EP0881325B1 - Silicone softening agents for jeans - Google Patents
Silicone softening agents for jeans Download PDFInfo
- Publication number
- EP0881325B1 EP0881325B1 EP98109267A EP98109267A EP0881325B1 EP 0881325 B1 EP0881325 B1 EP 0881325B1 EP 98109267 A EP98109267 A EP 98109267A EP 98109267 A EP98109267 A EP 98109267A EP 0881325 B1 EP0881325 B1 EP 0881325B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- radicals
- plasticizer
- radical
- organopolysiloxane
- silicone
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
Classifications
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/52—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing synthetic macromolecular substances
- D06P1/5264—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds
- D06P1/5292—Macromolecular compounds obtained otherwise than by reactions involving only unsaturated carbon-to-carbon bonds containing Si-atoms
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/44—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders
- D06P1/46—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using insoluble pigments or auxiliary substances, e.g. binders using compositions containing natural macromolecular substances or derivatives thereof
- D06P1/48—Derivatives of carbohydrates
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P5/00—Other features in dyeing or printing textiles, or dyeing leather, furs, or solid macromolecular substances in any form
- D06P5/02—After-treatment
- D06P5/04—After-treatment with organic compounds
- D06P5/08—After-treatment with organic compounds macromolecular
-
- D—TEXTILES; PAPER
- D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
- D06P—DYEING OR PRINTING TEXTILES; DYEING LEATHER, FURS OR SOLID MACROMOLECULAR SUBSTANCES IN ANY FORM
- D06P1/00—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed
- D06P1/22—General processes of dyeing or printing textiles, or general processes of dyeing leather, furs, or solid macromolecular substances in any form, classified according to the dyes, pigments, or auxiliary substances employed using vat dyestuffs including indigo
- D06P1/228—Indigo
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2311—Coating or impregnation is a lubricant or a surface friction reducing agent other than specified as improving the "hand" of the fabric or increasing the softness thereof
- Y10T442/2328—Organosilicon containing
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T442/00—Fabric [woven, knitted, or nonwoven textile or cloth, etc.]
- Y10T442/20—Coated or impregnated woven, knit, or nonwoven fabric which is not [a] associated with another preformed layer or fiber layer or, [b] with respect to woven and knit, characterized, respectively, by a particular or differential weave or knit, wherein the coating or impregnation is neither a foamed material nor a free metal or alloy layer
- Y10T442/2352—Coating or impregnation functions to soften the feel of or improve the "hand" of the fabric
Definitions
- the invention relates to tissue dyed with indigo. method for the treatment of a fabric stained with indigo.
- Tissue dyed with indigo is mostly the so-called denim fabric, which is a coarse Cotton fabrics are mainly used to manufacture the so-called blue jeans, i.e. around jeans and other items of clothing based on denim fabrics, e.g. Shirts, Jackets, skirts etc., is used. These clothes are made according to special and characteristic of this type of clothing Process manufactured.
- T-shirts can also be the undyed, ready-made garment subsequently colored according to need.
- Classic jeans are predominantly made of cotton and dyed blue. There are denim articles in a wide variety of colors, but the classic jeans are blue. "Blue Jeans” is a linguistically firmly anchored generic term. Traditionally, the coloring of the jeans must be done with indigo. Indigo is a natural dye, but today it is mainly manufactured synthetically.
- the invention relates to indigo-dyed fabric, which thereby is characterized in that it is at least one organopolysiloxane and contains at least one alkyl polyglycoside.
- Indigo-dyed fabric is basically any form of fabric, but preferably cotton fabric dyed with indigo, Linen fabrics, viscose fabrics, fabrics made of synthetic fibers, whereby Cotton fabrics preferred and denim fabrics particularly preferred is.
- the organopolysiloxanes are preferably Organopolysiloxanes (a), which polar groups on Si-C-bonded Have hydrocarbon radicals, such as preferably amino, Ammonium, epoxy, hydroxy, amido, mercapto, carboxy and / or sulfonic acid groups, their salts or esters.
- hydrocarbon radicals such as preferably amino, Ammonium, epoxy, hydroxy, amido, mercapto, carboxy and / or sulfonic acid groups, their salts or esters.
- optionally substituted hydrocarbyloxy R are preferably a directly bonded to a silicon atom of oxygen atom-bonded substituted or unsubstituted hydrocarbon radicals R according to the examples above-mentioned, in particular alkoxy groups having 1 to 18 carbon atoms and phenoxy radicals, especially the methoxy, ethoxy, n-propoxy , iso-propoxy and phenoxy.
- Preferably at most 5% of the radicals R are optionally substituted hydrocarbonoxy radicals.
- Examples of the divalent C 1 to C 18 hydrocarbon radicals R 1 are preferably saturated straight-chain or branched-chain or cyclic alkylene radicals such as the methylene and ethylene radical and propylene, butylene, pentylene, hexylene, 2-methylpropylene, cyclohexylene and and octadecylene radicals or unsaturated alkylene or arylene radicals, such as the hexenylene radical and phenylene radicals, the n-propylene radical and the 2-methylpropylene radical being particularly preferred.
- saturated straight-chain or branched-chain or cyclic alkylene radicals such as the methylene and ethylene radical and propylene, butylene, pentylene, hexylene, 2-methylpropylene, cyclohexylene and and octadecylene radicals or unsaturated alkylene or arylene radicals, such as the hexenylene radical and phenylene radicals
- hydrocarbon radicals R 2 are preferably the examples given for R.
- halogen-substituted hydrocarbon radicals R 2 are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radical, the heptafluoroisopropyl radical, and haloaryl radicals, such as the above -, m- and p-chlorophenyl.
- Examples of mineral acids that deal with the above amino functional hydrocarbon residues to the corresponding have ammonium-functional residues implemented preferably salt, perchlor, sulfur, sulfurous, saltpetre, nitrous, hydrofluoric, phosphoric, diphosphoric and polyphosphoric acids.
- suitable carboxylic acids are preferred Formic, acetic, propionic, butanoic, citric, Trichloro, dichloro and chloroacetic acid, trifluoroacetic acid, Cyanoacetic acid, phenylacetic acid, benzoic acid, m- and p-nitrobenzoic acid, Oxalic acid, malonic acid and lactic acid.
- Especially the ammonium functional groups obtainable with acetic acid are preferred Hydrocarbon residues.
- amido-functional radicals are preferably the ⁇ -acetamidopropyl radical, partially or fully acetylated ⁇ -aminoethyl- ⁇ -aminopropyl residues.
- epoxy-functional radicals R ' are radicals of the general formulas (III) and (IV) where A is an alkyl, alkoxyalkyl, aryl or alkaryl radical.
- the preferred epoxy numbers of the epoxy functional organopolysiloxanes (a) are 0.5 - 0.001 (equiv./100 g), in particular at 0.2 - 0.01 (equiv./100 g).
- the epoxy number of one epoxy functional organopolysiloxane gives the number of equivalents of epoxy, namely the number of moles of epoxy groups, which is contained in 100 grams of organopolysiloxane (a).
- radicals R ' are particularly preferred as the carboxy-functional radicals - (CH 2 ) 10 -COOH, -CH 2 CH (CH 3 ) -COOH and - (CH 2 ) 2 -S-CH 2 -COOH.
- the preferred acid numbers of the carboxy-functional organopolysiloxanes (a) are 1-100 (mg KOH / g), preferably 5-50 and especially 10-30.
- the acid number of a carboxy functional Organopolysiloxane (a) indicates the number Milligrams of potassium hydroxide, which is necessary to get the free Neutralize acids in one gram of carboxy functional Organopolysiloxane (a) are included.
- the radicals R are preferably methyl, ethyl, phenyl, methoxy and / or vinyl radicals. Because of the easier accessibility, preferably 50% of the R radicals, in particular at least 80% of the R radicals, are methyl radicals.
- the organopolysiloxane (mixture) used in emulsions is preferably liquid.
- Process used organopolysiloxanes preferably Viscosities from 100 mPa * s to 1,000,000 mPa * s, respectively measured at 25 ° C.
- an amino-functional organopolysiloxane is used to prepare the ammonium-functional organopolysiloxane (a) which is preferably used in the emulsions according to the invention, it is preferred that it has an amine number from 0.1 to 3.0, in particular from 0.2 to 0.9.
- the amine number of an amino-functional substance is determined as the consumption in cm 3 of 1N hydrochloric acid when titrating 1 g of the amino-functional substance.
- Alkyl polyglycosides with a saturated content are particularly preferred Alkyl radical with an average of 8 to 14 carbon atoms and one average degree of glycosidation n between 1.1 and 3.
- the emulsions used according to the invention have a higher one Stability to foreign electrolytes, such as magnesium and sodium salts, on as corresponding emulsions in which alkyl polyglycol ethers can be used as emulsifiers.
- the emulsions used according to the invention contain relatively small amounts of emulsifiers, in particular 5 to 100 parts by weight of alkyl polyglycosides (b) per 100 parts by weight organopolysiloxanes containing polar groups (a).
