EP0356381A1 - Wetting agents for hydrophobic capillary materials, and their uses - Google Patents

Abstract

Wetting agents for wetting hydrophobic capillary materials are described, which, in addition to a water-soluble anionic, nonionic, cationic or amphoteric surfactant or mixtures thereof, contain an amphiphilic, phosphorus-free, sparingly water-soluble, organic compound having a melting point below 4 DEG C and a boiling point above 200 DEG C.

Description

The present invention relates to a new agent and its use for wetting hydrophobic, capillary materials, whereby not only rapid wetting but also practically complete deaeration of the materials is achieved.

The agent according to the invention for wetting hydrophobic, capillary materials is characterized in that it contains a water-soluble surfactant and an amphiphilic, phosphorus-free, poorly water-soluble organic compound with a melting point below 4 ° C. and a boiling point above 200 ° C. (at 1013 hPa) .

Preferred amphiphilic phosphorus-free compounds used according to the invention are liquid.

Examples of amphiphilic organic compounds which are sparingly soluble in water are trialkyl esters of aliphatic hydroxytricarboxylic acids or acetylated hydroxytricarboxylic acids having 4 to 8 carbon atoms per alkyl part, such as preferably tributyl citrate and acetyltributyl citrate; Tetraalkylureas with 4 to 8 carbon atoms per alkyl part, such as preferably tetrabutylurea, di- or trialkylamines with 4 to 10 carbon atoms per alkyl part, such as preferably bis- (2-ethylhexyl) amine or tributylamine; Bis-alkylaminoalkanols with 4 to 8 carbon atoms per alkyl part and 2 to 6 carbon atoms in the alkanol part, such as preferably 2 -dibutylaminoethanol or alcohols of acyclic terpenes, such as preferably geraniol. Mixtures of these compounds can also be used.

In the present description, "poorly soluble in water" refers to an organic liquid, part of which dissolves in 1,000-10,000 parts of water at 20 ° C. (cf. Martindale Tne Extra Pharmacopeia, 28 edition London, The Pharmaceutical Press, 1982, Xiii).

The surfactants can be anionic, cationic, amphoteric or preferably nonionic. They can be used individually or in the form of mixtures.

Examples of suitable anionic surfactants are:
sulfated aliphatic alcohols, the alkyl chain of which has 8 to 18 carbon atoms, for example sulfated lauryl alcohol;
- Sulphated unsaturated fatty acids or fatty acid lower alkyl esters which have 8 to 20 carbon atoms in the fat residue, for example ricinoleic acid and oils containing such fatty acids, for example castor oil;
Alkane sulfonates, the alkyl chain of which contains 8 to 20 carbon atoms, for example dodecyl sulfonate; Alkylarylsulfonates with a straight-chain or branched alkyl chain with at least 6 carbon atoms, for example dodecylbenzenesulfonates or 3,7-diisobutyl-naphthalenesulfonates;
- Sulfonates of polycarboxylic acid esters, for example dioctyl sulfosuccinates or sulfosuccinimides;
- The so-called alkali metal, ammonium or amine salts of fatty acids with 10 to 20 carbon atoms, for example rosin salts;
- The adducts of 1 to 60 ethylene oxide and / or propylene oxide with fatty amines, fatty acids or fatty alcohols each converted to 8 with an organic dicarboxylic acid such as maleic acid or sulfosuccinic acid, but preferably with an inorganic polybasic acid such as o-phosphoric acid or sulfuric acid up to 22 carbon atoms, on benzylphenols or alkylphenols with 4 to 16 carbon atoms in the alkyl chain or on tri- to hexavalent alkanols with 3 to 6 carbon atoms.

In addition, derivatives of alkylene oxide adducts, such as, for example, acidic, ether groups or preferably ester groups of inorganic or organic acids, are addition products of anionic surfactants Alkylene oxides, especially ethylene oxide and / or propylene oxide or also styrene oxide on aliphatic hydrocarbon radicals with a total of at least 4 carbon atoms, organic hydroxyl, carboxyl, amino and / or amido compounds or mixtures of these substances. These acidic ethers or esters can be present as free acids or as salts, for example alkali metal, alkaline earth metal, ammonium or amine salts.

