EP0249126B1 - Hydrophobic and oleophobic finishes - Google Patents

Abstract

Waterproofing and oil-proofing agents contain A. compounds containing a perfluoroalkyl group, and B. quaternization products of basic fatty acid amides.

Description

• A. eine Verbindung mit einer Perfluoralkylgruppe mit 2 - 20 Kohlenstoffatomen, die durch Sauerstoff unterbrochen sein kann und die mit einer reaktiven oder polaren Trägergruppe oder mit der Kette eines Polymers verbunden ist, und
• B. Quaternierungsprodukte basischer Fettsäureamide aus Umsetzungen von Fettsäuren mit mehr als 8 C-Atomen, Polyaminen und 0,5 bis 5 Äquivalent Epichlorhydrin bezogen auf Aminogruppen im basischen Amid

enthalten,
sowie Verfahren zur Textilausrüstung mit diesen Mitteln.The invention relates to hydrophobic and oleophobicizing agents

• A. a compound having a perfluoroalkyl group of 2 to 20 carbon atoms which can be interrupted by oxygen and which is connected to a reactive or polar carrier group or to the chain of a polymer, and
• B. Quaternization products of basic fatty acid amides from reactions of fatty acids with more than 8 carbon atoms, polyamines and 0.5 to 5 equivalents of epichlorohydrin based on amino groups in the basic amide

contain,
and processes for textile finishing with these agents.

In the case of the compounds A, both the carrier group and the polymer serve to convert the inert fluorocarbon residue as carrier of the phobicization function into a stable preparation, e.g. B. to be transferred in an aqueous medium or to bring about the adhesion and permanence of the fluorocarbon group on the substrate. Examples of such perfluoro compounds are perfluorocarboxylic acids or sulfonic acids or their salts and derivatives such as amides and (co) polymers of unsaturated compounds which contain the perfluoroalkyl radical mentioned, with optionally fluorine-free monomers, e.g. B. in the form of polymer dispersions or latices. Suitable unsaturated compounds with a perfluoroalkyl radical are known, for example, from US Pat. No. 3,916,053.

Preferred compounds are acrylate (co) polymers with a fluorine content of 20-45, in particular 35-45% by weight. Compounds of this type are described, for example, in US-A-3,356,628, 3,329,661, 3,752,783 and 4,296,224.

Since these fluorine compounds are expensive and often have to be additionally fixed on the substrate with the aid of other auxiliaries to be incorporated in a phobing formulation, they are sometimes waxed in combination with paraffin fractions or paraffin waxes which act as extenders and / or fatty acid esters and melamine, urea resins or other resins mostly based on methylol compounds (e.g. compare Chwala / Anger: Handbuch der Textilhilfsmittel, Verlag Chemie-Weinheim - New York - 1977, pages 745 - 747, 771) .

Such formulations sometimes achieve sufficient to good phobing effects on a wide variety of substrates even at reduced fluorine component contents. B. with wool, relatively large quantities are required.

However, it is desirable not to achieve the intended phobing effect by increasing the amount of the coating, but by improving the phobia of the coating material or the coating of phobing material that may interact with the substrate. According to the prior art, this aim can be achieved by reducing the amount of extenders contained in the phobing formulations in addition to the fluorine compounds, but this loses the advantages sought by the use of extenders and other auxiliaries.

With the quaternized basic fatty acid amides, a group of extenders has now surprisingly been found which, in combination with the phobicizing fluorine compounds on a wide variety of substrates, results in surprisingly high quality and permanence and furthermore allows the required amount of fluorine compounds to be significantly reduced.

Preferred fatty acids are straight-chain or branched, saturated or unsaturated fatty acids with 12-22 carbon atoms or mixtures thereof, in particular those with melting points above 30 ° C.

Preferred polyamines are polyalkylene polyamines and in particular polyethylene-polyamine mixtures which are obtained when dihaloethane is reacted with ammonia. Of these mixtures, those which consist of polyethylene polyamines with at least 3 amino groups, in particular 3-7 amino groups, are again to be mentioned. They are obtained, for example, by distilling off the di- and triamine fraction from the reaction products of dichloroethane and ammonia mentioned above.