- the emulsions used according to the invention have a discontinuous Oil phase which the contains organopolysiloxanes (a) containing polar groups, and a continuous water phase.
- the proportions of the organopolysiloxane (a) and the continuous Water phase can be varied in a wide range, depending on which fixed content in the used according to the invention Emulsions and microemulsions is sought.
- the proportion of organopolysiloxane (a) is between 20 and 70 percent by weight, but especially between 40 and 60 percent by weight of the total weight of the emulsion.
- the emulsions used according to the invention preferably have an average particle size of at most 1 ⁇ m, in particular of at most 300 nm.
- the used according to the invention Microemulsions preferably have an average particle size of at most 150 nm, in particular of at most 20 nm, on.
- the term "emulsions” also includes microemulsions throughout the text.
- the term "microemulsions” only refers on emulsions with an average particle size of at most 150 nm, which are transparent to optically clear. Microemulsions of organopolysiloxanes with alkyl polyglycosides as emulsifiers are not prescribed.
- Examples of particularly suitable cosurfactants are preferred 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol and 4-octanol; Diethylene glycol monomethyl, ethyl and butyl ether; Diethylene glycol dimethyl and ethyl ether; 1-aminobutane, 2-aminobutane, 2-amino-2-methyl-propane, 1-aminopentane, 2-aminopentane, 1-aminohexane, 1-aminoheptane and 1-aminooctane; Ethyl, propyl, Isopropyl
- 1-Pentanol and 1-hexanol are particularly preferred as cosurfactants and 1-octanol, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether and butyl acetate.
- Emulsions still contain additives. They are special Bactericide, Fungicide, Algicide, Microbicide, fragrances, Corrosion inhibitors, dyes, pigments, thickeners and fillers.
- the used according to the invention Emulsions preferably contain additives in amounts of 0 up to 1 percent by weight, in particular from 0 to 0.2 percent by weight, each based on the total weight of the finished Emulsion.
- Emulsion can be used in any order of emulsifying devices or by stirring together without being charged high shear forces occur. However, it is preferred that first a homogeneous mixture of organopolysiloxane (a), Alkyl polyglycosides (b) and water produced and in this Mix the cosurfactants and additives, if used, be stirred in without applying high shear forces.
- the one exercised on the respective components or mixtures Pressure is preferably that which may be due to the action of Mixing elements increased (atmospheric) pressure; the corresponding the prevailing temperature is preferably the one where appropriate increased by the action of the mixing elements (Room) temperature.
- ammonium-functional organopolysiloxane (a) can be made by adding mineral acids or carboxylic acids to corresponding amino-functional organopolysiloxanes. This addition of acid to the organopolysiloxane (a) can be done before the organopolysiloxane (a) is used becomes.
- the emulsions used according to the invention are particularly suitable preferred amino and / or ammonium functional organopolysiloxanes (a) the ammonium functional residues however in situ when mixing organopolysiloxane (a), alkyl polyglycosides (b) and water by adding those described above Mineral and / or carboxylic acids, especially acetic acid, generated.
- the emulsions used according to the invention can in principle be made in any turbulent mixer, too has previously been used to prepare emulsions.
- mixers that can be used are stirrers such as blades, bars, Anchor, grid, screw, propeller, disc, impeller, Turbine, planetary stirrers, single and twin screw mixers, Mixing turbines, colloid mills, ultrasonic mixers, in-line mixers, Pumps, homogenizers, such as high pressure, turbine and circulation homogenizers.
- the fabric samples were padded with aqueous emulsions or solutions of the test substances, in the case of silicone oils with Solutions in white spirit, so applied that approx. 1.0% Active substance was applied to tissue weight. Finally was dried at 150 ° C for 5 minutes.
- Samples 7 x 5 cm were sewn together and gassed in a glass tube.
- the concentration of ozone / NO x was approx. 200 mg / h, the flow rate 2.0 l / h.
- the oxidizing agent was generated by electrical discharge in air from an ozone generator so that 0 3 was present in addition to NO x .
- the exposure time was 60 minutes at room temperature. The samples were then rinsed and dried.
- the samples are sewn together into a strip with a Weight (approx. 30 g) weighed down.
- the loss caused by plasticizers according to the invention % of color strength is therefore considerably less than when used conventional silicone emulsions (Example 1) and in same order of magnitude as when using e.g. B. polyethylene emulsions.
- the soft grip caused by aminosilicones is the one obtainable with polyethylene, like any textile specialist common, far superior.
- the activator is a long-known promotional product the pull-out capacity of plasticizer emulsions.
Landscapes
- Engineering & Computer Science (AREA)
- Textile Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Molecular Biology (AREA)
- Chemical & Material Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Detergent Compositions (AREA)
Description
Die Erfindung betrifft mit Indigo gefärbtes Gewebe. Verfahren zur Behandlung eines mit Indigo gefärbten Gewebes.The invention relates to tissue dyed with indigo. method for the treatment of a fabric stained with indigo.
Bei mit Indigo gefärbtem Gewebe handelt es sich überwiegend um das sogenannte Denimgewebe, bei dem es sich um ein grobes Baumwollgewebe handelt, das hauptsächlich zur Herstellung der sogenannten Blue Jeans, also um Jeanshosen und andere Kleidungsstücke auf der Basis von Denimgeweben, wie z.B. Shirts, Jacken, Röcke etc., Verwendung findet. Diese Kleidungsstücke werden nach speziellen und für diese Art von Bekleidung charakteristischen Verfahren hergestellt.Tissue dyed with indigo is mostly the so-called denim fabric, which is a coarse Cotton fabrics are mainly used to manufacture the so-called blue jeans, i.e. around jeans and other items of clothing based on denim fabrics, e.g. Shirts, Jackets, skirts etc., is used. These clothes are made according to special and characteristic of this type of clothing Process manufactured.
Zur Herstellung von gefärbten Textilien wird üblicherweise die zugrundeliegende Stoffbahn kontinuierlich oder diskontinuierlich gefärbt. Erst nach diesem Prozeß wird die Stoffbahn mit einer zweckdienlichen Endausrüstung weiterveredelt und schließlich meist bei einem anderen Betrieb konfektioniert.For the production of colored textiles, the underlying fabric continuous or discontinuous colored. It is only after this process that the fabric is joined refined an appropriate final equipment and finally usually made up at another company.
In Ausnahmefällen, wie z.B. bei kurzlebigen Modeartikeln (T-Shirts), kann auch das ungefärbte, konfektionierte Kleidungsstück nachträglich dem Bedarf entsprechend gefärbt werden. Man spricht hier von Stückfärbung.In exceptional cases, such as for short-lived fashion items (T-shirts), can also be the undyed, ready-made garment subsequently colored according to need. Man speaks here of piece coloring.
Bei Jeans (Denims) hingegen wird der Färbeprozeß in einem sehr frühen Produktionsstadium durchgeführt. So wird bereits vor dem Webprozeß die sogenannte "Kette" in einem kombinierten Arbeitsgang geschlichtet und gefärbt. Man spricht hier von "Schlichtfärbung". Diese Kette wird dann mit einem ungefärbten Schußfaden verwebt, wodurch das für Denims charakteristische Warenbild entsteht. Zum Schlichten dienen aus Preisgründen meist Stärke oder Stärkederivate.With jeans (denims), on the other hand, the dyeing process in one is very early production stage. So is already going on the weaving process the so-called "chain" in a combined operation finished and colored. One speaks here of "Finishing coloring". This chain is then unstained Weft thread interwoven, which is characteristic of denims Product image is created. Serve for finishing for price reasons mostly starch or starch derivatives.
Zur Textilfärbung stehen eine große Palette unterschiedlichster Farbtöne und je nach Faserart eine charakteristische Auswahl an Farbstoffklassen zur Verfügung. There is a wide range of different dye dyeing options Color shades and a characteristic selection depending on the type of fiber available in dye classes.
Klassische Jeans hingegen werden überwiegend aus Baumwolle
hergestellt und blau gefärbt.
Zwar gibt es Denimartikel in den unterschiedlichsten Farbtönen,
die klassische Jeans aber ist blau. "Blue Jeans" ist ein
sprachlich fest verankerter Gattungsbegriff. Ebenso traditionell
muß die Färbung der Jeans mit Indigo erfolgen. Indigo ist
ein Naturfarbstoff, der allerdings heute überwiegend synthetisch
hergestellt wird.Classic jeans, on the other hand, are predominantly made of cotton and dyed blue.
There are denim articles in a wide variety of colors, but the classic jeans are blue. "Blue Jeans" is a linguistically firmly anchored generic term. Traditionally, the coloring of the jeans must be done with indigo. Indigo is a natural dye, but today it is mainly manufactured synthetically.
Wie bereits erwähnt, erfolgt die Ausrüstung eines Textilsubstrates normalerweise nach der Färbung beim Textilveredler. Erst dann geht die Ware zum Konfektionär.As already mentioned, a textile substrate is finished usually after dyeing at the textile finishing company. Only then will the goods go to the manufacturer.