These anionic surfactants are prepared by known methods, e.g. at least 1 mole, preferably more than 1 mole, e.g. 2 to 60 mol, ethylene oxide or propylene oxide or alternatingly in any order ethylene oxide or propylene oxide and then etherifying or esterifying the addition products and, if appropriate, converting the ethers or the esters into their salts. Higher fatty alcohols, i.e. Alkanols or alkenols each with 8 to 22 carbon atoms, di- to hexavalent aliphatic alcohols with 2 to 9 carbon atoms, alicyclic alcohols, phenylphenols, benzylphenols, alkylphenols with one or more alkyl substituents, which together have at least 4 carbon atoms, fatty acids with 8 to 22 carbon atoms, amines which have aliphatic and / or cycloaliphatic hydrocarbon radicals of at least 8 carbon atoms, in particular fatty amines containing such radicals, hydroxyalkylamines, hydroxyalkylamides and aminoalkyl esters of fatty acids or dicarboxylic acids and higher alkylated aryloxycarboxylic acids.

Highly suitable anionic surfactants are acidic esters or their salts of a polyadduct of 2 to 30 moles of ethylene oxide with 1 mole of fatty alcohol with 8 to 22 carbon atoms or with 1 mole of a phenol which has at least one benzyl group, one phenyl group or preferably an alkyl group with at least 4 carbon atoms such as benzylphenol, dibenzylphenol, dibenzyl- (nonyl) -phenol, α-methylbenzylphenol, bis-α-methylbenzylphenol, tris-α-methylbenzylphenol, o-phenylphenol, butylphenol, tributylphenol, octylphenol, nonylphenol, dodecylphenol or pentadylphenol or pentadylphenol.

X,
worin R Alkyl oder Alkenyl mit 8 bis 22 C-Atomen, Alkylphenyl mit 4 bis 16 C-Atomen im Alkylteil oder o-Phenylphenyl, X den Säurerest einer anorganischen, Sauerstoff enthaltenden Säure, wie z.B. Phosphorsäure oder vorzugsweise Schwefelsäure oder auch den Rest einer organischen Säure,wie z.B. Maleinsäure, Bernsteinsäure, Sulfobernsteinsäure, und m 2 bis 30, vorzugsweise 2 bis 15 bedeuten, und vor allem der Formel
(2)      R₁―O―(CH₂CH₂O

X₁
worin R₁ Alkyl oder Alkenyl mit 8 bis 22 C-Atomen, X₁ Carboxy-C₁-C₃-­Alkyl, wie z.B. Carboxymethyl, Carboxyethyl oder Carboxypropyl und m 2 bis 30, vorzugsweise 2 bis 15 bedeuten.Particularly suitable anionic surfactants correspond to the formula
(1) R ― O― (CH₂CH₂O

X,
wherein R is alkyl or alkenyl with 8 to 22 carbon atoms, alkylphenyl with 4 to 16 carbon atoms in the alkyl part or o-phenylphenyl, X is the acid residue of an inorganic, oxygen-containing acid, such as phosphoric acid or preferably sulfuric acid or the rest of an organic Acid, such as maleic acid, succinic acid, sulfosuccinic acid, and m are 2 to 30, preferably 2 to 15, and especially the formula
(2) R₁ ― O― (CH₂CH₂O

X₁
wherein R₁ is alkyl or alkenyl having 8 to 22 carbon atoms, X₁ carboxy-C₁-C₃-alkyl, such as carboxymethyl, carboxyethyl or carboxypropyl and m is 2 to 30, preferably 2 to 15.

The alkyl radical in the alkylphenyl is preferably in the para position. The alkyl radicals in the alkylphenyl can be butyl, hexyl, n-octyl, n-nonyl, p-ter.octyl, p-iso-nonyl, decyl or dodecyl. Alkyl radicals having 8 to 12 carbon atoms, in particular octyl or nonyl radicals, are preferred.

The fatty alcohols for the preparation of the anionic surfactants of the formulas (1) and (2) are e.g. those with 8 to 22, especially 8 to 18 carbon atoms, such as e.g. Octyl, decyl, lauryl, tridecyl, myristyl, cetyl, stearyl, oleyl, arachidyl or behenyl alcohol.

