EP0420802A2 - Aqueous, storage stable, low foaming wetting agent - Google Patents

Abstract

There is described an aqueous, storage-stable, low-foam wetting agent comprising a nonionic surfactant selected from the group of the partially end-capped alkoxylated fatty alcohols, characterised in that it comprises (a) from 10 to 80% of a nonionic surfactant of the general formula <IMAGE> where R is an aliphatic radical of at least 8 carbon atoms, R1 is hydrogen, C1-C8-alkyl, a cycloaliphatic radical of at least 5 carbon atoms, phenyl(lower alkyl) or styryl, "Alkylen" is an alkylene radical of 2 to 14 carbon atoms, and p is a number from 2 to 24, and (b) from 1 to 10% by weight of a hydrotrope. The novel wetting agent is used in textile treatment, in particular in pretreatment.

Description

The present invention relates to a new aqueous, storage-stable, low-foaming wetting agent in use, and to its production and use in textile treatment.

It is e.g. known from DE-A 33 15 961 and 3625078 to use low-foaming wetting agents in the treatment of textiles in order to improve the treatment in alkaline liquors. However, the wetting agents proposed here have a low cloud point, which has an unfavorable effect on their storage stability. At temperatures above the cloud point, phase separation occurs, which means that the use of these wetting agents is no longer possible.

The object of the present invention is to provide a wetting agent whose cloud point enables storage stability up to 40 ° C. and at the same time shows low-foaming behavior in use.

• (a) 10 bis 80 Gew.% eines nichtionogenen Tensids der allgemeinen Formel
  (1) R-O(̵Alkylen-)̵
  
  R₁
  worin
  R einen aliphatischen Rest mit mindestens 8 Kohlenstoffatomen,
  R₁ Wasserstoff, C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens 5 C-Atomen, Phenylniederalkyl oder Styryl,
  "Alkylen" einen Alkylenrest von 2 bis 4 Kohlenstoffatomen und
  p eine Zahl von 2 bis 24 bedeuten und
• (b) 1 bis 10 Gew.% eines Hydrotropiermittels

enthält.The aqueous, storage-stable, low-foaming wetting agent according to the invention, containing a nonionic surfactant from the group of partially end-capped alkoxylated fatty alcohols, is characterized in that it

• (a) 10 to 80% by weight of a nonionic surfactant of the general formula
  (1) RO (̵alkylene-) ̵
  
  R₁
  wherein
  R is an aliphatic radical with at least 8 carbon atoms,
  R₁ is hydrogen, C₁ to C₈-alkyl, a cycloaliphatic radical having at least 5 C atoms, phenyl-lower alkyl or styryl,
  "Alkylene" means an alkylene radical of 2 to 4 carbon atoms and
  p is a number from 2 to 24 and
• (b) 1 to 10% by weight of a hydrotroping agent

contains.

The substituent R in formula (1) advantageously represents the hydrocarbon radical of an unsaturated or saturated aliphatic monoalcohol with 8 to 22 carbon atoms. The hydrocarbon radical can be straight-chain or branched. R is preferably an alkyl or alkenyl radical having 9 to 14 carbon atoms.

As aliphatic saturated monoalcohols, natural alcohols such as e.g. Lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, as well as synthetic alcohols, e.g. 2-ethylhexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethylnonyl alcohol, decanol, C₉-C₁₁ oxo alcohol, tridecyl alcohol, isotridecanol or linear primary alcohols (alfoles) with 8 to 18 carbon atoms in Come into consideration. Some representatives of these alfoles are Alfol (8-10), Alfol (9-11), Alfol (10-14), Alfol (12-13) or Alfol (16-18). ("Alfol" is a registered trademark).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexanedecenyl alcohol or oleyl alcohol.

The alcohol residues can be present individually or in the form of mixtures of two or more components, e.g. Mixtures of alkyl and / or alkenyl groups, which are derived from soy fatty acids, palm kernel fatty acids or tallow oils.

(Alkylene-O) _p chains are preferably of the ethylene glycol, ethylene propylene glycol or ethylene isopropylene glycol type; p is preferably 4 to 20.