The basic amides are obtained from this by reacting 0.75-1.5, in particular 0.8-1.1, equivalents of fatty acid per primary amino group of the polyethylene polyamine.

Quaternized basic amides B., which are preferably prepared by quaternization in an aqueous medium, are described, for example, in GB-A-711 404, in DE-A-35 15 479 and 35 27 976. Particularly preferred amides B. are known from EP-A-0 008 761 and DE-A-35 15 480. From these publications is the use of the amides reacted with epichlorohydrin in aqueous medium as paper sizing agents is known.

However, the agents according to the invention serve in particular as textile finishing agents. They are preferably in the form of aqueous dispersions. The quantitative ratio of A: B is, for example, 2: 1 to 1:10, in particular 1: 1 to 1: 6, based on the solids content. The aqueous dispersions preferably contain a total solids content of 0.5-50, preferably 5-25% by weight.
The dispersions are stable and can be marketed as such. You can add other ingredients such as other textile auxiliaries, e.g. B. synthetic resins. These further constituents are preferably nonionic or cationic.

The aqueous dispersions can be further diluted with water before use on the textile materials. The ratio of aqueous dispersion to textile material is chosen so that a coating quantity of 0.5-15.0 g, preferably 0.5-5.0 g and in particular 0.5-1.5 g, total solids of the mixture according to the invention per kg Textile material is achieved.

Surprisingly, it was found that excellent hydrophobicizing and oleophobicizing effects can be achieved even with these relatively small application quantities.

With the mixtures according to the invention, natural and synthetic materials such as fibers, filaments, yarns, nonwovens, fabrics, knitted fabrics and knitted fabrics made in particular of cellulose and its derivatives but also of polyester, polyamide and polyacrylonitrile materials, wool or silk can be successfully finished.

The hydrophobized or oleophobicized textile structures, such as nonwovens or in particular fabrics, are found, for. B. Use for the production of umbrella coverings, tents, water-repellent clothing or covers, balloon covers, awnings, textile floor coverings, packaging materials or footwear.

The finishing is carried out by known methods, preferably by the pull-out or padding method, for example between room temperature and 40 ° C., but also by splashing or spraying with a subsequent temperature treatment at 80-180, preferably 120-150 ° C.

Of interest is the observation that, on the one hand, the textile finishing agents according to the invention have no advantages with regard to a sizing effect on paper compared to the components B. This behavior of the mixtures used according to the invention shows that the known action of the quaternized basic fatty acid amides used as paper sizes does not indicate their suitability as a component of the invention Phobierung formulations allow, although the paper sizing is an effect that appears to be comparable to a hydrophobing.

The parts and percentages given in the following examples relate to the weight, unless stated otherwise.

Paper equipment

It is shown here that the combination of a quaternized basic fatty amide B., which is well suited for paper sizing, with a polymeric perfluoroalkane active ingredient A. used for the purposes of textile waterproofing according to the prior art, does not improve the ink swimming times or Cobb values at Brings about paper. It was therefore not to be expected that this combination would show an excellent hydrophobic effect in the textile sector.

As dispersion A., an acrylate copolymer containing perfluoroalkane groups and having an F content of approx. 40% by weight in solids, used in the market for textile hydrophobization and present in approx. 15% aqueous dispersion, is used.

An approximately 15% aqueous dispersion according to EP-A-0 008 761, size G, is used as dispersion B.

Dispersions A. and B. are now mixed in a weight ratio of 1: 2.

Dispersion B.:

21 Sek.

Dispersion A. + B.:

16 Sek.

With an application amount of 0.46% based on paper stock, the following ink floating times are measured in the paper equipment and sizing test carried out in accordance with EP-A-0 008 761:

Dispersion B .:

21 sec

Dispersion A. + B .:

16 sec

Textile equipment Products

Komponente I:

ca. 15 %ige wäßrige Dispersion gemäß EP-A-0 008 761, Leimungsmittel G.