The acid residue X is derived, for example, from low molecular weight dicarboxylic acids, such as, for example, from maleic acid, malonic acid, succinic acid or sulfosuccinic acid and is connected to the ethylene oxide part of the molecule via an ester bridge. In particular, however, X is derived from inorganic polybasic acids, such as orthophosphoric acid and especially sulfuric acid. The acid residue X can be in salt form, ie for example as an alkali metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts.

Anionic surfactants of formula (2) are prepared in a manner known per se, e.g. by reacting a fatty alcohol ethoxylate with a halogenated lower carboxylic acid (C₂-C₄) in the presence of e.g. Caustic soda. They can also be in the form of their salts, e.g. used as alkali metal, ammonium or amine salt. Examples of such salts are lithium, sodium, potassium, ammonium, trimethylamine, ethanolamine, diethanolamine or triethanolamine salts. The sodium salts are preferred.

Suitable nonionic surfactants are alkylene oxide addition products of 4 to 100 moles of alkylene oxide, e.g. Ethylene oxide and / or propylene oxide, on 1 mol of an aliphatic monoalcohol with at least 4 C atoms, a 3- to 6-valent aliphatic alcohol, a phenol which is optionally substituted by alkyl, benzyl or phenyl or a fatty acid with 8 to 22 C atoms. Adducts of monoalcohols having 8 to 22 carbon atoms with 8 to 40 moles of ethylene oxide are preferred. The addition products can in some cases be etherified terminally with alkyl groups having preferably 1 to 5 carbon atoms.

Such terminally blocked surfactants are prepared in a manner known per se, e.g. by reaction of the alkylene oxide addition products with thionyl chloride and subsequent reaction of the chlorine compound formed with a fatty alcohol or short-chain alcohol.

The aliphatic monoalcohols are, for example, water-insoluble monoalcohols with preferably 8 to 22 carbon atoms. These alcohols can be saturated or unsaturated and branched or straight-chain and can be used alone or in a mixture. Natural alcohols such as myristyl alcohol, cetyl alcohol, stearyl alcohol or oleyl alcohol or synthetic alcohols such as in particular 2-ethylhexanol, also trimethylhexanol, trimethylnonyl alcohol, hexadecyl alcohol or linear primary alcohols with average carbon atom numbers of (8-10), (10-14), (12 ), (16), (18) or (20-22) with the alkylene oxide, especially ethylene oxide.

Other aliphatic alcohols that can be reacted with alkylene oxide are 3- to 6-valent alkanols. These contain 3 to 6 carbon atoms and are in particular glycerol, trimethylolpropane, erythritol, mannitol, pentaerythritol and sorbitol. The 3- to 6-valent alcohols are preferably reacted with propylene oxide or ethylene oxide or mixtures of these alkylene oxides.

Suitable optionally substituted phenols are, for example, phenol, α-methylbenzylphenol, bis-α-methylbenzylphenol, tris-α-methylbenzylphenol, o-phenylphenol or alkylphenols, the alkyl radical of which has 1 to 16, preferably 4 to 12, carbon atoms. Examples of these alkylphenols are p-cresol, butylphenol, tributylphenol, octylphenol, and especially nonylphenol.

The fatty acids preferably have 8 to 22 carbon atoms and can be saturated or unsaturated, e.g. capric, lauric, myristic, palmitic or stearic acid or decenic, dodecenic, tetradecenic, hexadecenic, oleic, linoleic, linolenic or preferably ricinoleic acid.