Bei Jeans hingegen wird bereits das stuhlrohe Gewebe zum Bekleidungsstück
konfektioniert. Eine "Veredlung" erfolgt erst
beim Waschen der bereits genähten Stücke in dafür besonders
spezialisierten Betrieben, den sogenannten "Jeanswäschern".
Benutzt werden hierfür meist spezielle Trommelwaschmaschinen.
Die starren und steifen Stücke werden zunächst zur Vermeidung
von Knitterfalten vorsichtig geweicht, störende Chemikalien,
wie Alkali und Überschußfarbstoff werden abgewaschen.
Dann wird, nach Einstellung eines optimalen pH, vorzugsweise
enzymatisch entschlichtet, d. h. die Stärkeschlichte wird
durch die Amylaseenzyme zu löslichen Bruchstücken abgebaut und
diese ausgespült. Dadurch verliert das Gewebe wenigstens teilweise
seine Starre.
Der heutigen Mode entsprechend wird dann ein beträchtlicher
Prozentsatz der aufgebrachten Farbe durch Bleichen entfernt,
bis das Kleidungsstück nicht mehr dunkelblau, sondern in definierten
mittel- bis hellblauen Tönen erscheint. Dieses Bleichen
geschieht vorwiegend durch Chlorierung. Alternative Verfahren,
wie z. B. die reduktive Bleiche (Sugar Wash) sind
ebenfalls bekannt.
Falls modisch erforderlich, wird die Wäsche mit Lavasteinen
durchgeführt (sogenannte "Stone-Wash"-Prozess), was den durch
Abrasion geschädigten Hosen den sogenannten "Worn Out Look"
verleiht. In the case of jeans, on the other hand, the raw chair fabric is already made into a garment. A "finishing" takes place only when the already sewn pieces are washed in specially specialized companies, the so-called "jeans washers". Special drum washing machines are usually used for this. The rigid and stiff pieces are first carefully soaked to avoid creases, disruptive chemicals such as alkali and excess dye are washed off.
Then, after setting an optimal pH, desizing is preferably carried out enzymatically, ie the starch size is broken down into soluble fragments by the amylase enzymes and these are rinsed out. As a result, the tissue at least partially loses its rigidity.
According to today's fashion, a considerable percentage of the applied color is then removed by bleaching until the garment no longer appears dark blue, but in defined medium to light blue tones. This bleaching is mainly done by chlorination. Alternative methods, such as. B. reductive bleaching (sugar wash) are also known.
If fashionably necessary, the washing is carried out with lava stones (so-called "stone-wash" process), which gives the trousers damaged by abrasion the so-called "worn-out look".
In jüngster Zeit wird der Einsatz von Cellulase-Enzymen in der
Wäsche forciert. Diese Enzyme greifen die Baumwolle des Gewebes
jedoch selbst an und machen es damit weicher.
Hochwertige Jeans aber werden zusätzlich noch im Spülbad mit
Textilweichmacher versetzt, um ihnen einen besonders guten und
weichen Griff zu verleihen.The use of cellulase enzymes in laundry has recently been forced. However, these enzymes attack the cotton of the fabric itself, making it softer.
High-quality jeans are also mixed with fabric softener in the rinsing bath to give them a particularly good and soft feel.
Da die Weichmacher für Jeansbekleidung im Spülbad der Waschmaschine
appliziert werden, müssen sie eine gewisse Tendenz besitzen,
aus langer Flotte substantiv auf die Ware aufzuziehen.
Die heute verwendeten Produkte auf Basis von Polyethylen- oder
Wachs-Dispersionen sowie Weichmacher auf Basis von Fettsäurepolyglykolethern
sind in den Kriterien "Weichgriff" und "Ausziehvermögen"
nicht optimal. Ausziehfähige kationische Fettweichmacher
verhalten sich noch weniger günstig.
Die Verwendung aminofuktioneller Silicone als Weichmacher wäre
an sich erwünscht, da diese Substanzen besonders guten Weichgriff
ergeben und dank ihrer kationischen Ladung auch Substantivität
zur negativ geladenen Baumwolle aufweisen.
Leider besteht - zu Recht - eine Abneigung gegen Siliconweichmacher
bei Jeans:
Im Ladengeschäft liegen Jeanswaren oft längere Zeit vor dem
Verkauf. Bei Lagerung im Stapel sind dabei nur die Kanten unmittelbar
der Wirkung der Atmosphäre ausgesetzt.
Luftvereinigungen, wie Ozon oder Stickoxide (NOx) aber können
den blauen Indigofarbstoff schädigen, d. h. zu gelbem Isathin
oxydieren.
Jeans können also, speziell an Lagerkanten, ihre Farbe verlieren.
Dieses "Ozonfading" macht, speziell, da es nur örtlich
auftritt, diese Waren unverkäuflich.
In der Fachwelt besteht Einigkeit, daß Siliconweichmacher dieses
Ozonfading zwar nicht verursachen, wohl aber fördern und
verstärken. Daher werden die eigentlich besonders effektiven
Siliconweichmacher für diesen Einsatzzweck abgelehnt. Siehe
auch Melliand Textilberichte, "Vergilbung von indigohaltiger
Jeanswear" 11/96, S. 786f, 1996, wo auf Seite 787 unter 6.
Einfluß von Weichgriffmittel und Lagerdauer ausgeführt wird:
"Von den untersuchten Weichgriffmitteln (verschiedene Fettsäurekondensationsprodukte,
ein aminofunfuntionelles Polysiloxan
und ein Griffmittel auf der Basis von Polyurethan) verursacht
keines unter Einwirkung von Schadgas Eigenvergilbung. Siliconhaltige
Produkte jedoch beschleunigen den Indigoabbau durch
Schadgas. Einzelne Fettsäurekondensationsprodukte vermindern
die Vergilbung von Jeanswear deutlich.
Je länger Jeanswear der Einwirkung von Schadgas ausgesetzt
ist, desto größer ist die Wahrscheinlichkeit der Entstehung
irreparabler Aufhellung und Vergilbung. Beobachtungen aus der
Praxis zufolge entsteht ein Vergilbungsmaximum, das unter andauernder
Aufhellung stationär ist."Since the softeners for jeans clothing are applied in the washing machine's rinsing bath, they must have a certain tendency to substantively draw onto the goods from a long fleet. The products used today based on polyethylene or wax dispersions and plasticizers based on fatty acid polyglycol ethers are not optimal in the criteria of "soft feel" and "pull-out capacity". Extendable cationic fat softeners behave even less favorably.
The use of amino-functional silicones as plasticizers would be desirable per se, since these substances give particularly good softness and, thanks to their cationic charge, also have substantivity to the negatively charged cotton.
Unfortunately - rightly so - there is an aversion to silicone softeners in jeans:
In the retail store, jeans goods are often long before sales. When stored in a stack, only the edges are directly exposed to the atmosphere.
Air associations such as ozone or nitrogen oxides (NO x ) can damage the blue indigo dye, ie oxidize it to yellow isathine.
Jeans can lose their color, especially on bearing edges. This "ozone fading", especially since it occurs only locally, makes these goods unsaleable.
There is general agreement among experts that silicone plasticizers do not cause this ozone fading, but do promote and intensify it. Therefore, the actually particularly effective silicone plasticizers for this purpose are rejected. See also Melliand Textile Reports, "Yellowing of Indigo Jeanswear" 11/96, pp. 786f, 1996, where on page 787 under 6. Influence of softening agents and storage time is stated:
"None of the soft grip agents examined (various fatty acid condensation products, an amino-functional polysiloxane and a grip agent based on polyurethane) cause yellowing under the influence of harmful gas. However, silicone-containing products accelerate the degradation of indigo by harmful gas. Individual fatty acid condensation products significantly reduce the yellowing of jeanswear.
The longer jeanswear is exposed to harmful gas, the greater the likelihood of irreparable lightening and yellowing. According to observations from practice, there is a yellowing maximum that is stationary under constant brightening. "
Eigene Versuche haben ergeben, daß diese Ablehnung nicht auf einem Vorurteil beruht. Tatsächlich läßt sich auch experimentell eine Verstärkung der Farbabweichung von Denim-Geweben feststellen, wenn diese vor der Einwirkung von Ozon oder NOx mit handelsüblichen Siliconweichmachern behandelt wurden. (Beispiel 1)Our own experiments have shown that this rejection is not based on a prejudice. In fact, an increase in the color deviation of denim fabrics can also be determined experimentally if these have been treated with commercially available silicone plasticizers before the action of ozone or NO x . (Example 1)
Dieser Effekt ist praktisch unabhängig davon, ob der Weichmacher in Form einer Micro- oder Macroemulsion vorliegt, und welche Viskosität, Aminzahl oder Struktur das Silicon aufweist.This effect is practically independent of whether the plasticizer is in the form of a micro or macro emulsion, and what viscosity, amine number or structure the silicone having.