Examples of nonionic surfactants are:
- Addition products of preferably 4 to 20 moles of alkylene oxides, in particular ethylene oxide, it being possible for individual ethylene oxide units to be replaced by substituted epoxides, such as isopropylene oxide and / or propylene oxide, with higher unsaturated or saturated fatty alcohols with 8 to 22 carbon atoms.

worin von Y₁ und Y₂ der eine Rest Methyl oder Ethyl und der andere Wasserstoff,
n₁ eine ganze Zahl von 2 bis 24 und
ml eine ganze Zahl von 0 bis 15 bedeutet,
wobei die Summe von m₁ und n₁ maximal 24 ist und
R und R₁ die in Formel (1) angegebene Bedeutung haben.Practically important, non-ionic surfactants correspond to the formula

in which one of Y₁ and Y₂ is methyl or ethyl and the other is hydrogen,
n₁ is an integer from 2 to 24 and
ml is an integer from 0 to 15,
the sum of m₁ and n₁ is a maximum of 24 and
R and R₁ have the meaning given in formula (1).

worin
R₂ C₉ bis C₁₄-Alkyl,
R₃ Wasserstoff, Butyl, einen cycloaliphatischen Rest mit mindestens 6 C-Atomen oder Benzyl,
von Y₃ und Y₄ der eine Rest Wasserstoff oder Methyl und der andere Wasserstoff,
m₂ eine ganze zahl von 4 bis 8 und
n₂ eine ganze Zahl von 4 bis 8 bedeuten.Of particular interest are non-ionic surfactants of the formula

wherein
R₂ C₉ to C₁₄ alkyl,
R₃ is hydrogen, butyl, a cycloaliphatic radical with at least 6 carbon atoms or benzyl,
of Y₃ and Y₄ one residue is hydrogen or methyl and the other hydrogen,
m₂ is an integer from 4 to 8 and
n₂ is an integer from 4 to 8.

worin R₂ die in Formel (3) angegebene Bedeutung hat,
R₄ Wasserstoff, C₁ bis C₄-Alkyl oder Phenylniederalkyl,
von Y₅ und Y₆ der eine Rest Wasserstoff und der andere Ethyl,
n₃ eine ganze Zahl von 4 bis 8 und
m₃ eine ganze Zahl von 1 bis 3 bedeuten.Other important nonionic surfactants correspond to the formula

wherein R₂ has the meaning given in formula (3),
R₄ is hydrogen, C₁ to C₄-alkyl or phenyl-lower alkyl,
of Y₅ and Y₆ one residue is hydrogen and the other is ethyl,
n₃ is an integer from 4 to 8 and
m₃ is an integer from 1 to 3.

The nonionic surfactants of the formulas (1) to (4) are prepared in a manner known per se, for example by reaction of the corresponding alkylene oxide addition products with thionyl chloride and subsequent reaction of the chlorine compound formed with a short-chain, cycloaliphatic, fatty, phenyl-lower alkyl or styryl alcohol.

worin X -(CH₂)₁₋₆-, -CH=CH-CH₂- oder -O-(CH₂)₂₋₆- und
R₅, R₆ und R₇, unabhängig voneinander, Wasserstoff, Hydroxy, Halogen oder
C₁-C₆-Alkoxy bedeuten, wie z.B. Benzylalkohol, 2,4-Dichlorbenzylalkohol, Phenylethanol, Phenoxyethanol, 1-Phenoxy-2-propanol (Phenoxy-isopropanol) und Zimtalkohol;
- Sulfonate von Terpenoiden oder ein- oder zweikernigen aromatischen Verbindungen, z.B. die Sulfonate des Camphers, Toluols, Xylols, Cumols und Naphthols;
- Aliphatische gesättigte und ungesättigte C₁-C₁₁-Monocarbonsäuren, wie die Essig­säure, Propionsäure, Capronsäure, Undecylensäure;
- Gesättigte oder ungesättigte C₃-C₁₂-Di- oder Polycarbonsäuren, z.B. die Malon-, Bernstein-, Glutar-, Adipin-, Pimelin-, Kork-, Azelain- und Sebacinsäure, die Undecan- und Dodecandicarbonsäure, die Fumar-, Malein-, Wein- und Apfelsäure sowie die Citronen- und Aconitsäure;
Alle erwähnten organischen Säuren können auch in Form ihrer wasserlöslichen Salze, wie der Alkalimetall-, insbesondere Natrium- oder Kaliumsalze oder der Aminsalze vorliegen.The following compounds are suitable as component (b) of the composition according to the invention:
- Monohydric C₄ to C₁₈ aliphatic and monocyclic alcohols, such as C₂-C₁₈ alkanols, C₂-C₁₈ alkenols and terpene alcohols, for example ethanol, propanol, isopropanol, hexanol, cis-3-hexen-1-ol, trans-2-hexene -1-ol, 1-octen-3-ol, heptanol, octanol, trans-2-cis6-nonadien-1-ol, decanol, linanol, geraniol, dihydroterpinol, myrcenol, nopol and terpineol;
- Aromatic alcohols of the formula