Examples of nonionic surfactants are:
- Addition products of preferably 4 to 30 mol of alkylene oxide, in particular ethylene oxide, where individual ethylene oxide units can be replaced by substituted epoxides, such as styrene oxide and / or propylene oxide, with higher unsaturated or saturated fatty alcohols, fatty acids, fatty amines or fatty amides with 8 to 22 carbon atoms or with Phenylphenol, α-methylbenzylphenol, bis-α-methylbenzylphenol, tris-α-methylbenzylphenol or alkylphenols, the alkyl radicals of which have at least 4 carbon atoms;
- Alkylene oxide, especially ethylene oxide and / or propylene oxide condensation products;
- Reaction products of a fatty acid having 8 to 22 carbon atoms and a primary or secondary amine or alkylene oxide adducts of these hydroxyalkyl groups containing at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group Reaction products, the reaction taking place in such a way that the molecular quantitative ratio between hydroxyalkylamine and fatty acid can be 1: 1 and greater than 1, for example 1.1: 1 to 2: 1,
Addition products of propylene oxide onto a trihydric to hexavalent aliphatic alcohol of 3 to 6 carbon atoms, for example glycerol or pentaerythritol, the polypropylene oxide adducts having an average molecular weight of 250 to 1800, preferably 400 to 900, and
- Esters of polyalcohols, especially mono- or diglycerides of fatty acids with 12 to 18 carbon atoms, for example monoglycerides of lauric, stearic or oleic acid.

Well-suited nonionic surfactants are addition products of 10 to 15 moles of ethylene oxide with 1 mole of fatty alcohol or fatty acid each with 8 to 22 carbon atoms or with 1 mole of alkylphenol with a total of 4 to 12 carbon atoms in the alkyl part or especially fatty acid diethanolamides with 8 to 22 carbon atoms in the fatty acid residue, as before all lauryl diethanolamide or coconut fatty acid diethanolamide.

Nonionic surfactants of the amine oxide or sulfoxide type can also be considered.

Compounds which contain amino, imino, quaternary ammonium or immonium, tertiary phosphino, quaternary phosphonium or sulfonium groups, furthermore thioronium or guanidinium groups can be considered as cationic surfactants. Fatty amines and their acid salts or quaternary ammonium compounds, each with at least one aliphatic hydrocarbon radical having 6 to 22 carbon atoms, which can be interrupted by oxygen atoms, are preferred.

Also suitable as cationic surfactants are monoamines or polyamines with 2 or more, preferably 2 to 5, basic nitrogen atoms, which amines have at least one polyglycol ether chain and at least one lipophilic substituent, for example alkyl or alkenyl, each having 8 to 22 carbon atoms, and some or all of them can be quaternized.

Other cationic surfactants are N-alkylated cyclic ammonium compounds e.g. from unsaturated heterocyclic compounds, e.g. Pyridinium, quinolinium, isoquinolinium, phthalazinium, benzimidazolium, benzothiazolium, benzotriazolium and imidazolinium derivatives or from saturated heterocyclic compounds, such as pyrrolidinium, piperidinium, morpholinium, thiamorpholinium, piperoxazinium, 1,3-benzoxium , 1,3,5-trialkylhexahydro-1,3,5-triazinium and N-hexahydroazepinium derivatives. Such surfactants are e.g. in E. Jungermann Cationic Surfactants, Marcel Dekker, Inc., New York and Basel, 1970, page 71 ff.

Polyammonium polymers are also suitable as cationic surfactants, e.g. those described in US-A-4,247,476 and 4,349,532.

As amphoteric surfactants e.g. Carboxyl derivatives of imidazole, carboxybetaines, sulfobetaines, sulfoniobetaines and phosphoniobetaines as well as other phosphorine-containing betaines should be mentioned. Such surfactants are described in B.R. Bluestein and C.L. Hilton "Amphoteric Surfactant", Marcel Dekker, Inc., New York and Basel, 1982, pages 1-173.

Other amphoteric surfactants are e.g. those of the amino acid type with carboxyl, sulfonate or sulfate anion such as the N-fatty amine propionates, the asparagine derivatives, the alkyldimethylammonium acetates, the fatty alkyldimethylcarboxymethylammonium salts and monoamines or polyamines with 2 and more, preferably 2 to 5, basic nitrogen atoms, which amines per basic nitrogen atom, at least have an acidic, etherified or esterified polyglycol ether chain and at least one lipophilic substituent and to which some or all of them may be quaternized (cf. the above-mentioned literature BR Bluestein and CC Hilton, pages 175-228).

Mainly fiber materials come into consideration as hydrophobic, capillary materials. But it can also be powdered materials.