Komponente II:

156 Teile einer hydrierten Fischölfettsäure mit einem Gehalt von ca. 80 % Behensäure, Säurezahl 167, Erstarrungspunkt ca. 67° C, werden mit 56 Teilen eines Mischamins aus ca. 40 % Triethylentetramin, 30 % Tetraethylenpentamin und 30 % Pentaethylenhexamin bei 175° C unter Abdestillieren des Reaktionswassers zum Amid umgesetzt.
Dann werden unter Rühren 1390 Teile Wasser zugesetzt und die Temperatur auf 80° C eingestellt. Nun werden 60 Teile Epichlorhydrin eingerührt. Man läßt 2 Stunden rühren und fügt nach Abkühlung auf 50° C eine Lösung von 1,3 Teilen NaCl in 100 Teilen Wasser hinzu.
Man erhält eine ca. 15 %ige Dispersion.

Komponente III:

wie Komponente II; als Fettsäure wird jedoch ein Gemisch aus gleichen Teilen technischer Behensäure und technischer Ölsäure verwendet.

Komponente IV:

Eine Mischung aus 50 % eines Kondensationsproduktes, hergestellt aus 1 Mol Hexamethylol-melamin-pentamethyläther, 1,5 Mol Behensäure und 0,9 Mol Methyldiäthanolamin bei 130° C währen 3 Stunden und 50 % Paraffin (Schmelzpunkt 52° C).

The products listed below were used for the following examples to illustrate the improvement in the oleo- and hydrophobization of textiles:
Quaternized basic fatty amides:

Component I:

15% aqueous dispersion according to EP-A-0 008 761, sizing agent G.

Component II:

156 parts of a hydrogenated fish oil fatty acid with a content of approx. 80% behenic acid, acid number 167, freezing point approx. 67 ° C, with 56 parts of a mixed amine of approx. 40% triethylene tetramine, 30% tetraethylene pentamine and 30% pentaethylene hexamine at 175 ° C Distilling off the water of reaction converted to the amide.
Then 1390 parts of water are added with stirring and the temperature is set to 80.degree. Now 60 parts of epichlorohydrin are stirred in. The mixture is stirred for 2 hours and, after cooling to 50 ° C., a solution of 1.3 parts of NaCl in 100 parts of water is added.
An approximately 15% dispersion is obtained.

Component III:

like component II; however, a mixture of equal parts of technical behenic acid and technical oleic acid is used as the fatty acid.

Component IV:

A mixture of 50% of a condensation product, prepared from 1 mol of hexamethylol-melamine-pentamethyl ether, 1.5 mol of behenic acid and 0.9 mol of methyl diethanolamine at 130 ° C for 3 hours and 50% paraffin (melting point 52 ° C).

Komponente V:

Ein als 15 %ige wäßrige Dispersion vorliegendes Perfluoralkan-Gruppen enthaltendes Acrylat-Copolymeres mit einem Fluorgehalt von ca. 40 % im Feststoff.

Perfluoroalkyl group-containing phobing agent:

Component V:

An acrylate copolymer containing perfluoroalkane groups as a 15% aqueous dispersion with a fluorine content of about 40% in the solid.

Kunstharz A:

Fixapret CPN (BASF)

Kunstharz B:

ACRAFIX M (Bayer)

Katalysator:

Zinknitrat

For the surface stabilization of the textile substrates made of cotton and cotton / synthetic fibers or for the design of the handle of the PAC awning fabrics, commercially available synthetic resins and corresponding catalysts are also used.

Resin A:

Fixapret CPN (BASF)

Resin B:

ACRAFIX M (Bayer)

Catalyst:

Zinc nitrate

Phobierungsflotten are made from these components, which contain different amounts of the components depending on the textile fiber substrate.

Test methods

• 1. Die Beregnungsprüfung erfolgt in Anlehnung an DIN 53 888 mit dem Beregnungsprüfgerät nach Dr. Bundesmann.
  Bewertung
  • a) Abperlzeit in Minuten
  • b) Abperleffekt in Noten 5-1
    Note 5 bedeutet höchster Abperleffekt
    Note 1 bedeutet geringster Abperleffekt
  • c) Wasseraufnahme W in %
  • d) Wasserdurchschlag in cm³
• 2. Die Wasserdichtheitsprüfung erfolgt in Anlehnung an DIN 53 886 (Schoppertest).
• 3. Der Ölabweisungstest erfolgt in Anlehnung an ATTCC Test Methode 118-1978.