wherein X - (CH₂) ₁₋₆-, -CH = CH-CH₂- or -O- (CH₂) ₂₋₆- and
R₅, R₆ and R₇, independently of one another, hydrogen, hydroxy, halogen or
C₁-C₆-alkoxy such as benzyl alcohol, 2,4-dichlorobenzyl alcohol, phenylethanol, phenoxyethanol, 1-phenoxy-2-propanol (phenoxy-isopropanol) and cinnamon alcohol;
- Sulfonates of terpenoids or mononuclear or dinuclear aromatic compounds, for example the sulfonates of camphor, toluene, xylene, cumene and naphthol;
- Aliphatic saturated and unsaturated C₁-C₁₁ monocarboxylic acids such as acetic acid, propionic acid, caproic acid, undecylenic acid;
- Saturated or unsaturated C₃-C₁₂-di- or polycarboxylic acids, such as the malonic, Succinic, glutaric, adipic, pimelic, cork, azelaic and sebacic acids, undecanoic and dodecanedicarboxylic acids, fumaric, maleic, tartaric and malic acids as well as citric and aconitic acids;
All of the organic acids mentioned can also be in the form of their water-soluble salts, such as the alkali metal, in particular sodium or potassium, salts or the amine salts.

Particularly preferred hydrotroping agents of component (b) according to the invention are alkyl sulfates of the formula
(5) R₈O - SO₃X,
wherein
R₈ is an aliphatic saturated, branched or straight chain radical having 4 to 24 carbon atoms and
X represents hydrogen, alkali metal or ammonium.

If the alkyl sulfate is in the form of a salt, sodium, potassium or ammonium salts can be used, for example. The sodium salt is preferred.

Very particularly preferred hydrotroping agents of component (b) are alkyl sulfates in which the substituent R₈ in formula (5) is the hydrocarbon radical of an aliphatic saturated monoalcohol having 4 to 24 carbon atoms. The hydrocarbon residue can be straight-chain or branched.

Suitable aliphatic saturated monoalcohols are natural alcohols, such as lauryl, myristyl, cetyl, stearyl, arachnidyl or behenyl alcohol. Preferred are compounds in which the substituent R₈ is derived from branched aliphatic synthetic alcohols having 4 to 12, in particular 4 to 8, carbon atoms, for example. Isobutyl alcohol, sec-butanol, tert-butanol, isoamyl alcohol, 2-ethylbutanol, 2-methylpentanol, 5-methylheptan-3-ol, 2-ethylhexanol, 1-1-3-3-tetramethylbutanol, octan-2-ol, isononyl alcohol, Trimethylhexanol, trimethylnonyl alcohol, decanol or C₉-C₁₁-oxo alcohol. The alkyl sulfates can already be in the form of their salts and can be used alone or as a (technical) mixture with one another in the wetting agent according to the invention.

The alkyl sulfonates of formula (8) and their alkali metal or amine salts can also be used together with other compounds as hydrotroping agents, e.g. with polymerized acrylic acid, C₁ to C₁₀ - alkylphosphonic acid or C₁ to C₁₀ - alkylphosphonic acid esters.

