixtures of cellulose and synthetic organic materials, such as linear polyesters or modified cellulose (cellulose esters). 3. As cellulose, both natural cellulose and regenerated cellulose are considered. For example, it can be hemp, flax, jute, viscose rayon, stable rayon or especially cotton. In the case of mixed fiber materials, the polyester parts can also be dyed before or after cellulose dyeing. In addition, the dyed or printed product of cellulose-containing fiber material as used herein is understood to mean a dyed or printed product obtained by dyeing or printing a cellulose-containing fiber material by any method using a reactive dye. I want to be

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 can be in the form of flocks, twisted and predrawn stable fiber bundles, filaments, yarns, especially woven or knitted fabrics. Reactive dyes are ordinary anionic dyes that chemically bond with cellulose, such as color dyes.
Index 3rd edition (1971), Volume 3, 3391
This refers to the dyes described as "Reactive Dyes" on pages 3562 to 3562.

The composition according to the invention makes it possible to wash dyed or printed articles produced using the above-mentioned reactive dyes with good results even when hard water (miscellaneous water) such as tap water is used directly. Using the compositions according to the invention, water hardness can be eliminated without the conventional addition of electrolytes, ion exchangers and/or complexing agents. Of particular note is that water hardness may be eliminated without the use of phosphate-containing compounds such as phosphonic acids or inorganic phosphates. This indicates that the use of phosphate-containing compounds is increasingly being restricted in recent years from the standpoint of ecological protection, and that legislative measures are being strengthened mandating the use of phosphate-free products. This is an important advantage if you consider it.

The invention therefore also relates to a method for washing prints or dyeings of cellulose-containing textile materials printed or dyed with reactive dyes using the detergents according to the invention. A feature of the method of the invention is that the printed or dyed material is preferably
The treatment is carried out in an aqueous washing bath containing the composition according to the invention, preferably in an amount of 1 to 10 g/l, at a temperature of 0 to 100°C.

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 product is obtained in which the white background area is not contaminated.

Furthermore, dyeings having the desired wet fastness properties, especially washing fastness properties, are obtained by the exhaust method.

Hereinafter, the present invention will be further explained by examples. In the examples, parts are parts by weight and percentages are percent by weight.

Production Example "Example 1" 2 800 g of sodium metasilicate nonahydrate and 200 g of trisodium citrate are mixed in a ball mill to make them homogeneous.

An aqueous formulation can be prepared from the powdered mixture of Part 1 before use. However, the powder mixture can also be added directly to the bath at the time of use.

1 liter Load the following ingredients into a stirring container and mix by continuous stirring at room temperature.

Sodium metasilicate nonahydrate 500g.

400 g of hydrolyzed polymaleic anhydride (50%) (sodium salt).

Sugar 100g.

This results in a storage-stable, homogeneous, low-viscosity solution.

The following ingredients are loaded into a negative stirring vessel and mixed by continuous stirring at room temperature.

Sodium metasilicate nonahydrate 500g.

Polyacrylic acid (viscosity 1600m/Pa-5 at 23°C)
300g.

200g water
.

This results in a storage-stable, homogeneous solution.

Support Team A: Load the following ingredients into a stirring container and mix by continuous stirring at room temperature.

Sodium metasilicate nonahydrate% 500g.

Sodium gluconate 45g.

Monomer of phosphate ester of the following formula and oligosaccharide 100g.

water 309g.

This results in a storage-stable solution.

A) Made of bleached and mercerized cotton #! (19
5g/rrr') L OKg was placed in a closed Wince dyeing machine and immersed in 400 g of water to which the following substances were added.

The dyeing process was carried out using an Ahiba dyeing machine under boiling for 20 minutes at a bath ratio of 1:50.

■, Deionized water.

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

3. Hardness 20° (IH water + 4 g/day of the composition prepared in Production Example 1).

Subsequently, each sample piece was put together and a Permuchit
It was washed with cold water treated with Tit (trade name of ion exchange resin).

These stained and treated sample pieces were centrifugally dehydrated to a reduction rate of 100%, and then subjected to Swiss standard 5NV-Nor■19.
832 for wet iron fastness. That is, put a white cotton cloth in distilled water, moisten it, and reduce the squeezing rate to 1.
Centrifuge to dehydrate to 00%. A sample piece of the wet dyed knitted fabric is placed on a dry white cotton cloth, and the above-mentioned wet white cotton cloth (W1 lining cloth) is placed over it. The dyed sample pieces are then ironed together using an iron set at a temperature of 180° C. on top of the thus stacked cloth. For ironing, use 400g of dye of the following formula.

Sodium chloride 32Kg, m-nitrobenzenesulfonic acid sodium salt)
800g.

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

After this, 8 kg of sodium carbonate and 1.2 g of sodium hydroxide solution (3H) were added to the dyebath, and the knitted fabric was dyed at 85° C. for an additional 60 minutes. The bath was allowed to cool and the dyeing was rinsed and dried.

B) Each of the three sample pieces of the cotton knitted fabric dyed in (A) above was subjected to the following three types of washing baths for 2 minutes. Color transfer (contamination) to the white cotton accompanying cloth that had been pre-moistened afterwards.
The iron fastness of the stained sample piece is determined by checking the presence or absence of .