As fiber materials that can be treated with agents according to the invention are synthetic fibers, such as Polyamide, polyester; Polyacrylonitrile, polypropylene, polycarbonate fibers, polyurethane elastomer fibers, regenerated cellulose fibers or natural fibers such as raw cotton, flax, wool and silk.

Among polyamide fibers, fiber material is made from synthetic polyamide, e.g. Polyamide-6, polyamide-6,6 or also polyamide-12 understood.

Fully synthetic, high molecular weight fibers made from linear aromatic polyesters (in general polycondensation products from terephthalic acid and glycols, especially ethylene glycol, or polycondensation products from terephthalic acid and 1,4-bis (hydroxymethyl) hexahydrobenzene) are suitable as polyester fibers.

Among polyacrylonitrile fibers are e.g. To understand fibers that contain at least 85% polymerized acrylonitrile. Such polyacrylonitrile fibers generally consist of ternary copolymers with 89-95% acrylonitrile, 4-10% of a nonionic comonomer and 0.5-1% of an ionogenic comonomer with a sulfonate or sulfonate group.

Polycarbonate fibers are mainly homo- and copolymer polycarbonates, e.g. the polymer from bisphenol A and phosgene.

Polyurethane elastomer fibers include e.g. understand the elastic fibers that are obtained by reacting low molecular weight diisocyanates with long-chain, low-melting dihydroxy compounds, e.g. Mixed polyesters from adipic acid and a mixture of diols, e.g. from ethylene glycol and 1,2-propanediol or 1,6-hexanediol.

Polypropylene fibers are understood to mean, in particular, fibers which consist of homopolymers of propylene and copolymers of propylene and other aliphatic 1-olefins having 2 to 8 carbon atoms.

Powdery materials which can be treated with agents according to the invention are e.g. Activated carbon, vat and dispersion dyes to mention.

Agents according to the invention may also contain other additives, e.g. Defoamers, viscosity regulators, electrolytes or preservatives.

As defoamers e.g. those in question, as described in DE-B-26 25 706. However, those based on silicone oil or alkylenediamides with amide groups of the formula RCONH- in which R is an aliphatic or cycloaliphatic radical, such as e.g. Is C₉-C₂₃-alkyl or cyclohexyl. Further defoaming agents are known from DE-A-1 519 967 or EP-A-207 002. Defoamers based on silicone oils are preferred.

The agents according to the invention are prepared by mixing the water-soluble surfactant with water, if necessary with heating, and adding the water-insoluble amphiphilic organic compound and optionally also the defoamer to the homogeneous solution.

The agents according to the invention contain the water-soluble surfactants and the amphiphilic organic compound in a weight ratio to one another of 20: 1 to 1: 1, preferably 10: 1 to 2: 1.

The agents according to the invention can be used undiluted or diluted with water. Application baths for textile treatment can contain 0.01 to 50 g / l, preferably 3 to 20 g / l and in particular 3 to 5 g / l of the agent according to the invention.

Preferred agents according to the invention contain 10-60% by weight, in particular 10-50% by weight, water-soluble surfactant,
2-10% by weight amphiphilic organic compound, preferably liquid
0.2-2% by weight defoamer,
87.8-38 wt% water.

The present invention is to be explained in more detail with the aid of the following examples. % Figures are% by weight and parts mean parts by weight.

Manufacturing examples Example 1:

50 parts of sodium dodecylbenzenesulfonate are mixed with 36.25 parts of water while heating to 50-60 ° C. and stirred until homogeneous. Thereafter, 12.5 parts of tributyl citrate and 1.25 parts of defoamer, e.g. from 85% silicone oil and 15% fumed silica. A highly viscous liquid is obtained.

Example 2:

20 parts of lauryldiethanolamide are mixed with 74.5 parts of water at 50-60 ° C. and stirred until homogeneous. 5 parts of tributyl citrate and 0.5 part of the defoamer according to Example 1 are then added to the homogeneous solution. A pourable, storage-stable liquid is obtained.

Example 3:

20 parts of hexadecylpyridinium chloride are mixed with 75 parts of water at 50-60 ° C. and stirred until homogeneous. Then 5 parts of tributyl citrate are added to the homogeneous solution. A viscous, storage-stable liquid is obtained.