These alkyl sulfates are prepared in a manner known per se by reacting the corresponding alcohols with e.g. Sulfuric acid, oleum, chlorosulfonic acid or sulfur trioxide.

The wetting agent according to the invention can additionally contain an optional component (c).

Non-polar organic solvents with a flash point above 65 ° C are suitable. For example, cyclic straight-chain or in particular branched alcohols are used, such as e.g. Cyclohexanol, methylcyclohexanol, tetralin, n-hexanol, 2-ethylhexanol-1, isooctyl alcohol, isononyl alcohol and especially trimethylhexanol-3,5,5. Furthermore, esters such as tributyl citrate or tributyl phosphate can be used as non-polar organic solvents.

The new wetting agents can be prepared by simply stirring the components (a), (b) and, if appropriate, (c).

The preparation is preferably carried out by mixing components (a), (b) and optionally (c) with stirring and adding deionized water until a homogeneous solution is obtained.

Preferred wetting agents according to the invention particularly advantageously contain, based on the mixture as a whole,
15 to 60% by weight of component (a),
2 to 10% by weight of component (b),
0 to 4% by weight of component (c) and
ad 100% water.

The new wetting agents are aqueous formulations with low foaming in use, which are characterized by a cloud point which is above 40 ° C. and which are stable up to 40 ° C.

They are used as wetting agents in textile treatment, especially in pretreatment, such as in long liquor bleaching or in chlorine and peroxide hot bleaching.

• (a) 10 bis 80 Gew.% eines nichtionogenen Tensids der allgemeinen Formel
  (1)      R-O(̵Alkylen-O)̵
  
  R₁
  worin
  R einen aliphatischen Rest mit mindestens 8 Kohlenstoffatomen,
  R₁ Wasserstoff, C₁ bis C₈-Alkyl, einen cycloaliphatischen Rest mit mindestens 5 C-Atomen, Phenylniederalkyl oder Styryl,
  "Alkylen" einen Alkylenrest von 2 bis 4 Kohlenstoffatomen und p eine Zahl von 2 bis 24 bedeuten,
• (b) 1 bis 10 Gew. % eines Hydrotropiermittels
• (c) 0 bis 4 Gew.% eines unpolaren Lösungsmittels und ad 100 % Wasser

enthält.The present invention accordingly also relates to a method for wetting fiber materials. The process is characterized in that these materials are treated in the presence of a wetting agent which

• (a) 10 to 80% by weight of a nonionic surfactant of the general formula
  (1) RO (̵alkylene-O) ̵
  
  R₁
  wherein
  R is an aliphatic radical with at least 8 carbon atoms,
  R₁ is hydrogen, C₁ to C₈-alkyl, a cycloaliphatic radical having at least 5 C atoms, phenyl-lower alkyl or styryl,
  "Alkylene" means an alkylene radical of 2 to 4 carbon atoms and p is a number from 2 to 24,
• (b) 1 to 10% by weight of a hydrotroping agent
• (c) 0 to 4% by weight of a non-polar solvent and ad 100% water

contains.

The amounts in which the wetting agent according to the invention is added to the treatment liquors are between 0.1 and 10, preferably 0.5 and 5 g per liter of treatment liquor. The fleet can also contain other additives, e.g. Desizing agents, dyes, optical brighteners, synthetic resins and alkalis such as sodium hydroxide.

The following are considered as fiber materials:
Cellulose, in particular untreated natural cellulose such as hemp, linen, jute, cellulose, viscose, acetate treyon, native cellulose fiber and especially raw cotton, wool, polyamide, polyacrylonitrile or polyester fiber materials as well as fiber blends, e.g. those made of polyacrylonitrile / cotton or polyester / cotton.

The fiber material to be treated can be in various processing stages, e.g. the cellulose-containing material as loose material, yarn, woven or knitted fabric. As a rule, these are always textile fiber materials which are produced from pure textile cellulose fibers or from mixtures of textile cellulose fibers with textile synthetic fibers. The fiber material can be treated continuously or discontinuously in an aqueous liquor.