After a 24-hour air conditioning at 20 ° C ± 2 ° C and 65% relative humidity, the finished textile samples are subjected to the appropriate tests.

• 1. The irrigation test is carried out in accordance with DIN 53 888 with the irrigation tester according to Dr. Bundesmann.
  rating
  • a) beading time in minutes
  • b) Pearl effect in notes 5-1
    Grade 5 means the highest water repellency
    Grade 1 means the lowest beading effect
  • c) water absorption W in%
  • d) water penetration in cm³
• 2. The water tightness test is based on DIN 53 886 (Schoppertest).
• 3. The oil repellency test is based on ATTCC test method 118-1978.

rating

The grade for oil repellency corresponds to the highest numbered test liquid that does not wet the fiber material within 30 seconds:
Grade 1 lowest value
Grade 8 highest value.

example 1

A cotton gabardine fabric with a m² weight of approx. 240 g was equipped with the following formulations on the foulard. a b c d Synthetic resin A 60 60 60 60 g / l catalyst 4th 4th 4th 4th g / l Component V 20th 20th 20th 20th g / l Component II - 20th - - g / l Component III - - 20th - g / l Component IV - - - 10th g / l

The cotton fabric was soaked in a chassis with the above-mentioned liquors and squeezed between 2 rubber rollers (foulard). The liquor absorption afterwards was 70% based on the textile weight. The swatches were dried at 100 ° C and treated at 150 ° C for 5 minutes. The test showed the following values: a b c d 1a) beading time (minutes) 0 10th 10th 10th 1b) Beading off effect (grade 5-1) 2nd 5 5 5 1c) water absorption (%) 38 7 19th 12 1d) water penetration (cm³) 20th 10th 11 13 3) Oil repellency (grade 1-8) 1 3rd 5 3rd

The evaluation shows that the amount of fluorine component V used is too small for equipment without an extender and gives no water-repellent effects.

The addition of components II, III and IV results in the water repellency test (a-d) which corresponds to the standard of rainwear equipment.

The components II and III claimed according to the invention give this increase of 3 g / l, based on the solid substance, while component IV, which is not according to the invention, is effective only when the amount used is 10 g / l.

There is also a major difference in the lack of grip on the treated textile substrate: Component IV does not improve the grip compared to textile goods treated only with Component V, but rather affects the character of the grip on the rougher, harder side.

Components II and III, on the other hand, create a soft, smooth and flowing handle.

It is known that extenders, in combination with fluorine-based phobing agents, increase the oil-repellent effect (for example, formulation d). However, the increase in effect with component III represents an improvement that cannot be achieved with known extenders.

Example 2

A colored polyester / cotton poplin fabric (67% PES / 33% cotton) with a weight of approx. 160 g m² was equipped with the following formulations on the foulard: a b c Synthetic resin A 60 60 60 g / l catalyst 4th 4th 4th g / l Component V 20th 20th 20th g / l Component II - - 20th g / l Component IV - 10th - g / l

The liquor absorption was 65%, the subsequent treatment was carried out as described in Example 1.

The test showed the following values: a b c 1a) beading time (minutes) 10th 10th 10th 1b) Beading off effect (grade 5-1) 5 5 5 1c) water absorption (%) 17th 12 3rd 1d) water penetration (cm³) 2nd 4th 2nd 3) Oil repellency (grade 1-8) 1 3rd 3rd

The finished samples were then washed 5 times at 40 ° C on a Miele washing machine type W 763 with the easy-care program with the addition of a household detergent and dried at 80 ° C in a Miele household dryer.