Überraschend wurde nun gefunden, daß für dieses Ozonfading nicht das Silicon, sondern der zur Emulgierung üblicherweise verwendete nichtionische Emulgator verantwortlich ist, gleichgültig, ob auf Basis Fettalkohol- oder Alkylphenolethoxylat (Beispiel 2):It has now surprisingly been found that for this ozone fading not the silicone, but usually the one used for emulsification non-ionic emulsifier used is responsible, indifferent, whether based on fatty alcohol or alkylphenol ethoxylate (Example 2):
Silicone, die praxisunüblich, rein zu Versuchszwecken, in unpolaren
Lösungsmitteln gelöst auf das Gewebe aufgetragen wurden,
haben keine effektverstärkende Wirkung.
Ethoxylierte Emulgatoren hingegen fördern das Ozonfading.Silicones that have been applied to the fabric in a manner that is unusual in practice, purely for experimental purposes, dissolved in non-polar solvents, have no effect-enhancing effect.
In contrast, ethoxylated emulsifiers promote ozone fading.
Diese Wirkung scheint weitgehend unabhängig vom hydrophoben Rest (gerade- oder verzweigtkettiger Fettalkohol, Alkylphenol), unabhängig vom Ethoxylierungsgrad ( n = 5 - 10 ) und unabhängig vom Hersteller des Tensides. Eventuelle Unterschiede in der Gauß Verteilung, der Prozeßführung und eventuell der Katalyse beim Ethoxylieren scheinen also keine Rolle zu spielen.This effect seems largely independent of the hydrophobic Rest (straight or branched chain fatty alcohol, Alkylphenol), regardless of the degree of ethoxylation (n = 5 - 10) and regardless of the manufacturer of the surfactant. Any differences in the Gauss distribution, litigation and possibly catalysis does not seem to matter in ethoxylation to play.
Es ist daher Aufgabe der Erfindung, diese Nachteile des Standes der Technik zu überwinden und insbesondere Weichmacher auf Silicon Basis zu Verfügung zu stellen, die diese Nachteile, wie die Vergilbung von Jeansgewebe, nicht zeigen, Diese Aufgabe wird durch die Erfindung gelöst.It is therefore an object of the invention to overcome these disadvantages of the prior art to overcome the technology and especially plasticizers To provide silicon base that has these disadvantages, such as the yellowing of denim fabrics, does not show this task is solved by the invention.
Überraschend wurde gefunden, daß Emulsionen aminofunktioneller Silicone zu deren Herstellung Alkylpolyglycoside als Emulgatoren eingesetzt wurden, das Ozonfading damit weichgemachter indigogefärbter Denimgewebe nicht verstärken. Dies gilt für die Einwirkung von Ozon, wie von NOx. (Beispiele 3 und 4)It was surprisingly found that emulsions of amino-functional silicones were used as emulsifiers for their production, alkyl polyglycosides, which did not intensify the ozone fading of indigo-dyed denim fabric softened therewith. This applies to the effects of ozone, such as NO x . (Examples 3 and 4)
Solche Emulsionen sind in EP 0622397 (Wacker) und DE 4131551 (Pfersee) beschrieben.Such emulsions are in EP 0622397 (Wacker) and DE 4131551 (Pfersee) described.
Gegenstand der Erfindung sind Indigo gefärbtes Gewebe, das dadurch gekennzeichnet ist, daß es zumindest ein Organopolysiloxan und zumindest ein Alkylpolyglykosid enthält.The invention relates to indigo-dyed fabric, which thereby is characterized in that it is at least one organopolysiloxane and contains at least one alkyl polyglycoside.
Indigo gefärbtes Gewebe ist grundsätzlich jede Form von Gewebe, vorzugsweise aber mit Indigo gefärbtes Baumwollgewebe, Leinengewebe, Viskosegewebe, Gewebe aus Kunstfaser, wobei Baumwollgewebe bevorzugt und Denimgewebe besonders bevorzugt ist.Indigo-dyed fabric is basically any form of fabric, but preferably cotton fabric dyed with indigo, Linen fabrics, viscose fabrics, fabrics made of synthetic fibers, whereby Cotton fabrics preferred and denim fabrics particularly preferred is.
Bei den Organopolysiloxanen handelt es sich vorzugsweise um Organopolysiloxane (a), welche polare Gruppen an Si-C-gebundenen Kohlenwasserstoffresten aufweisen, wie vorzugsweise Amino-, Ammonium-, Epoxy-, Hydroxy-, Amido-, Mercapto-, Carboxy- und/oder Sulfonsäuregruppen, deren Salze oder Ester. The organopolysiloxanes are preferably Organopolysiloxanes (a), which polar groups on Si-C-bonded Have hydrocarbon radicals, such as preferably amino, Ammonium, epoxy, hydroxy, amido, mercapto, carboxy and / or sulfonic acid groups, their salts or esters.
Vorzugsweise weisen die Organopolysiloxane (a) die allgemeine
Formel (I)
Vorzugsweise besitzt die Summe n + m einen durchschnittlichen Wert von 1,9 bis 2,1.The sum n + m preferably has an average value of 1.9 to 2.1.
Beispiele für Kohlenwasserstoffreste R sind vorzugsweise Alkylreste, wie der Methyl-, Ethyl-, n-Propyl-, iso-Propyl-, n-Butyl-, iso-Butyl-, tert.-Butyl-, n-Pentyl-, iso-Pentyl-, neo-Pentyl-, tert.-Pentylrest; Hexylreste, wie der n-Hexylrest; Heptylreste, wie der n-Heptylrest; Octylreste, wie der n-Octylrest und iso-Octylreste, wie der 2,2,4-Trimethylpentylrest; Nonylreste, wie der n-Nonylrest; Decylreste, wie der n-Decylrest; Dodecylreste, wie der n-Dodecylrest; Octadecylreste, wie der n-Octadecylrest; Alkenylreste, wie der Vinyl-, Allyl- und der 5-Hexen-1-ylrest; Cycloalkylreste, wie Cyclopentyl-, Cyclohexyl-, Cycloheptylreste und Methylcyclohexylreste; Arylreste, wie der Phenyl-, Naphthyl- und Anthryl- und Phenanthrylrest; Alkarylreste, wie o-, m-, p-Tolylreste, Xylylreste und Ethylphenylreste; Aralkylreste, wie der Benzylrest, der alpha- und der β-Phenylethylrest.Examples of hydrocarbon radicals R are preferably alkyl radicals, such as methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, tert-butyl, n-pentyl, iso-pentyl -, neo-pentyl, tert-pentyl; Hexyl radicals, such as the n-hexyl radical; Heptyl residues, such as the n-heptyl residue; Octyl radicals, such as the n-octyl radical and iso-octyl radicals, such as the 2,2,4-trimethylpentyl radical; Nonyl radicals, such as the n-nonyl radical; Decyl radicals, such as the n-decyl radical; Dodecyl radicals, such as the n-dodecyl radical; Octadecyl radicals, such as the n-octadecyl radical; Alkenyl radicals, such as the vinyl, allyl and 5-hexen-1-yl radicals; Cycloalkyl residues such as cyclopentyl, cyclohexyl, cycloheptyl residues and methylcyclohexyl residues; Aryl radicals, such as the phenyl, naphthyl and anthryl and phenanthryl radical; Alkaryl groups such as o-, m-, p-tolyl groups, xylyl groups and ethylphenyl groups; Aralkyl radicals, such as the benzyl radical, the alpha and the β-phenylethyl radical.
Beispiele für gegebenfalls substituierte Kohlenwasserstoffoxyreste R sind vorzugsweise über ein direkt an ein Siliciumatom gebundenes Sauerstoffatom gebundene substituierte und unsubstituierte Kohlenwasserstoffreste R gemäß den vorstehend genannten Beispielen, insbesondere Alkoxyreste mit 1 bis 18 Kohlenstoffatomen und Phenoxyreste, speziell der Methoxy-, Ethoxy-, n-Propoxy-, iso-Propoxy- und Phenoxyrest. Vorzugsweise sind höchstens 5 % der Reste R gegebenfalls substituierte Kohlenwasserstoffoxyreste.Examples of optionally substituted hydrocarbyloxy R are preferably a directly bonded to a silicon atom of oxygen atom-bonded substituted or unsubstituted hydrocarbon radicals R according to the examples above-mentioned, in particular alkoxy groups having 1 to 18 carbon atoms and phenoxy radicals, especially the methoxy, ethoxy, n-propoxy , iso-propoxy and phenoxy. Preferably at most 5% of the radicals R are optionally substituted hydrocarbonoxy radicals.
Beispiele für bevorzugte aminofunktionelle Reste R' sind Reste
der allgemeinen Formel (II)
Beispiele für die zweiwertigen C1- bis C18-Kohlenwasserstoffreste R1 sind vorzugsweise gesättigte gerad- oder verzweigtkettige oder cyclische Alkylenreste wie der Methylen- und Ethylenrest sowie Propylen-, Butylen-, Pentylen-, Hexylen-, 2-Methylpropylen-, Cyclohexylen- und Octadecylenreste oder ungesättigte Alkylen- oder Arylenreste wie der Hexenylenrest und Phenylenreste, wobei der n-Propylenrest und der 2-Methylpropylenrest besonders bevorzugt sind.Examples of the divalent C 1 to C 18 hydrocarbon radicals R 1 are preferably saturated straight-chain or branched-chain or cyclic alkylene radicals such as the methylene and ethylene radical and propylene, butylene, pentylene, hexylene, 2-methylpropylene, cyclohexylene and and octadecylene radicals or unsaturated alkylene or arylene radicals, such as the hexenylene radical and phenylene radicals, the n-propylene radical and the 2-methylpropylene radical being particularly preferred.