The aqueous treatment liquors can be applied to the fiber materials in a known manner, advantageously by impregnation on the padder, the liquor absorption being about 50 to 120% by weight. The padding process is used in particular in the pad-steam process, the pad-thermofix process and the pad-batch process.

The impregnation can be carried out at 10 to 60 ° C, but preferably at room temperature. After impregnation and squeezing, the cellulose material is optionally after intermediate drying, heat treatment, e.g. Subject to temperatures from 95 to 210 ° C. For example, the heat treatment can be carried out after intermediate drying of the goods at 80 to 120 ° C, by heat setting at a temperature of 120 to 210 ° C, preferably 140 to 180 ° C. Preferably the heat treatment is direct, i.e. without intermediate drying, by steaming at 95 to 120 ° C, preferably 100 to 106 ° C. Depending on the type of heat development and the temperature range, the heat treatment can take 30 seconds to 30 minutes. In the pad-batch process, the impregnated goods are rolled up without drying and then optionally packed with a plastic film and stored at room temperature for 1 to 24 hours.

The treatment of the fiber materials can also in so-called long liquors with a liquor ratio of e.g. 1: 3 to 1: 100, preferably 1: 8 to 1:25 and at 10 to 100, preferably 80 to 98 ° C for about 1/4 to 3 hours under normal conditions, i.e. under atmospheric pressure in conventional equipment, e.g. a jigger, jet or reel runner. If necessary, however, the treatment can also be carried out up to 150 ° C., preferably 105 to 140 ° C., under pressure in so-called high-temperature apparatus (HT apparatus).

Then, if the process requires, the fiber materials are washed with hot water at around 90 to 98 ° C and then with warm and finally with cold water rinsed thoroughly, neutralized if necessary and then dried preferably at elevated temperatures.

The main advantages of the wetting agents according to the invention, in addition to their excellent wetting action, are their good storage stability and their low-foaming behavior in use.

In the following examples, the percentages always refer to the weight.

Manufacturing examples of the formulations Example 1:

Formulations A, B, C and D are prepared by mixing the components listed in Table I according to their weight proportions with stirring until a homogeneous solution is obtained. Table I: A B C. D Nonionic surfactant of formula (1), for example 15 moles of the ethylene / propylene oxide adduct with 1 mole of a C₉ - C₁₁ fatty alcohol 25th 25th 25th 25th 2-ethylhexanol sulfate sodium salt (40% solution) 9 9 3,5,5-trimethylhexanol 3rd 2nd Sodium cumene sulfonate 100% 10th 10th Isopropanol 5 water 66 63 63 60 Cloud point [° C] * 40.5 41.5 45.3 55.5 Foam height [ml] of 2 g / l of the formulation ** 70 50 50 80 * Cloud point of the formulation tel quel; ** Foam test based on DIN 53902

Application examples Example 2:

A raw cotton jersey is bleached in a ®AHIBA dyeing machine in a bath, which is per liter
2g of formulation B
0.2g of the aqueous mixture of the oligomer mixture of phosphoric acid esters acc. US-PS 4254063, Na-gluconate and magnesium chloride (ratio 2: 1: 1)
1g NaOH solid and
Contains 5 ml H₂O₂ (35%).

The bleach bath is heated to 90 ° C. within 20 minutes and then held at this temperature for a further 30 minutes. The substrate is then washed out hot and cold and neutralized. No disruptive foaming occurs during bleaching. The result is a uniform degree of whiteness, which is increased from ⁻72 to 50 CIBA-GEIGY whiteness units.

Example 3:

A raw cotton jersey with a running weight of 80 g is passed through a chlorine bleaching bath per liter in a Galaxy system (Benninger, Switzerland) at a speed of 54 m / min
4g active chlorine
1.5g NaOH (100%) and
Contains 2 g of formulation B. The residence time is 15 minutes at 16 ° C.
The goods are evenly wetted and the chlorine bleach bath is foam-free. After a rinsing process, the goods are squeezed and passed through an H₂O₂ bleaching bath, which is per liter
2 g of the aqueous mixture of the oligomer mixture of phosphoric acid esters acc. US Pat. No. 4,254,063, Na gluconate and magnesium chloride (ratio 2: 1: 1)
3g NaOH (100%)
3 ml water glass 38 ° Be
0.5 g of formulation B and
Contains 15 ml H₂O₂ (35%).