As a result of this test, the dyed sample pieces obtained in washing bath 3 did not stain the white cotton fabric at all. In contrast, the dyed sample pieces washed in washing baths 1 and 2 strongly stained the white cotton-associated fabric.

Branch 1 Group 1 A) Bleached and mercerized cotton satin (120
g/nf') was applied to a Rouleaux type printing machine and printed using a printing paste IKg having the following composition.

Base glue consisting of the following ingredients: 900 g + 5z algin glue: 550 parts Urea: 150 parts Sodium m-nitrobenzenesulfonate: 10 parts 30% sodium carbonate solution: 60 parts Water: 230 parts Formula below 50 g of dye.

wood 50g
6 After printing, the fabric was steamed at 101° C. for 8 minutes and then rinsed in cold water for 5 minutes.

B) Prepare the following three types of washing baths and adjust the enema temperature (98℃)
It was heated up.

l, deionized water.

2. Water with hardness of 20°dH.

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

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

As a result, no contamination was observed in the non-printed white background portion of the printed sample piece obtained using Washing Bath 3. In contrast, the white background portions of the printed specimens treated in Washing Baths 1 and 2 were heavily contaminated.

Aim for supporting lid 1 A) Mixed fabric of 67% polyester and 33% cotton (20
8g/rrf> was applied to a Schablone type printing machine and printed using a printing paste having the following composition.

Original glue consisting of the following ingredients: 938g Nialgin glue: 500 parts Urea: 50 parts Carbonic acid: 1~
Lithium... 8 parts Water... 442 parts Dye of the following formula 30 g.

Dye of the following formula 2 go was not found. In contrast, the white areas of the printed specimens treated in washing baths 1 and 2 were heavily contaminated.

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

B) Prepare the following three types of washing baths and boil them at boiling temperature (98°C).
).

1. Deionized water.

2. Water with a hardness of 20'dll.

3. Water with a hardness of 20° dFl + 4 g/liter of the composition prepared in Preparation Example 1.

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

Claims (1)

[Claims] 1. (A) at least one inorganic salt belonging to polyphosphates or silicates of alkali metals and soluble or dispersible in water; and (B) a salt of a monomeric hydroxycarboxylic acid or A water-free or aqueous detergent, characterized in that it contains a salt of a polymeric aliphatic carboxylic acid. 2. The detergent according to claim 1, wherein component (A) is an alkali metal metasilicate. 3. Component (A) has a ratio of Na_2O:SiO_2 of 1:1
Claim 1: Sodium silicate having a ratio of 1:3.5 to 1:3.5.
Detergents listed. 4. The detergent according to claim 1, wherein component (A) is sodium metasilicate nonahydrate. 5. Detergent according to claim 1, wherein component (B) is an alkali metal salt of an aliphatic mono- or poly-carboxylic acid containing from 3 to 10 carbon atoms and hydroxyl groups. 6. The detergent according to claim 5, wherein the hydroxycarboxylic acid is citric acid. 7. Claim 5 wherein the hydroxycarboxylic acid is gluconic acid.
Detergents listed. 8. A detergent according to claim 1, wherein component (B) is a polymeric aliphatic carboxylic acid in the form of a sodium, potassium or ammonium salt having a molecular weight of at least 450. 9. The detergent according to claim 8, wherein the polymeric carboxylic acid is incompletely hydrolyzed polymaleic anhydride having a molecular weight of 500 to 5,000. 10. The detergent according to claim 8, wherein the polymer carboxylic acid is polyacrylic acid having a viscosity of 1000 to 3000 m·Pa·s at 20°C. 11. The detergent (1) according to claim 1, which additionally contains a mixture of monomers and oligomer phosphorus compounds of the following formula as component (C). represents hydrogen or -CO-T; R, T, and X each represent alkyl having 1 to 4 carbon atoms; m is a number from 1 to 15). 12. The detergent according to claim 1, comprising sodium metasilicate (A) and trisodium citrate (B). 13. A detergent according to claim 1, comprising sodium metasilicate (A) and an aqueous solution (B) of a polymerized ethylenically unsaturated mono- or dicarboxylic acid having 3 to 5 carbon atoms. 14. Monomers and oligomers of sodium metasilicate (A), sodium gluconate (B), and formula (2) ▲ There are mathematical formulas, chemical formulas, tables, etc. ▼ (In the formula, m_1 is a number from 1 to 12) The detergent according to claim 11, containing an aqueous solution (C) of the mixture. 15. Detergent according to claim 1, containing: 65 to 85% by weight of sodium metasilicate and 15 to 35% by weight of trisodium citrate, based on the total mixture. 16. Claim comprising: 40-60% by weight of sodium silicate, 5-35% by weight of component (B) and additionally 5-15% by weight of component (C), based on the total mixture. 11. The detergent described in 11. 17. The detergent according to claim 16, which contains 3 to 12% by weight of monosaccharides as additional component (D). 18. A method for washing a printed or dyed product obtained by printing or dyeing a cellulose-containing fiber material with a reactive dye, in which the printed or dyed product is treated with an aqueous washing bath containing the detergent according to claim 1. A method characterized by: