EP0280206A2 - Lubricating agent for textile fibre materials - Google Patents

Abstract

Agents for lubricating textile fibre materials, containing symmetrical and/or asymmetrical dialkyl ethers of the general formula R<1>-O-R<2> where R<1> and R<2> are each straight-chain and/or branched saturated and/or unsaturated, optionally OH-substituted C6-24-alkyl groups of natural and/or synthetic origin alone or combined with known lubricating agents.

Description

The invention relates to agents for smoothing textile fiber materials, a method for smoothing textile fiber materials and the use of dialkyl ethers as smoothing agents.

Higher running speeds of yarns and threads as well as differentiated and sophisticated techniques for the production of textile fabrics have led to ever increasing demands being placed on the running behavior of yarns in the modern textile industry. In order to meet these requirements, smoothing and softening substances have to be applied to the yarns and the fabric made from them to improve their further processing properties.

The smoothing agents used must on the one hand reduce the friction between the individual fibers as well as between fibers or yarns and metal, and on the other hand ensure that fabric can be sewn perfectly. If excessive frictional forces occur during sewing, sewing damage occurs if threads are struck, broken or thermally damaged. The consequence of sewing damage is particularly serious in the case of knitwear, because drop stitches occur at the latest when the goods are mechanically stressed. For this reason, the mobility of the threads in the stitch structure is of great importance. The reduction in needles Stitch forces during sewing on modern high-speed sewing machines have become particularly important, since high-speed sewing machines can perform up to 7,000 punctures per minute purely mechanically. However, this requires thicker, more vibration-stable needles, which in turn more easily cause stitch damage.

Paraffins, esters, polyethylenes, silkones and polyalkylene glycols are known smoothing agents (see, for example, in "Melliand Textile Reports" 3 , 203 to 207 (1977)), the effectiveness of which in many cases depends on the type of fiber substrate. From the German patent application DE-OS 32 38 395 polyethylenes with an average molecular weight of 3000 to 8000, a density of 0.94 to 1.01, an acid number of 25 to 60 and a saponification number of 40 to 80 are known as smoothing agents for textile fiber materials .

The object of the present invention was to develop smoothing agents which, compared to smoothing agents from the prior art, show a significant improvement, i.e. Reduce the friction between individual fibers and between fibers and metal as well as a significant reduction in puncture forces and their effectiveness is independent of the type of fiber substrate.

The invention is based on the surprising finding that with symmetrical and / or non-symmetrical dialkyl ethers of the general formula
R¹ - O - R²
textile fiber materials treated with R 1, R 2 = straight and / or branched-chain, saturated and / or unsaturated, optionally substituted with OH groups, C _6-24 alkyls, have greatly reduced coefficients of friction and significantly reduced puncture forces.

The invention accordingly relates to agents for smoothing textile fiber materials in the form of solutions, emulsions or dispersions, which are characterized in that they are symmetrical and / or non-symmetrical dialkyl ethers of the general formula
R¹ - O - R²
contain with R¹, R² = straight and / or branched, saturated and / or unsaturated, optionally substituted with OH groups, C _6-24 alkyls of natural and / or synthetic origin alone or in combination with known smoothing agents.

Another object of the invention is a method for smoothing textile fiber materials, which is characterized in that textile fiber materials are smoothed with agents that have symmetrical and / or non-symmetrical dialkyl ethers of the general formula
R¹ - O - R²
contain with R¹, R² = straight and / or branched, saturated and / or unsaturated, optionally substituted with OH groups, C _6-24 alkyls of natural and / or synthetic origin alone or in combination with known smoothing agents.

Furthermore, the use of symmetrical and / or non-symmetrical dialkyl ethers of the general formula
R¹ - O - R²
with R¹, R² = straight and / or branched, saturated and / or unsaturated, optionally substituted with OH groups ized C _6-24 alkyls of natural and / or synthetic origin alone or in combination with known smoothing agents as a smoothing agent for textile fiber materials.

In the present invention, the term "alkyl" stands for saturated and / or unsaturated alkyl radicals, that is to say for alkyl and / or alkenyl radicals.

Dialkyl ethers which contain 8 to 22 carbon atoms in the alkyl radicals of natural and / or synthetic origin are preferably present in the smoothing agents according to the invention, for example octyl dodecyl ether, didodecyl ether, tallow stearyl ether, ditalgia, distearyl ether, oleyl stearyl ether and / or 2-hydroxyhexadecyl-talgether. Dialkyl ethers having 16 to 18 carbon atoms in the alkyl chains of natural and / or synthetic origin, for example ditalgal, distearyl ether, tallow stearyl ether and / or 2-hydroxyhexadecyl tallow, are particularly preferred.