Similar formulations are obtained if 5 parts of tetrabutylurea, tributylamine, bis- (2-ethylhexyl) amine, dibutylaminoethanol or geraniol are used instead of tributyl citrate in Examples 1 to 3.

Example 4:

50 parts of sodium dodecylbenzenesulfonate are mixed with 37.5 parts of water at 50-60 ° C. and stirred until homogeneous. Then 12.5 parts of tetrabutylurea are added to the homogeneous solution. A highly viscous liquid is obtained.

Example 5:

60 parts of the adduct etherified with a carboxymethyl group of 5 moles of ethylene oxide and 1 mole of lauryl alcohol are mixed with 26 parts of water and stirred until homogeneous. After that 8 parts of tributyl citrate, 1 part of the defoamer according to Example 1 and 5 parts of 2-methyl-2,4-pentanediol are added in succession. A viscous, storage-stable preparation is obtained.

Example 6:

30 parts of coconut fatty acid diethanolamide are mixed with 10 parts of the adduct etherified with a carboxymethyl group of 2.5 mol of ethylene oxide and 1 mol of lauryl alcohol and 45.9 parts of water and stirred until homogeneous. 3.5 parts of tributyl citrate, 0.6 part of the defoamer according to Example 1 and 10 parts of the aqueous mixture of the oligomer mixture of phosphoric acid esters according to US Pat. No. 4,254,063, sodium gluconate and magnesium chloride (ratio 2: 1: 1) are then added with stirring . A viscous, storage-stable preparation is obtained.

Example 7:

30 parts of coconut fatty acid diethanolamide are mixed with 10 parts of the adduct etherified with a carboxymethyl group of 2.5 mol of ethylene oxide and 1 mol of lauryl alcohol and 27.9 parts of water and stirred until homogeneous. Then 3.5 parts of tributyl citrate, 0.6 part of the defoamer according to Example 1, 10 parts of the oligomer mixture of phosphoric acid esters according to US Pat. No. 4,254,063, 11 parts of 50% strength KOH and 7 parts of 70% sorbitol solution are added in succession with constant stirring. A viscous, storage-stable preparation is obtained.

Example 8:

30 parts of coconut fatty acid diethanolamide are mixed with 10 parts of the adduct etherified with a carboxymethyl group of 2.5 moles of ethylene oxide and 1 mole of lauryl alcohol and 54.5 parts of water and stirred until homogeneous. Then 4.5 parts of acetyltributyl citrate and 1 part of the defoamer according to Example 1 are added in succession. A viscous, storage-stable preparation is obtained.

Example 9:

Instead of the acetyl tributyl citrate used in Example 8, 4.5 parts of tetrabutyl urea are used. A viscous, storage-stable preparation is obtained.

Example 10:

30 parts of coconut fatty acid diethanolamide are mixed with 10 parts of the adduct etherified with a carboxymethyl group of 2.5 mol of ethylene oxide and 1 mol of lauryl alcohol and 49.5 parts of water and stirred until homogeneous. Then 4.5 parts of tributyl citrate and 5 parts of a defoamer consisting of 47 parts of butyl acrylate / maleic acid 2-ethylhexyl ester, 39 parts of isopalmityl alcohol, 7 parts of an ethoxylated polydimethylsiloxane, 3.5 parts of the adduct of 9 moles of ethylene oxide and 1 mole of styrene oxide are added 1 mol of C₁₃ oxo alcohol and 3.5 parts of oleic acid were added. A viscous, storage-stable preparation is obtained.

Example 11:

Instead of the defoamer used in Example 10, 5 parts of a preparation consisting of 1.65 parts of N, N'-ethylene-bis-stearamide, 2 parts of magnesium stearate, 37 parts of maleic acid-bis-2-ethylhexyl ester, 37.35 parts of paraffin oil (Shelloil L 6189), 11 parts of a nonionic emulsifier, for example: Tween 65® and 11 parts of an anionic emulsifier, for example Phospholan PNP9® used. A viscous, stable preparation is obtained.