Beispiele für die Kohlenwasserstoffreste R2 vorzugsweise sind die für R angegebenen Beispiele. Beispiele für halogensubstituierte Kohlenwasserstoffreste R2 sind Halogenalkylreste, wie der 3,3,3-Trifluor-n-propylrest, der 2,2,2,2',2',2'-Hexafluorisopropylrest, der Heptafluorisopropylrest, und Halogenarylreste, wie der o-, m- und p-Chlorphenylrest.Examples of the hydrocarbon radicals R 2 are preferably the examples given for R. Examples of halogen-substituted hydrocarbon radicals R 2 are haloalkyl radicals, such as the 3,3,3-trifluoro-n-propyl radical, the 2,2,2,2 ', 2', 2'-hexafluoroisopropyl radical, the heptafluoroisopropyl radical, and haloaryl radicals, such as the above -, m- and p-chlorophenyl.
In der vorstehenden allgemeinen Formel (II) bedeuten vorzugsweise
- R1
- einen zweiwertigen C2- bis C6-Kohlenwasserstoffrest,
- R2
- ein Wasserstoffatom, einen Methyl- oder Cyclohexylrest,
- a
- die Werte 2 oder 3 und
- b
- die Werte 0 oder 1.
- R 1
- a divalent C 2 to C 6 hydrocarbon residue,
- R 2
- a hydrogen atom, a methyl or cyclohexyl radical,
- a
- the values 2 or 3 and
- b
- the values 0 or 1.
Besonders bevorzugt sind lineare Polydimethylsiloxane, die gegebenenfalls als Reste R neben Methylresten höchstens 5 % C1- bis C3-Alkoxy- oder Hydroxyendgruppen aufweisen. Vorzugsweise weisen diese Polydimethylsiloxane als Reste R' die Reste H2N(CH2)2NH(CH2)3-, H2N(CH2)2NHCH2CH(CH3)CH2-, Linear polydimethylsiloxanes are particularly preferred, which optionally have as radicals R in addition to methyl radicals at most 5% C 1 -C 3 -alkoxy or hydroxyl end groups. Preferably, these polydimethylsiloxanes have, as R 'represent the radicals H 2 N (CH 2) 2 NH (CH 2) 3 -, H 2 N (CH 2) 2 NHCH 2 CH (CH 3) CH 2 -,
Beispiele für Mineralsäuren, die sich mit den vorstehend genannten aminofunktionellen Kohlenwasserstoffresten zu den entsprechenden ammoniumfunktionellen Resten umsetzen lassen, sind vorzugsweise Salz-, Perchlor-, Schwefel-, schweflige, Salpeter-, salpetrige, Fluß-, Phosphor-, Diphosphor- und Polyphosphorsäuren. Beispiele für geeignete Carbonsäuren sind vorzugsweise Ameisen-, Essig-, Propion-, Butansäuren, Citronensäure, Trichlor-, Dichlor- und Chloressigsäure, Trifluoressigsäure, Cyanessigsäure, Phenylessigsäure, Benzoesäure, m- und p-Nitrobenzoesäure, Oxalsäure, Malonsäure und Milchsäure. Besonders bevorzugt sind die mit Essigsäure erhältlichen ammoniumfunktionellen Kohlenwasserstoffreste.Examples of mineral acids that deal with the above amino functional hydrocarbon residues to the corresponding have ammonium-functional residues implemented preferably salt, perchlor, sulfur, sulfurous, saltpetre, nitrous, hydrofluoric, phosphoric, diphosphoric and polyphosphoric acids. Examples of suitable carboxylic acids are preferred Formic, acetic, propionic, butanoic, citric, Trichloro, dichloro and chloroacetic acid, trifluoroacetic acid, Cyanoacetic acid, phenylacetic acid, benzoic acid, m- and p-nitrobenzoic acid, Oxalic acid, malonic acid and lactic acid. Especially the ammonium functional groups obtainable with acetic acid are preferred Hydrocarbon residues.
Beispiele für amidofunktionelle Reste sind vorzugsweise der γ-Acetamidopropylrest, teil- oder vollacetylierte β-Aminoethyl-γ-aminopropylreste.Examples of amido-functional radicals are preferably the γ-acetamidopropyl radical, partially or fully acetylated β-aminoethyl-γ-aminopropyl residues.
Beispiele für epoxyfunktionelle Reste R' sind Reste der allgemeinen Formeln (III) und (IV) wobei A einen Alkyl-, Alkoxyalkyl-, Aryl- oder Alkarylrest bedeutet. Examples of epoxy-functional radicals R ' are radicals of the general formulas (III) and (IV) where A is an alkyl, alkoxyalkyl, aryl or alkaryl radical.
Beispiele für bevorzugte epoxyfunktionelle Reste R' sind Examples of preferred epoxy-functional radicals R ' are
Besonders bevorzugte epoxyfunktionelle Reste R' sind Particularly preferred epoxy-functional radicals R ' are
Die bevorzugten Epoxydzahlen der epoxyfunktionellen Organopolysiloxane (a) liegen bei 0,5 - 0,001 (equiv./100 g), insbesondere bei 0,2 - 0,01 (equiv./100 g). Die Epoxydzahl eines epoxyfunktionellen Organopolysiloxans gibt die Anzahl an Equivalenten an Epoxyd, nämlich die Molzahl an Epoxydgruppen an, die in 100 Gramm Organopolysiloxan (a) enthalten ist. The preferred epoxy numbers of the epoxy functional organopolysiloxanes (a) are 0.5 - 0.001 (equiv./100 g), in particular at 0.2 - 0.01 (equiv./100 g). The epoxy number of one epoxy functional organopolysiloxane gives the number of equivalents of epoxy, namely the number of moles of epoxy groups, which is contained in 100 grams of organopolysiloxane (a).
Beispiele für bevorzugte carboxyfunktionelle Reste R' sind Reste
der allgemeinen Formel (V)
Als carboxyfunktionelle Reste R' sind besonders bevorzugt die
Reste
Insbesondere bevorzugt als carboxyfunktionelle Reste R' sind
vorzugsweise die Reste
Beispiele für Basen zur Umsetzung mit carboxyfunktionellen Resten R' aufweisenden Organopolysiloxanen (a) sind vorzugsweise Ammoniak, Amine, Alkali- und Erdalkalihydroxide, wie LioH, NaOH, KOH, RbOH, CsOH, Mg(OH)2, Ca(OH)2, Sr(OH)2 und Ba(OH)2.Examples of bases for reaction with organopolysiloxanes (a) having carboxy-functional radicals R ' are preferably ammonia, amines, alkali and alkaline earth metal hydroxides, such as LioH, NaOH, KOH, RbOH, CsOH, Mg (OH) 2 , Ca (OH) 2 , Sr (OH) 2 and Ba (OH) 2 .
Die bevorzugten Säurezahlen der carboxyfunktionellen Organopolysiloxane (a) liegen bei 1 - 100 (mg KOH/g), vorzugsweise bei 5 - 50 und insbesondere bei 10 - 30. Die Säurezahl eines carboxyfunktionellen Organopolysiloxans (a) gibt die Anzahl an Milligramm Kaliumhydroxid an, die notwendig ist, um die freien Säuren zu neutralisieren, die in einem Gramm des carboxyfunktionellen Organopolysiloxans (a) enthalten sind.The preferred acid numbers of the carboxy-functional organopolysiloxanes (a) are 1-100 (mg KOH / g), preferably 5-50 and especially 10-30. The acid number of a carboxy functional Organopolysiloxane (a) indicates the number Milligrams of potassium hydroxide, which is necessary to get the free Neutralize acids in one gram of carboxy functional Organopolysiloxane (a) are included.
Vorzugsweise sind die Reste R Methyl-, Ethyl-, Phenyl-, Methoxy- und/oder Vinylreste. Wegen der leichteren Zugänglichkeit sind vorzugsweise 50 % der Reste R, insbesondere mindestens 80 % der Reste R, Methylreste. The radicals R are preferably methyl, ethyl, phenyl, methoxy and / or vinyl radicals. Because of the easier accessibility, preferably 50% of the R radicals, in particular at least 80% of the R radicals, are methyl radicals.
Es kann ein organopolysiloxan (a), vorzugsweise ein solches der Formel (I), eingesetzt werden; es können auch mehrere Organopolysiloxane eingesetzt werden.It can be an organopolysiloxane (a), preferably one of formula (I) can be used; several organopolysiloxanes can also be used be used.
Das in Emulsionen eingesetzte Organopolysiloxan(gemisch) ist vorzugsweise flüssig. Insbesondere besitzen die im erfindungsgemäßen Verfahren eingesetzten organopolysiloxane vorzugsweise jeweils Viskositäten von 100 mPa*s bis 1.000.000 mPa*s, jeweils gemessen bei 25°C.The organopolysiloxane (mixture) used in emulsions is preferably liquid. In particular, in the invention Process used organopolysiloxanes preferably Viscosities from 100 mPa * s to 1,000,000 mPa * s, respectively measured at 25 ° C.