The dialkyl ethers according to the invention are prepared in a manner known per se, for example by reacting alkali metal or ammonium salts of C _6-24 alkyl sulfates with C _6-24 alkyl alcohols at 180 ° C. or the ring having terminally alkoxylated C _6-24 olefins C _6-24 alkyl alcohols, optionally in the presence of a catalyst, is opened at 120-150 ° C.

Symmetrical and / or asymmetrical dialkyl ethers are used as the only smoothing agent component or in combination with known smoothing agents in smoothing agent mixtures. Known smoothing agents are preferably paraffins with softening points between 35 and 80 ° C, polyethylenes, for example anoxidized polyethylene waxes, which are described in DE-OS 32 38 395, fatty acid esters with 8 to 22 carbon atoms in the fat residue and 1 to 22 carbon atoms in the Alcohol residue, for example methyl palmitate, stearyl stearate, behenyl behenate and / or isotridecyl stearate, silicones for example dimethylpolysiloxane and / or polyalkylene glycols, for example polyethylene glycols with average molecular weights from 600 to 2000, are used. In the case of smoothing agent mixtures, the weight ratio of dialkyl ether to smoothing agents from the prior art is preferably between 10: 1 and 1: 4, particularly preferably between 4: 1 and 1: 1.

The smoothing agents according to the invention are applied in the form of solutions, emulsions or dispersions to textile fiber materials. The application can be carried out both from water and from organic solvents, for example aliphatic and / or aromatic hydrocarbons, such as gasoline, cyclohexane, toluene, xylene or halogenated, preferably chlorinated hydrocarbons, such as methylene chloride, per-chloroethylene. The smoothing agent content in solutions is between 5 and 10 percent by weight, in emulsions and dispesions between 5 and 30 percent by weight. The smoothing agents according to the invention are preferably applied in the form of aqueous dispersions to textile fiber materials. The term “textile fiber materials” is understood to mean natural fibers, for example cotton, wool and / or cellulose, synthetic fibers, for example polyacrylonitrile, polyester, polyamide, triacetate, polyethylene and / or polypropylene, and mixtures of natural and synthetic fibers. The textile fiber materials can be in the form of a flock, sliver, knitting yarn, weaving yarn, sewing thread, knitted fabric, fabric or nonwoven fabric, preferably knitting yarn, weaving yarn, sewing thread, knitted fabric or fabric. The material can be raw white, bleached or colored. The yarns can be both filament and fiber yarns.

The aqueous dispersions containing the smoothing agents according to the invention are prepared in a manner known per se, either by mixing all the components at from 80 to 170 ° C. or by melting all the components with the exception of water and then water, if appropriate under pressure, at 80 to 170 ° C is added. However, it is also possible to add the melt to hot water at 80 to 100 ° C. The resulting finely divided aqueous dispersions have solids contents of 5 to 40 percent by weight and pH values of 3.5 to 11.

The smoothing agents according to the invention are applied to the textile fiber materials with the aid of conventional apparatus, such as dyeing apparatus for cross-wound bobbins, skeins or muffs, reel runners or jet dyeing systems. The application after an exhaust process, for example a drawing process from a dye or rinsing bath, is carried out from an aqueous liquor with a liquor ratio between 1: 2 and 1:40 and a pH value in the liquor between 2 and 8 at temperatures between 25 and 80 ° C and a concentration, based on the weight of the goods, of from 0.2 to 3.0, preferably from 0.2 to 2.5, percent by weight of smoothing agent. The smoothing agents according to the invention can also be applied to textile fiber materials by a forced application process, for example padding, immersion centrifugal process, godet application, via metering pump systems as are customary in the production of synthetic filament yarns or by spraying. In the padding process - based on 100% active ingredient content - a concentration of 1 to 50 g / l of liquor, preferably of 5 to 20 g / l of liquor, is used, and at the same time high-finishing agents such as anti-crease or anti-shrinkage finishing agents can be used.