The test showed the following values: a b c 1a) beading time (minutes) 0 3rd 10th 1b) Beading off effect (grade 5-1) 2nd 2nd 5 1c) water absorption (%) 32 24th 12 1d) water penetration (cm³) 15 15 0 3) Oil repellency (grade 1-8) 1 1 2nd

Component II claimed according to the invention improves the washing resistance of fluorine finishes in such a way that even after 5 machine washes, the phobic values are completely retained, while the finishes without extender or with component IV drop off significantly or are no longer present.

Example 3

The textile goods described in Example 2 were equipped with the following liquors using the same process and the same treatment. a b c d Synthetic resin A 60 60 60 60 g / l catalyst 4th 4th 4th 4th g / l Component V 30th 30th 30th 30th g / l Component I - - - 20th g / l Component IV - 10th 20th - g / l

Exam values:
The irrigation test showed very good beading values for the 4 pieces of equipment during the 10-minute irrigation time.

The irrigation time was now continued and the point in time at which the surface of the textile was completely wetted was determined. The tests of the textile sample finished according to recipe d were carried out after 30 Hours stopped after the sample with component I according to the invention showed no network points and beaded off with the highest grade 5. The beading grade was determined at the same time. a b c d 1a) beading time (hours) 0.5 1 1.5 30th 1b) beading 2nd 2nd 2nd 5

Example 4

The textile goods described in Examples 2 and 3 were equipped with the following liquors using the same process and the same treatment: a b c d e f G Synthetic resin A 60 60 60 60 60 60 60 g / l catalyst 4th 4th 4th 4th 4th 4th 4th g / l Component V 8th 12 16 8th 12 8th 12 g / l Component II - - - - - 20th 20th g / l Component IV - - - 10th 10th - - g / l a b c d e f G 1a) beading time (minutes) 0 0 10th 0 10th 10th 10th 1b) Beading off effect (grade 5-1) 1 2nd 5 2nd 4th 5 5 1c) water absorption (%) 29 18th 13 17th 7 7 4th 1d) water penetration (cm³) 6 4th 0 3rd 1 0 0 3) Oil repellency (grade 1-8) 0 1 2nd 1 1 1 1

If the component II claimed according to the invention is also used in the equipment fleet, optimum results are achieved Hydrophobic values achieved with half the amount of fluorine normally used. The use of component IV in the finishing bath still requires 75% of the amount of fluorine.

Example 5

The material available for finishing is a polyacrylic awning fabric: 290 g / m², spinneret-dyed, sold under the brand name DRALON (Bayer AG). The equipment is applied as a pad. The fleet intake is 75% of the weight of the goods. After drying at 100 ° C, the awning fabric is treated at 150 ° C for 4 minutes. a b c Component V 15 15 15 g / l Component I - 20th - g / l Component IV - - 10th g / l a b c 1a) beading time (minutes) 0 10th 8th 1b) Beading off effect (grade 5-1) 1 5 3rd 1c) water absorption (%) 28 7 14 1d) Schopper value (mm water column) 370 440 400 3) Oil repellency (grade 1-8) 4th 5 4th

Here, too, the improvement in the irrigation and watertightness values can be clearly seen with the use of component I. The use of component IV with 3 times the amount of solid substance does not reach the test values. The oil repellency is in no way worsened.

Example 6

A polyamide taffeta fabric for umbrella covering (m² - weight: 70 g) is equipped with the following liquor formulations on the foulard: a b c d Component V 10th 10th 10th 10th Component I - 10th - - Component IV - - 3rd 10th

The wet weight gain is approximately 62%. After drying for 10 minutes at 100 ° C in the drying cabinet, the polyamide fabric is treated for 5 minutes at 150 ° C. a b c d 1a) beading time (minutes) 8th 10th 0 10th 1b) Beading off effect (grade 5-1) 3rd 5 3rd 5 1c) water absorption (%) 13 4th 12 16 1d) water penetration (cm³) 40 10th 50 40 3) Oil repellency (grade 1-8) 6 6 6 6

The admixture of component I to the fluorine component V results in optimal irrigation values, the water penetration rate being significantly reduced. The combination with component IV shows a significant deterioration in the irrigation values when using 3 g / l solid substance (compared to component I with 1.5 g / l solid substance), which is only compensated for by increasing the amount used to 10 g / l. Component I does not change the oil repellency.