The residence time is 35 minutes at 85 ° C. No annoying foam formation occurs in the peroxide bleaching bath either. The result is a high, uniform whiteness of R 46 = 86.2 (measured with the Elrepho device).

Claims (14)

1. Aqueous, storage-stable, low-foaming wetting agent in use, containing a nonionic surfactant from the group of partially end-capped alkoxylated fatty alcohols, characterized in that it
(a) 10 to 80% by weight of a nonionic surfactant of the general formula
(1) RO (̵alkylene-O) ̵

R₁
wherein
R is an aliphatic radical with at least 8 carbon atoms,
R₁ is hydrogen, C₁ to C₈-alkyl, a cycloaliphatic radical having at least 5 C atoms, phenyl-lower alkyl or styryl,
"Alkylene" means an alkylene radical of 2 to 4 carbon atoms and
p is a number from 2 to 24 and
(b) 1 to 10% by weight of a hydrotroping agent
contains. 2. Wetting agent according to claim 1, characterized in that component (a) of the formula

corresponds to, in which one of Y₁ and Y₂ is methyl or ethyl and the other is hydrogen,
n₁ is an integer from 2 to 24,
m₁ is an integer from 0 to 15,
the sum of ml and n₁ is a maximum of 24 and
R and R₁ have the meaning given in formula (1). 3. wetting agent according to claim 1, characterized in that the nonionic surfactant component (a) of the formula

corresponds to what
R₂ C₉ to C₁₄ alkyl,
R₃ is hydrogen, butyl, a cycloaliphatic radical with at least 6 carbon atoms or benzyl,
of Y₃ and Y₄ one residue is hydrogen or methyl and the other hydrogen,
m₂ is an integer from 0 to 8 and
n₂ is an integer from 4 to 8. 4. Wetting agent according to one of claims 1 or 2, characterized in that the nonionic surfactant of component (a) of the formula

corresponds to what
R₂ C₉ to C₁₄ alkyl,
R₄ is hydrogen, C₁ to C₄-alkyl or phenyl-lower alkyl,
of Y₅ and Y₆ one is hydrogen and the other is ethyl, n₃ is an integer from 4 to 8 and
m₃ is an integer from 1 to 3. 5. wetting agent according to claim 1, characterized in that it is 1 to 10 wt.% Of an alkyl sulfate of the formula
(5) R₈O-SO₃X,
wherein
R₈ is an aliphatic saturated, branched or straight chain radical having 4 to 24 carbon atoms and
X represents hydrogen, alkali metal or ammonium. 6. wetting agent according to claim 5, characterized in that R₈ is an aliphatic branched radical of 4 to 12 carbon atoms. 7. Wetting agent according to one of claims 5 or 6, characterized in that R₈ is an aliphatic branched radical of 4 to 8 carbon atoms. 8. Wetting agent according to one of claims 1 to 7, characterized in that it additionally contains a non-polar solvent as an optional component (c). 9. wetting agent according to one of claims 1 to 8, characterized in that it, based on the agent
(a) 15 to 60% by weight of component (a),
(b) 2 to 10% by weight of component (b),
(c) 0 to 4% by weight of component (c) and
ad 100% water
contains. 10. Use of the wetting agent according to one of claims 1 to 9 as a wetting agent in textile pretreatment. 11. A process for wetting fiber materials, characterized in that these materials are treated in an aqueous medium in the presence of a wetting agent which
(a) 10 to 80% by weight of a nonionic surfactant of the formula (1) defined in claim 1
(b) 1 to 10% by weight of a hydrotroping agent and
(c) 0 to 4% by weight of a non-polar solvent
contains. 12. The method according to claim 11, characterized in that the wetting agent is used in an amount of 0.1 to 10 g, preferably 0.5 to 5 g per liter of liquor. 13. The method according to any one of claims 11 or 12, characterized in that the Fiber material is treated continuously or discontinuously. 14. The fiber material treated according to one of claims 12 to 13.