In addition to reducing the friction between individual fibers and between fibers and metal and reducing the puncture forces, textile and / or fiber auxiliaries also require further properties: for example, these should lead to little or no yellowing, shear stable, softening, little, if not non-foaming and thermally stable. In order to meet these requirements, the smoothing agents according to the invention, which are preferably in In the form of aqueous dispersions, are mixed with plasticizers and conventional auxiliaries, such as antioxidants, defoamers, stabilizers, antistatic agents, preservatives, pH regulators and / or fragrances, contained in textile and / or fiber auxiliaries. Textile and / or fiber auxiliaries containing smoothing agents according to the invention preferably contain
5 to 30 percent by weight of dialkyl ether alone or in combination with paraffins, polyethylenes, fatty acid esters, silicones and / or polyalkylene glycols
1 to 20 weight percent dispersants
0 to 15 weight percent plasticizer
0 to 6% by weight of customary auxiliaries contained in textile and / or fiber auxiliaries, for example antioxidants, defoamers, stabilizers, antistatic agents, preservatives, pH regulators and / or fragrances
ad 100 weight percent water.

The smoothing agents according to the invention, preferably in the form of aqueous dispersions, can be dispersed in water by methods known per se using nonionic, cationic, anionic and / or amphoteric dispersants. Suitable nonionic dispersants are alkoxylated, preferably ethoxylated and / or propoxylated fats, oils, fatty alcohols with 8 to 24 carbon atoms in the fat residue, fatty amines with 8 to 24 carbon atoms in the fat residue and / or C _8-18 alkylphenols, for example castor oil 25 ethylene oxide units, tallow alcohol with 5 ethylene oxide units, tallow alcohol with 20 ethylene oxide units, C _12-18 coco alcohol with 10 ethylene oxide units and / or nonylphenol with 10 ethylene oxide units. For example, fatty amines contain 2 to 10 ethylene oxide units. Suitable cationic dispersants are alkoxylated, preferably ethoxylated and / or propoxylated, alkylamines having 10 to 22 carbon atoms in the form of their ammonium salts, for example stearylamine with 10 moles of ethylene oxide. Suitable anionic dispersants are, for example, alkali and / or ammonium salts of C _6-24 fatty acids, C _8-22 alkyl and / or C _8-22 alkyl _ether sulfates, C _8-22 alkyl and / or C _{8 22} alkyl benzene sulfonates, C _8-22 alkyl and / or C _8-22 alkyl _benzene sulfosuccinates and / or C _8-22 alkyl and / or C _8-22 alkyl _ether phosphates. Examples of suitable amphoteric dispersants are C _8-22- alkyldimethylbetaines, NC _8-22 -alkylamido betaines and / or _amphoteric surfactants to be derived from amino acids.

Fatty acid amidopolyamines, which preferably consist of saturated C _16-22 fatty acids or C _16-22 fatty acid mixtures and their esters and polyalkylene polyamines such as diethylene triamine, triethylene tetramine, tetraethylene pentamine or Aminoethylethanolamine can be obtained, the reaction being carried out in such a molar ratio that amine nitrogen atoms capable of salt formation are retained. The fatty acid amidopolyamines are in the form of their salts with preferably lower carboxylic acids or hydroxycarboxylic acids with 1 to 4 carbon atoms, for example acetic acid or glycolic acid. In the context of the present invention, inorganic acids, for example hydrogen halides, such as hydrogen chloride, oxygen acids of phosphorus, such as orthophosphoric acid, phosphoric and hypophosphorous acid, oxygen acids of sulfur, such as sulfuric acid and sulfurous acid, and also boric acid and phosphonic acids are suitable for the formation of fatty acid amidopolyamine salts.

Quaternary ammonium salts such as lauryl trimethyl ammonium chloride and dodecyl benzyl trimethyl ammonium metho are also suitable sulfate, dimethyl-distearylammonium chloride and / or 3-ethyl-1-hydroxyethyl-2-heptadecyl-imidazolinium-ethyl sulfate as a plasticizer in textile and / or fiber auxiliaries containing smoothing agents according to the invention. Furthermore, mono- and / or diethanolamides, such as tallow fatty acid diethanolamide, can also be present as softening constituents in the smoothing agents according to the invention.

Textile and / or fiber auxiliaries containing smoothing agents according to the invention contain 0 to 0.5 percent by weight of antioxidants, for example oxygen acids of phosphorus, such as phosphorous and hypophosphorous acid, or alkali disulfites, 0 to 1.0 percent by weight of silicone-based defoamer, 0 to 1, 0% by weight stabilizers, for example starch derivatives and gum arabic, 0 to 5% by weight of antistatic agents, for example alkoxylated, preferably ethoxylated and / or propoxylated, C _6-24 fatty amines, 0 to 0.05% by weight of preservatives, for example formaldehyde, pH regulators, for example C _1-4 -carboxylic acids and / or C _1-4 hydroxycarboxylic acids, such as acetic acid, glycolic acid, alkali hydroxides such as potassium hydroxide and / or amino alcohols such as 2-diethylaminoethanol and / or 0 to 0.1 weight percent of fragrances.