Example 7

Textiles containing wool and wool require extremely high amounts of fluorine-containing products in order to achieve practical hydro- and oleophobic treatment compared to pure synthetic fiber materials.

The following example is intended to show that the formulations claimed according to the invention also have good effects here.

A polyester wool blend fabric (45% wool and 55% polyester, weight: 311 g / m²) is padded as follows: a b c Component V 50 50 50 g / l Component II - 25th - g / l Component IV - - 15 g / l

The fleet intake was 75%. After drying at 100 ° C, the fabrics are treated at 140 ° C for 3 minutes. a b c 1a) beading time (minutes) 0 10th 3rd 1b) Beading off effect (grade 5-1) 1 5 2nd 1c) water absorption (%) 26 13 20th 1d) water penetration (cm³) 17th 15 17th 3) Oil repellency (grade 8-1) 5 5 5

While no hydrophobic values are achieved with the fluorine component V, the addition of the component II claimed according to the invention achieves optimal irrigation values. Component IV achieves only a slight improvement over the textile goods that are only equipped with component V.

Example 8

A wool fabric with a weight of 288 g / m² is given the following formulations in the pull-out process: a b c Component V 2nd 2nd 2nd % of the weight of the goods Component I - 2nd - "" Component IV - - 2nd ""

The liquor ratio (product weight to liquor quantity) is 1: 30. The liquors are adjusted to a pH of 6 using 60% acetic acid.

The treatment is first carried out at 18 ° C for 20 minutes. Then the liquor temperature is increased to 40 ° C and treated again for 20 minutes. The goods are moved evenly in the fleet throughout the period. The wool samples are then centrifuged in a dewatering centrifuge to a residual moisture content of 30%, dried at 100 ° C and reheated at 140 ° C for 3 minutes. a b c 1a) beading time (minutes) 0 10th 0 1b) Beading off effect (grade 5-1) 1 4th 1 1c) water absorption (%) 39 20th 38 1d) water penetration (cm³) 1 4th 1 3) Oil repellency (grade 8-1) 5 6 4th

Component V and the mixture V with IV do not give any hydrophobic effect. Only the use of component I with component V show very good water-repellent effects in the irrigation test. The oil repellency is increased by one or two notes compared to formula a or c.

Excellent results are also obtained in the tests mentioned if, instead of component I, a compound is used which was obtained by reaction with 72 parts of epichlorohydrin (instead of 36 parts) and / or instead of component V, the following fluoroalkyl compounds are used:
US-A-3 356 628, Examples 1A and 1B,
US-A-3 329 661, Examples 2A, 2B, 6A and 6B,
US-A-3 752 783, Examples 1a, 2a, 3a, 4a and 10a,
US-A-4,296,224, Examples 1-9.

Claims (6)

1. Waterproofing and oil-proofing agents which contain
   

   A. a compound containing a perfluoroalkyl group having 2-20 carbon atoms, which may be interrupted by oxygen and which is bonded to a reactive or polar support group or to the chain of a polymer, and

   B. quaternization products of basic fatty acid amides from reactions of fatty acids having more than 8 C atoms, polyamines and 6.5 to 5 equivalents of epichlorohydrin, relative to amino groups in the basic amide.
2. Agents according to claim 1 which contain, as component A., acrylate (co)polymers having a fluorine content of 20-45% by weight.
3. Agents according to claim 1 which contain, as component B., products of the reaction of saturated or unsaturated fatty acids having 12-22 carbon aroms, polyalkylene polyamines and 0.5 to 5 equivalents of epichlorohydrin.
4. Agents according to claim 3 which contain, as component B., reaction products in which the polyalkylene/polyamine component represents a polyethylene/polyamine mixture which is obtained on the reaction of dichloroethane with ammonia and separation of the diamine and, if appropriate, triamine component.
5. Agents according to claim 3 which contain, as component B, epichlorohydrin reaction products which are obtained by quaternization using epichlorohydrin in aqueous medium.
6. Process for the finishing of textiles, characterized in that agents of claims 1-5 are used.