Example 12:

25 parts of the adduct (OH-127) of 4 moles of ethylene oxide and 1 mole of styrene oxide in 1 mole of C₉-C₁₁-oxo alcohol are mixed with 72 parts of water and stirred until homogeneous. Then 2.5 parts of tributyl citrate and 0.5 part of a silicone defoamer are added in succession. A low-viscosity, storage-stable preparation is obtained.

Example 13:

25 parts of the acidic maleic acid half ester of the adduct of 35 moles of ethylene oxide and 1 mole of styrene oxide and 1 mole of stearyl alcohol are mixed with 72 parts of water and stirred until homogeneous. Then 2.5 parts of tributyl citrate and 0.5 part of a silicone defoamer are added in succession. A storage-stable, viscous preparation is obtained.

Example 14:

20 parts of lauryldiethanolamide and 5 parts of the adduct etherified with a carboxylmethyl group of 10 moles of ethylene oxide and 1 mole of lauryl alcohol are mixed at 50 ° C. with 59 parts of water and stirred until homogeneous. Then 5 parts of tributyl citrate, 1 part of the defoamer according to Example 1, 5 parts of polyethylene glycol 400 and 5 parts of 2-methyl-2,4-pentadiol are added to the homogeneous solution in succession. A viscous, storage-stable preparation is obtained.

Examples of use Example A:

To desize a fabric made from starch-sized raw cotton, it is padded with an aqueous liquor that contains the following components per liter:
1 g enzymatic desizing agent, e.g. amylase,
4 g sodium chloride and
3 g of the agent according to Example 2.

The tissue is squeezed to a liquor pick-up of 100 and stored at 80 ° C. for 2 hours. The fabric is then rinsed with hot, warm and cold water as usual and then dried.

To check the quality of the desizing, the tissue is treated with an iodine-iodine-potassium solution. The blue coloration that occurs when starch size is still present is assessed.

By adding the agent according to Example 2, the tissue is quickly wetted and completely deaerated.

Example B

To dye a knitted cotton fabric, the material is passed through a padder at a temperature of 20-30 ° C and a dipping time of 3-5 seconds and squeezed to a liquor absorption of 100%.

5 g des Mittels gemäss Beispiel 4,
5 g des gemäss Vorschrift 2 des EP-A-111454 hergestellten Pfropfpoly­merisates, als Flottenbindemittel,
2 g eines Dispergiermittels, z.B. Sulfonaphthalin/Formaldehyd-Kondensat
3 g m-Nitrobenzolsulfonsäure (Natriumsalz)
70 ml Wasserglas 37-40 Bé und
18 ml Natronlauge 36 Bé.The padding fleet contains the following components per liter:
18 g of the dye of the formula

5 g of the agent according to Example 4,
5 g of the graft polymer prepared according to regulation 2 of EP-A-111454, as a liquor binder,
2 g of a dispersant, eg sulfonaphthalene / formaldehyde condensate
3 g m-nitrobenzenesulfonic acid (sodium salt)
70 ml water glass 37-40 Bé and
18 ml sodium hydroxide solution 36 Bé.

The knitted fabric is stored at 20-30 ° C for 8 hours, the dye being fixed.

By adding the agent according to Example 4, the knitted fabric is quickly wetted and completely deaerated.

A uniform and genuine dyeing of the cotton treated in this way is obtained.

Example C

A yarn winding spool made of raw cotton yarn is placed in a circulation apparatus which contains an aqueous, 30 ° C warm preparation of 3 g / l of the agent according to Example 2.

Due to the strong wetting and deaeration effect of the agent, the winding body is quickly wetted and deaerated and can be dyed in the usual way with a dyeing liquor in a liquor ratio of 1:40
7 g / kg product of a vat dye, consisting of a mixture of Vat. Blue 4 CI 69800 and Vat. Blue 6 CI 69825 in a ratio of 1: 3
2 g / l of a fatty alkyl benzimidazole sulfonate
9 g / l sodium hydrosulfite
25 ml / l aqueous 30% sodium hydroxide solution
contains.

After the additives have been uniformly distributed, the dyeing liquor is heated to 60 ° C. in the course of 30 minutes and the cotton yarn is dyed at this temperature for 60 minutes. The material to be dyed is then oxidized, soaped, rinsed and dried as usual. By adding the agent according to Example 2, the yarn winding spool is quickly wetted and completely vented. A uniform coloring of the winding body is obtained.