The textile fiber materials treated with the smoothing agents according to the invention, regardless of the way in which the smoothing agents are applied to the textile fiber material, have significantly lower friction values and greatly reduced puncture forces. The smoothing agents according to the invention have a high thermal stability in the production of high-strength filament yarns and are color-stable and non-volatile under thermal stress, for example when drying or fixing.

Examples example 1

After the immersion centrifugal process, xylene solutions, each containing a smoothing agent, were applied to various yarn substrates and the corresponding coefficients of friction were measured on the coefficient of friction from the company Schlafhorst (Table 1). Compared to smoothing agents of the prior art, the smoothing agent Ditalgether according to the invention shows significantly reduced coefficients of friction.

(Bw = cotton, PES = polyester, PAC = polyacrylic, Wo = wool, MG = molecular weight)

Example 2

EO means ethylene oxide

Production of stable aqueous dispersions A to E which contain smoothing agents according to the invention.

A)

115.5 g of 2-hydroxyhexadecyl tallow (produced by ring opening a terminally epoxidized C₁₆ olefin with technical tallow alcohol)
38.5 g of oxidized high pressure (HD) polyethylene (average molecular weight = 4500; acid number (SZ) = 30
4.5 g of 2-diethylaminoethanol
13.3 g tallow alcohol5 EO
6.7 g tallow alcohol20 EO
20.0 g C _12-18 coconut alcohol.10 EO
0.6 g sodium disulfite
600.9 g water

The starting materials listed were heated for 1 hour at 155-160 ° C. with stirring in a cup autoclave. After cooling, 800 g of a finely divided dispersion with a pH of 8.8 were obtained.

B)

100.0 g of tallow stearyl ether (produced by reaction of sodium tallow alkyl sulfate with n-octadeconal)
10.0 g castor oil · 25 EO
25.0 g ditallow dimethyl ammonium chloride
2.5 g acetic acid
372.5 g water

With the exception of water, the feed materials were in one simple stirring apparatus melted homogeneously. At 80 ° C., the water, likewise heated to 80 ° C., was allowed to flow in over 15 minutes, the mixture was stirred for another 30 minutes and then cooled.

The fine-particle dispersion had a pH of 5.2.

C)

100.0 g tallow stearyl ether (produced analogously to B)
54.0 g of anoxidized HD polyethylene analog A
4.8 g potassium hydroxide solution, 45%
20.0 g C _12-18 coconut alcohol.10 EO
20.0 g nonylphenol.10 EO
0.8 g sodium disulfite
600.4 g water

800 g of a finely divided dispersion, the pH of which was 9.8, were prepared from the starting materials by the method described in A.

D)

86.6 g octyldodecyl ether (prepared by reacting Na dodecyl sulfate with n-octanol)
28.9 g of anoxidized HD polyethylene analogous to A
3.4 g of 2-diethylaminoethanol
10.0 g tallow alcohol · 5 EO
5.0 g tallow alcohol20 EO
15.0 g C _12-18 coconut alcohol10 EO
0.6 g sodium disulfite
454.5 g water

604 g of a finely divided dispersion with a pH of 9.1 were produced from the starting materials by the method described in A.

E)

250.0 g of the dispersion obtained according to D and
250.0 g of a conventional, pseudo-cationic, textile plasticizer dispersion (fatty acid amidoamine from hardened beef tallow and aminoethylethanolamine in the form of the acetate) with 20% active ingredient
were mixed together. A finely divided, storage-stable dispersion was obtained.

Example 3 (comparison)

Formulations of stable aqueous dispersions F to K which contain smoothing agents from the prior art.

F)

190.0 g low pressure (LD) - polyethylene (average molecular weight = 1650; SZ = 26; melting point = 98 - 102 ° C)
24.7 g oleyl alcohol · 5 EO
24.7 g coconut alcohol10 EO
20.0 g potassium hydroxide solution, 20%
1.0 g formalin, 30%
741.0 g water

G)

192.5 g HD polyethylene (average molecular weight = 4700; SZ = 29; melting point = 130 - 140 ° C)
11.2 g diethylethanolamine
20.0 g coconut alcohol10 EO
13.3 g tallow alcohol5 EO
6.7 g tallow alcohol20 EO
1.65 g Na₂S₂O₅
755.0 g water

H)

200.0 g LD polyethylene analog F
55.0 g tallow amine10 EO
6.3 g acetic acid, 10%
750.0 g water

I)