Wird ein aminofunktionelles organopolysiloxan zur Herstellung des vorzugsweise in den erfindungsgemäßen Emulsionen eingesetzten ammoniumfunktionellen organopolysiloxans (a) verwendet, so ist bevorzugt, daß es eine Aminzahl von 0,1 bis 3,0, insbesondere von 0,2 bis 0,9, besitzt. Die Aminzahl eines aminofunktionellen Stoffes wird bestimmt als Verbrauch in cm3 an 1n Salzsäure bei der Titration von 1 g des aminofunktionellen Stoffes.If an amino-functional organopolysiloxane is used to prepare the ammonium-functional organopolysiloxane (a) which is preferably used in the emulsions according to the invention, it is preferred that it has an amine number from 0.1 to 3.0, in particular from 0.2 to 0.9. The amine number of an amino-functional substance is determined as the consumption in cm 3 of 1N hydrochloric acid when titrating 1 g of the amino-functional substance.
Als Alkylpolyglykoside können beispielsweise die in der EP-A
418 479 beschriebenen Alkylpolyglykoside der allgemeinen Formel
(VI)
wobei
in which
Besonders bevorzugt sind Alkylpolyglykoside mit gesättigtem Alkylrest mit im Mittel 8 bis 14 Kohlenstoffatomen und einem mittleren Glykosidierungsgrad n zwischen 1,1 und 3. Alkyl polyglycosides with a saturated content are particularly preferred Alkyl radical with an average of 8 to 14 carbon atoms and one average degree of glycosidation n between 1.1 and 3.
Ein weiter Gegenstand der Erfindung ist ein Verfahren zur Behandlung eines mit Indigo gefärbten Gewebes, bei dem zumindest ein Organopolysiloxan und zumindest ein Alkylpolyglykosid aufgebracht werden.Another object of the invention is a method for treatment a fabric dyed with indigo, in which at least an organopolysiloxane and at least one alkyl polyglycoside applied become.
Dies wird vorzugsweise durch die Behandlung des mit Indigo gefärbtem
Gewebe mit einer wäßrigen Emulsion auf der Grundlage
von
Im Gegensatz zu den wäßrigen Emulsionen von Polydimethylsiloxanölen und Polydiphenylsiloxanölen mit Alkylpolyglykosiden weisen die erfindungsgemäß eingesetzten Emulsionen eine höhere Stabilität gegenüber Fremdelektrolyten, wie Magnesium- und Natriumsalzen, auf als entsprechende Emulsionen, bei denen Alkylpolyglykolether als Emulgatoren verwendet werden.In contrast to the aqueous emulsions of polydimethylsiloxane oils and polydiphenylsiloxane oils with alkyl polyglycosides the emulsions used according to the invention have a higher one Stability to foreign electrolytes, such as magnesium and sodium salts, on as corresponding emulsions in which alkyl polyglycol ethers can be used as emulsifiers.
Die erfindungsgemäß eingesetzten Emulsionen enthalten relativ geringe Mengen an Emulgatoren, insbesondere 5 bis 100 Gewichtsteile an Alkylpolyglykosiden (b) pro 100 Gewichtsteile polare Gruppen enthaltender Organopolysiloxane (a).The emulsions used according to the invention contain relatively small amounts of emulsifiers, in particular 5 to 100 parts by weight of alkyl polyglycosides (b) per 100 parts by weight organopolysiloxanes containing polar groups (a).
Die erfindungsgemäß eingesetzten Emulsionen weisen eine diskontinuierliche Ölphase, welche die polare Gruppen enthaltenden Organopolysiloxane (a) enthält, und eine kontinuierliche Wasserphase auf.The emulsions used according to the invention have a discontinuous Oil phase which the contains organopolysiloxanes (a) containing polar groups, and a continuous water phase.
Die Anteile des Organopolysiloxans (a) und der kontinuierlichen Wasserphase können in weiten Bereichen variiert werden, je nachdem, welcher Festgehalt in den erfindungsgemäß eingesetzten Emulsionen und Mikroemulsionen angestrebt wird. Vorzugsweise liegt der Anteil des Organopolysiloxans (a) zwischen 20 und 70 Gewichtsprozent, insbesondere jedoch zwischen 40 und 60 Gewichtsprozent, des Gesamtgewichts der Emulsion.The proportions of the organopolysiloxane (a) and the continuous Water phase can be varied in a wide range, depending on which fixed content in the used according to the invention Emulsions and microemulsions is sought. Preferably the proportion of organopolysiloxane (a) is between 20 and 70 percent by weight, but especially between 40 and 60 percent by weight of the total weight of the emulsion.
Die erfindungsgemäß eingesetzten Emulsionen weisen vorzugsweise eine mittlere Teilchengröße von höchstens 1 µm, insbesondere von höchstens 300 nm auf. Die erfindungsgemäß eingesetzten Mikroemulsionen weisen vorzugsweise eine mittlere Teilchengröße von höchstens 150 nm, insbesondere von höchstens 20 nm, auf. Der Ausdruck "Emulsionen" umfaßt im ganzen Text auch Mikroemulsionen. Der Ausdruck "Mikroemulsionen" bezieht sich nur auf Emulsionen mit einer mittleren Teilchengröße von höchstens 150 nm, die transparent bis optisch klar sind. Mikroemulsionen von Organopolysiloxanen mit Alkylpolyglykosiden als Emulgatoren sind nicht vorbeschrieben.The emulsions used according to the invention preferably have an average particle size of at most 1 µm, in particular of at most 300 nm. The used according to the invention Microemulsions preferably have an average particle size of at most 150 nm, in particular of at most 20 nm, on. The term "emulsions" also includes microemulsions throughout the text. The term "microemulsions" only refers on emulsions with an average particle size of at most 150 nm, which are transparent to optically clear. Microemulsions of organopolysiloxanes with alkyl polyglycosides as emulsifiers are not prescribed.
Beispielsweise zur Verkleinerung der Teilchengröße und zur Verringerung der benötigten Menge an Alkylpolyglycosiden (b) können die erfindungsgemäß eingesetzten Emulsionen, insbesondere die Mikroemulsionen, auch Cotenside vorzugsweise in Mengen von 0 bis 30 Gewichtsteilen, insbesondere höchstens 20 Gewichtsteilen, jeweils bezogen auf 100 Gewichtsteile der Organopolysiloxane (a), enthalten.For example, to reduce the particle size and Reduction in the amount of alkyl polyglycosides required (b) the emulsions used according to the invention, in particular the microemulsions, including cosurfactants, preferably in quantities from 0 to 30 parts by weight, in particular at most 20 parts by weight, each based on 100 parts by weight of the organopolysiloxanes (a) included.
Unter Cotensiden versteht man polare Verbindungen mittlerer Molmasse, wie vorzugsweise Alkohole der Molekülgröße C4 bis C8, geeignete Glykolether, Amine, Ester oder Ketone.Co-surfactants are understood to mean polar compounds of medium molecular weight, such as preferably alcohols of molecular size C 4 to C 8 , suitable glycol ethers, amines, esters or ketones.
Beispiele für besonders geeignete Cotenside sind vorzugsweise 1-Butanol, 2-Butanol, 2-Methyl-2-propanol, 1-Pentanol, 2-Pentanol, 3-Pentanol, 1-Hexanol, 2-Hexanol, 3-Hexanol, 1-Heptanol, 2-Heptanol, 3-Heptanol, 4-Heptanol, 1-Octanol, 2-Octanol, 3-Octanol und 4-Octanol; Diethylenglycolmonomethyl-, -ethyl-, und -butylether; Diethylenglycoldimethyl- und -ethylether; 1-Aminobutan, 2-Aminobutan, 2-Amino-2-methyl-propan, 1-Aminopentan, 2-Aminopentan, 1-Aminohexan, 1-Aminoheptan und 1-Aminooctan; Ethyl-, Propyl-, Isopropyl-, Butyl-, Iso-butyl-, Pentyl-, Isopentyl- und Hexylacetat; Methyl-, Ethyl-und tert.-Butylpropionat; Methyl-, Ethyl-, Propyl- und Butylbutyrat; 2-Butanon, 2-Pentanon, 3-Pentanon, 4-Methyl-2-pentanon, 2-Hexanon, 3-Hexanon, 2-Heptanon, 3-Heptanon, 4-Heptanon, 5-Methyl-3-Heptanon, 2-Octanon und 3-Octanon.Examples of particularly suitable cosurfactants are preferred 1-butanol, 2-butanol, 2-methyl-2-propanol, 1-pentanol, 2-pentanol, 3-pentanol, 1-hexanol, 2-hexanol, 3-hexanol, 1-heptanol, 2-heptanol, 3-heptanol, 4-heptanol, 1-octanol, 2-octanol, 3-octanol and 4-octanol; Diethylene glycol monomethyl, ethyl and butyl ether; Diethylene glycol dimethyl and ethyl ether; 1-aminobutane, 2-aminobutane, 2-amino-2-methyl-propane, 1-aminopentane, 2-aminopentane, 1-aminohexane, 1-aminoheptane and 1-aminooctane; Ethyl, propyl, Isopropyl, butyl, iso-butyl, pentyl, isopentyl and hexyl acetate; Methyl, ethyl and tert-butyl propionate; Methyl-, Ethyl, propyl and butyl butyrate; 2-butanone, 2-pentanone, 3-pentanone, 4-methyl-2-pentanone, 2-hexanone, 3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 5-methyl-3-heptanone, 2-octanone and 3-octanone.