Example D

To bleach a raw cotton fabric, the substrate is passed through a padder at room temperature and a dipping time of 3-5 seconds and squeezed to a liquor absorption of 95%.

The bleaching liquor contains the following components per liter:
10 ml sodium silicate solution 30 ° Bé,
5 g of the preparation according to Example 11,
75 ml 36 Bé sodium hydroxide solution,
60 ml of hydrogen peroxide and
5 g sodium persulfate.

The tissue is stored for 16 hours at 25-30 ° C and then washed hot and cold and neutralized.

The addition of the wetting agent according to Example 11 brings about a homogeneous, complete wetting of the tissue.

A uniformly bleached fabric is obtained, the CIBA-GEIGY degree of whiteness being increased from -72 to 47, the average degree of polymerization of cotton (DP) falling from 2740 to only 2530 and the degree of desizing according to TEGEWA being improved from grade 1 to grade 4.

Claims (17)

1. Means for wetting hydrophobic, capillary materials, characterized in that it is a water-soluble surfactant and an amphiphilic, phosphorus-free, poorly water-soluble organic compound with a melting point below 4 ° C and a boiling point above 200 ° C (at 1013 hPa ) contains. 2. Composition according to claim 1, characterized in that the water-soluble organic compound is a trialky ester of an aliphatic hydroxytricarboxylic acid or acetylated hydroxytricarboxylic acid having 4 to 8 carbon atoms per alkyl part, tetraalkylurea having 4 to 8 carbon atoms per alkyl part, a di - or trialkylamine with 4 to 10 carbon atoms per alkyl part, a bis-alkylaminoalkanol with 4 to 8 carbon atoms per alkyl part and 2 to 6 carbon atoms in the alkanol part or an alcohol of an acyclic terpene. 3. Composition according to claim 2, which contains as a trialky ester of an aliphatic hydroxytricarboxylic acid tributyl citrate. 4. Composition according to claim 2, which contains as a trialky ester of an aliphatic acetylated hydroxytricarboxylic acid acetyltributyl citrate. 5. Composition according to claim 2, which contains tetrabutylurea as tetraalkylurea. 6. Composition according to claim 2, which contains bis- (2-ethylhexyl) amine or tributylamine as di- or trialkylamine. 7. Composition according to claim 2, which contains 2-dibutylaminoethanol as bis-alkylaminoalkanol. 8. Composition according to claim 2, which contains geraniol as alcohol of an acyclic terpene. 9. Composition according to one of claims 1 to 8, characterized in that it contains an anionic surfactant. 10. Composition according to claim 9, characterized in that the anionic surfactant is a compound of the formula
R₁ ― O― (CH₂CH₂O

X₁
wherein R₁ is alkyl or alkenyl having 8 to 22 carbon atoms, X₁ carboxy-C₁-C₃-alkyl and m is 2 to 30. 11. Composition according to claim 9, characterized in that the anionic surfactant is a compound of the formula
R ― O― (CH₂CH₂O

X,
in which R is alkyl or alkenyl with 8 to 22 C atoms, alkylphenyl with 4 to 16 C atoms in the alkyl part or o-phenylphenyl, X is the acid residue of an inorganic, oxygen-containing acid or the rest of an organic acid and m is 2 to 30, is. 12. Composition according to one of claims 1 to 11, characterized in that it contains a nonionic surfactant. 13. Composition according to claim 12, characterized in that the nonionic surfactant is a fatty acid diethanolamide with 8 to 22 carbon atoms in the fatty acid residue. 14. Composition according to one of claims 1 to 13, characterized in that it additionally contains a defoamer. 15. Composition according to claim 14, which contains such a defoamer based on silicone oil. 16. Composition according to one of claims 1 to 15, in which the water-soluble surfactant and the sparingly water-soluble organic compound are present in a weight ratio of 20: 1 to 1: 1, in particular 10: 1 to 2: 1. 17. Use of the agent according to one of claims 1 to 16 for wetting hydrophobic, capillary materials.