179.5 g HD polyethylene analog G
20.8 g glycolic acid, 70%
53.7 g tallow amine · 2 EO
3.1 g sodium disulfite
742.9 g water

J)

180.0 g paraffinum durum (melting point = 52 - 54 ° C)
120.0 g isotridecyl stearate
2.4 g stearyl alcohol20 EO
48.0 g fatty acid amidopolyamine, basis: behen / stearic acid and tetraethylene pentamine; N _titr. = 3.2%
9.6 g coconut fatty acid polydiethanolamide
48.0 g acetic acid, 60%
592.0 g water

K)

15.0 g stearyl stearate
5.0 g isotridecyl stearate
2.0 g castor oil · 25 EO
5.0 g dimethyl distearyl ammonium chloride
0.5 g acetic acid, 60%
72.5 g water

Application example 1

100% cotton yarn was dyed on a high temperature short liquor dyeing machine in the form of a press spool. The dyeing was carried out with reactive dyes, soaped and aftertreated to improve the wet fastness properties. The subsequent smoothing treatment was carried out from a fresh bath in acetic acid medium at a pH of 5.5 for 20 minutes at 50 ° C. The aqueous dispersions containing the smoothing agents B and E according to the invention and the known smoothing agents H, I and J were used with a respective Active ingredient requirement of 0.6 percent by weight. The yarns were dried on a pressure dryer.

The friction coefficients My were determined on the sleep hormone balance and are summarized in Table 2.

Example of use 2

BW / PES knitwear was dyed with reactive and disperse dyes on a laboratory jet dyeing machine. The finish was carried out from a fresh bath at a pH of 6 in 20 minutes at 45 ° C. using aqueous dispersions containing the smoothing agents B or E according to the invention or the known smoothing agents H, I or J, each with an active ingredient coating of 0.5 percent by weight . The drying of the product sections was carried out in a tumbler.

As a measure of the sewability, the sewing needle penetration forces were measured on a Pfaff industrial sewing machine type 483 with built-in penetration force sensor, 4000 stitches per minute. The mean values from 50 individual punctures are listed in Table 3.

Example of use 3

Cotton knitwear was refined on the padder using 50 g / l Flott Stabitex® FRD, Henkel KGaA (dimethyloldihydroxyethylene urea) and 5.0 g / l liquor magnesium chloride as a catalyst. Shock condensation was carried out on the stenter frame at 175 ° C. for 30 seconds. In order to improve the sewing ability and the handling, 50 g / l of each of the aqueous dispersions containing the smoothing agents A, B, C, D or E or the known smoothing agents F, G, H, I, J or K were added to the liquors. The squeeze effect on the foulard was about 80%.

The sewing needle puncture forces in cN were determined as in Application Example 2 and are summarized in Table 4.

Claims (8)

1. Means for smoothing textile fiber materials in the form of solutions, emulsions or dispersions, characterized in that these agents are symmetrical and / or non-symmetrical dialkyl ethers of the general formula
R¹ - O - R²
contain with R¹, R² = straight and / or branched, saturated and / or unsaturated, optionally substituted with OH groups, C _6-24 alkyls of natural and / or synthetic origin alone or in combination with known smoothing agents. 2. Composition according to claim 1, characterized in that the alkyl radicals R¹ and R² have 8 to 22, preferably 16 to 18 carbon atoms. 3. Agent according to one or both of claims 1 and 2, characterized in that these agents contain paraffins, polyethylenes, fatty acid esters, silicones and / or polyalkylene glycols as known smoothing agents. 4. Composition according to one or more of claims 1 to 3, characterized in that the weight ratio of dialkyl ether to known smoothing agents is between 10: 1 and 1: 4, preferably between 4: 1 and 1: 1. 5. Composition according to one or more of claims 1 to 4, characterized in that the compositions are in the form of aqueous dispersions. 6. Agent according to one or more of claims 1 to 5, characterized in that these agents contain:
5 to 30 percent by weight of dialkyl ether alone or in combination with known smoothing agents
1 to 20 weight percent dispersants
0 to 15 weight percent plasticizer
0 to 6% by weight of conventional auxiliaries contained in textile and / or fiber auxiliaries, for example antioxidants, defoamers, stabilizers, antistatic agents, preservatives, pH regulators and / or fragrances
ad 100 weight percent water. 7. A method for smoothing textile fiber materials, characterized in that textile fiber materials are treated with an agent according to one or more of claims 1 to 6. 8. Use of dialkyl ethers according to one or more of claims 1 to 6 as a smoothing agent for textile fiber materials.