Beispiele für bevorzugte Cotenside sind 1-Alkanole der vorstehend aufgeführten Beispiele mit C5- bis C8-Ketten, Diethylenglycolmonobutylether, Diethylenglycoldimethyl- und Diethylenglycoldiethylether, Propyl-, Butyl- und Pentylacetat sowie 2-Pentanon.Examples of preferred cosurfactants are 1-alkanols of the examples given above with C 5 to C 8 chains, diethylene glycol monobutyl ether, diethylene glycol dimethyl and diethylene glycol diethyl ether, propyl, butyl and pentyl acetate and 2-pentanone.
Als Cotenside besonders bevorzugt sind 1-Pentanol, 1-Hexanol und 1-Octanol, Diethylenglycolmonobutylether, Diethylenglycoldimethylether und Butylacetat.1-Pentanol and 1-hexanol are particularly preferred as cosurfactants and 1-octanol, diethylene glycol monobutyl ether, diethylene glycol dimethyl ether and butyl acetate.
Außer organopolysiloxan (a), Alkylpolyglykosiden (b), Wasser und gegebenenfalls Cotensid können die erfindungsgemäß eingesetzten Emulsionen noch Zusatzstoffe enthalten. Die sind insbesondere Bactericide, Fungicide, Algicide, Mikrobicide, Duftstoffe, Korrosionsinhibitoren, Farbstoffe, Pigmente, Verdikkungsmittel und Füllstoffe. Die erfindungsgemäß eingesetzten Emulsionen enthalten Zusatzstoffe vorzugsweise in Mengen von 0 bis 1 Gewichtsprozent, insbesondere von 0 bis 0,2 Gewichtsprozent, jeweils bezogen auf das Gesamtgewicht der fertigen Emulsion.Except organopolysiloxane (a), alkyl polyglycosides (b), water and optionally cosurfactant can be used according to the invention Emulsions still contain additives. They are special Bactericide, Fungicide, Algicide, Microbicide, fragrances, Corrosion inhibitors, dyes, pigments, thickeners and fillers. The used according to the invention Emulsions preferably contain additives in amounts of 0 up to 1 percent by weight, in particular from 0 to 0.2 percent by weight, each based on the total weight of the finished Emulsion.
Das Vermischen aller Komponenten der erfindungsgemäß eingesetzten Emulsion kann in beliebiger Reihenfolge unter Verwendung von Emulgiergeräten oder durch Zusammenrühren ohne Aufbietung hoher Scherkräfte erfolgen. Es ist jedoch bevorzugt, daß zuerst eine homogene Mischung von organopolysiloxan (a), Alkylpolyglykosiden (b) und Wasser hergestellt und in diese Mischung die Cotenside und Zusatzstoffe, sofern eingesetzt, ohne Aufbietung hoher Scherkräfte eingerührt werden.Mixing all components of the used according to the invention Emulsion can be used in any order of emulsifying devices or by stirring together without being charged high shear forces occur. However, it is preferred that first a homogeneous mixture of organopolysiloxane (a), Alkyl polyglycosides (b) and water produced and in this Mix the cosurfactants and additives, if used, be stirred in without applying high shear forces.
Der auf die jeweiligen Komponenten bzw. Mischungen ausgeübte Druck ist vorzugsweise der gegebenenfalls durch Einwirkung der Mischorgane erhöhte (Atmosphären-)Druck; die entsprechend herrschende Temperatur ist vorzugsweise die gegebenenfalls durch Einwirkung der Mischorgane erhöhte (Raum-)Temperatur.The one exercised on the respective components or mixtures Pressure is preferably that which may be due to the action of Mixing elements increased (atmospheric) pressure; the corresponding the prevailing temperature is preferably the one where appropriate increased by the action of the mixing elements (Room) temperature.
Das vorzugsweise in den erfindungsgemäß eingesetzten Emulsionen enthaltene eingesetzte ammoniumfunktionelle Organopolysiloxan (a) kann hergestellt werden durch Zugabe von Mineralsäuren oder Carbonsäuren zu entsprechenden aminofunktionellen Organopolysiloxanen. Diese Zugabe von Säure zum Organopolysiloxan (a) kann erfolgen, bevor das organopolysiloxan (a) eingesetzt wird.This is preferably in the emulsions used according to the invention contained contained ammonium-functional organopolysiloxane (a) can be made by adding mineral acids or carboxylic acids to corresponding amino-functional organopolysiloxanes. This addition of acid to the organopolysiloxane (a) can be done before the organopolysiloxane (a) is used becomes.
In einer besonders bevorzugten Ausführungsform zur Herstellung der erfindungsgemäß eingesetzten Emulsionen unter Einsatz besonders bevorzugter amino- und/oder ammoniumfunktioneller Organopolysiloxane (a) werden die ammoniumfunktionellen Reste jedoch in situ beim Mischen von organopolysiloxan (a), Alkylpolyglykosiden (b) und Wasser durch Zugabe der vorstehend beschriebenen Mineral- und/oder Carbonsäuren, insbesondere Essigsäure, erzeugt.In a particularly preferred embodiment for the production the emulsions used according to the invention are particularly suitable preferred amino and / or ammonium functional organopolysiloxanes (a) the ammonium functional residues however in situ when mixing organopolysiloxane (a), alkyl polyglycosides (b) and water by adding those described above Mineral and / or carboxylic acids, especially acetic acid, generated.
Die erfindungsgemäß eingesetzten Emulsionen können grundsätzlich in jedem turbulenten Mischer hergestellt werden, der auch bisher zur Herstellung von Emulsionen verwendet wurde. Beispiele für verwendbare Mischer sind Rührer, wie Blatt-, Balken-, Anker-, Gitter-, Schnecken-, Propeller-, Scheiben-, Impeller-, Turbinen-, Planetenrührer, Ein- und Doppelschneckenmischer, Mischturbinen, Kolloidmühlen, Ultraschallmischer, In-line-Mischer, Pumpen, Homogenisatoren, wie Hochdruck-, Turbinen- und Umlaufhomogenisatoren.The emulsions used according to the invention can in principle be made in any turbulent mixer, too has previously been used to prepare emulsions. Examples for mixers that can be used are stirrers such as blades, bars, Anchor, grid, screw, propeller, disc, impeller, Turbine, planetary stirrers, single and twin screw mixers, Mixing turbines, colloid mills, ultrasonic mixers, in-line mixers, Pumps, homogenizers, such as high pressure, turbine and circulation homogenizers.
Handelsübliches, indigogefärbtes Denim-Rohgewebe aus 100 % Baumwolle wurde in langer Flotte (500 %) mit 0,5 g/L Bakterienamylase (Mucilase, Freedom/ Diamalt) bei pH 6,0 2 Stunden bei 55 ° C entschlichtet und anschließend mit klarem Wasser tensidfrei gespült und bei Raumtemperatur getrocknet. Commercial, indigo-dyed denim from 100% Cotton was in a long liquor (500%) with 0.5 g / L bacterial amylase (Mucilase, Freedom / Diamalt) at pH 6.0 for 2 hours desized at 55 ° C and then with clear water Rinsed free of surfactants and dried at room temperature.
Die Stoffproben wurden am Foulard mit wässrigen Emulsionen bzw. Lösungen der Prüfsubstanzen, im Falle der Siliconöle mit Lösungen in Testbenzin, so beaufschlagt, daß ca. 1,0 % Wirksubstanz auf Gewebegewicht aufgebracht wurde. Schließlich wurde bei 150 ° C 5 Minuten getrocknet.The fabric samples were padded with aqueous emulsions or solutions of the test substances, in the case of silicone oils with Solutions in white spirit, so applied that approx. 1.0% Active substance was applied to tissue weight. Finally was dried at 150 ° C for 5 minutes.
Probenstücke 7 x 5 cm wurden aneinandergenäht und in einem Glasrohr begast. Die Konzentration an Ozon/NOx betrug ca. 200 mg/h, die Durchflußrate 2,0 l/h. Das oxydierende Agens wurde durch elektrische Entladung in Luft von einem Ozongenerator erzeugt, so daß 03 neben NOx vorlag. Die Einwirkzeit betrug jeweils 60 Minuten bei Raumtemperatur. Die Proben wurden anschließend gespült und getrocknet.Samples 7 x 5 cm were sewn together and gassed in a glass tube. The concentration of ozone / NO x was approx. 200 mg / h, the flow rate 2.0 l / h. The oxidizing agent was generated by electrical discharge in air from an ozone generator so that 0 3 was present in addition to NO x . The exposure time was 60 minutes at room temperature. The samples were then rinsed and dried.
Die Proben werden hängend mit Ozon behandelt. Ozon wird durch "stille Entladung" in einem Ozonisator aus reinem Sauerstoff hergestellt. Der Sauerstoffdurchfluß wird mit Hilfe eines Flowmeters eingestellt und am Ende der Apparatur mit einer Gasuhr gemessen. Bei der gewählten Ozonisatoreinstellung werden durchschnittlich 200 mg Ozon pro Stunde produziert.Hanging samples are treated with ozone. Through ozone "silent discharge" in an ozonizer made of pure oxygen manufactured. The oxygen flow is measured using a Flowmeters set and at the end of the apparatus with a Gas clock measured. With the chosen ozonizer setting produces an average of 200 mg of ozone per hour.
Um zu starke Warenbewegung durch den Gasfluß zu vermeiden, werden die zu einem Streifen zusammengenähten Proben mit einem Gewicht (ca. 30 g) beschwert.To avoid excessive movement of goods due to the gas flow, the samples are sewn together into a strip with a Weight (approx. 30 g) weighed down.
- Ozonkonzentration:Ozone concentration:
- ca. 200 mg/happrox. 200 mg / h
- Durchflußrate:Flow rate:
- 2,0 l/h2.0 l / h
- Behandlungsdauer:Treatment duration:
- 60 min, bei Raumtemperatur60 min, at room temperature
Nach der Ozonbehandlung werden die Prüflinge im Mathis Trockner bei Raumtemperatur 20 Minuten lang mit Umluft (maximale Lüftungsstufe) behandelt, um Restozon von der Ware zu entfernen.After the ozone treatment, the test specimens are in the Mathis dryer at room temperature for 20 minutes with circulating air (maximum Ventilation level) treated to rest ozone from the goods too remove.
Sie erfolgte an einem Farbmess-Gerät (Data Color Spectra Flash 600). Die Beurteilung erfolgte nach dem Verlust der Farbstärke in %.It was carried out on a color measurement device (Data Color Spectra Flash 600). The assessment was made after the loss of color strength in %.
Einfluß von Weichmachern auf den Verlust der Farbstärke bei 03
/ NOx Behandlung:
Microemulsion eines niedrigviskosen, gestopperten Siliconöles mit Aminoethyl-aminopropylgruppen; Ölviskosiät 200 mm2/s, Aminzahl 0,25; emulgiert mit Trimethylnonanol x 6 EO Silicone plasticizer 1:
Microemulsion of a low viscosity, blocked silicone oil with aminoethyl aminopropyl groups; Oil viscosity 200 mm 2 / s, amine number 0.25; emulsified with trimethylnonanol x 6 EO
Macroemulsion eines hochviskosen, niedrigaminierten, reaktiven Öls; Ölviskosität 8000 mm2/s; Aminzahl 0,15; emulgiert mit iso-C13 Fettalkohol x 10 EO Silicon plasticizer 2:
Macroemulsion of a highly viscous, low-aminated, reactive oil; Oil viscosity 8000 mm 2 / s; Amine number 0.15; emulsified with iso-C 13 fatty alcohol x 10 EO
Macroemulsion des gleichen Öles wie Weichmacher 2, emulgiert mit Alkyltrimethylammoniumchlorid und Nonylphenol x 7 EO Silicon plasticizer 3:
Macroemulsion of the same oil as plasticizer 2, emulsified with alkyltrimethylammonium chloride and nonylphenol x 7 EO
Macroemulsion eines reaktiven aminreichen Siliconöles; ölviskosität 1000 mm2/s, Aminzahl 0,6; emulgiert mit einem Gemisch aus C13-Fettalkohol x 6 EO und C13-Fettalkohol x 8 EO Silicone plasticizer 4:
Macroemulsion of a reactive amine-rich silicone oil; oil viscosity 1000 mm 2 / s, amine number 0.6; emulsified with a mixture of C 13 fatty alcohol x 6 EO and C 13 fatty alcohol x 8 EO
Microemulsion eines gestopperten, aminreichen öles; Ölsivkosität 1000 mm2/s, Aminzahl 0,6; emulgiert mit C13-Fettalkohol x 6 EO Silicone plasticizer 5:
Microemulsion of a stopped, amine-rich oil; Oil viscosity 1000 mm 2 / s, amine number 0.6; emulsified with C 13 fatty alcohol x 6 EO
Microemulsion eines reaktiven Öles mittleren Amingehalts; ölviskosität 1000 mm2/s; Aminzahl 0,3; emulgiert mit C13-Fettalkohol x 6 EO Silicone plasticizer 6:
Medium amine reactive oil microemulsion; oil viscosity 1000 mm2 / s; Amine number 0.3; emulsified with C 13 fatty alcohol x 6 EO
Microemulsion eines cyclohexylaminofunktionellen (thermovergilbungsarmen) Siliconöls; Ölviskosität 1000 mm2/ s; Aminzahl 0,3; emulgiert mit C13-Fettalkohol x 6 EO mit Butyldiglykol als Co-Emulgator Silicone plasticizer 7:
Microemulsion of a cyclohexylamino-functional (low-yellowing) silicone oil; Oil viscosity 1000 mm 2 / s; Amine number 0.3; emulsified with C 13 fatty alcohol x 6 EO with butyl diglycol as co-emulsifier
Einfluß der Reinsubstanzen auf den Verlust der Farbstärke bei
03/NOx-Behandlung
EO = Ethylenoxid
Herstellung von Weichmacheremulsionen für die Ausrüstung von
Denims:
17 Teile eines gestopperten hochaminierten Aminosiliconöles (Aminzahl = 0,6; Viscosität = 1000 mm2/s) wurden mit 8,6 Teilen Alkylplyglycosid (70%ig), 74 Teilen vollentsalztem Wasser und 0,3 Teilen Essigsäure 100 %ig zu einer Emulsion verrührt und mit 3,5 g/L Formalinlösung konserviert.
Das Öl war identisch mit dem im Weichmacher 5 verwendeten Produkt.
Als Emulgator diente Glucopon 225 DK (Henkel), ein C8 - C10 Alkylplyglycosid mit 1,7 Zuckereinheiten und 70 % Aktivgehalt.
Analog wurde aus dem auch in Weichmacher 4 eingesetzten reaktiven Öl nach Rezeptur von Weichmacher 8 eine Emulsion bereitet.
Das bereits in den Weichmachern 2 + 3 eingesetzte aminarme, hochviskose Siliconöl wurde zu 17 Teilen mit 9,5 Teilen Glucopon 215 CSUP (Henkel) und 0,08 Teilen Essigsäure emulgiert und mit 3,5 g/L Formalinlösung konserviert.
Glucopon 215 CSUP ist ein C8 - C10 Alkylpolyglykosid mit 1,5 Zuckereinheiten.
17 Teile des bereits in Weichmacher 6 benutzten Aminöles der Aminzahl 0,3 wurden mit 8,6 Teilen Glucopon 225 DK wie bei Weichmacher 8 beschrieben emulgiert, jedoch mit einer auf 0,15 Teile reduzierte Menge an Essigsäure.
17 parts of a stopped highly aminated amino silicone oil (amine number = 0.6; viscosity = 1000 mm 2 / s) were mixed with 8.6 parts of alkylplyglycoside (70%), 74 parts of completely demineralized water and 0.3 parts of acetic acid to form an emulsion stirred and preserved with 3.5 g / L formalin solution.
The oil was identical to the product used in plasticizer 5.
Glucopon 225 DK (Henkel), a C 8 - C 10 alkylplyglycoside with 1.7 sugar units and 70% active content, served as emulsifier.
Analogously, an emulsion was prepared from the reactive oil also used in plasticizer 4 according to the formulation of plasticizer 8.
The low-amine, highly viscous silicone oil already used in plasticizers 2 + 3 was emulsified to 17 parts with 9.5 parts Glucopon 215 CSUP (Henkel) and 0.08 parts acetic acid and preserved with 3.5 g / L formalin solution.
Glucopon 215 CSUP is a C 8 - C 10 alkyl polyglycoside with 1.5 sugar units.
17 parts of the amine oil of 0.3 amine already used in plasticizer 6 were emulsified with 8.6 parts of Glucopon 225 DK as described for plasticizer 8, but with a reduced amount of acetic acid to 0.15 parts.
Einfluß von Weichmachern auf Basis Aminosilicon/Alkylpolyglycoside
auf den Verlust der Farbstärke bei 03 / NOx Behandlung:
Der durch erfindungsgemäße Weichmacher hervorgerufene Verlust an Farbstärke in % ist also erheblich geringer als bei Verwendung konventioneller Siliconemulsionen (Beispiel 1) und in der gleichen Größenordnung, wie bei Verwendung von z. B. Polyethylen-Emulsionen. Der durch Aminosilicone bewirkte Weichgriff aber ist den mit Polyethylen erzielbaren, wie jedem Textilfachmann geläufig, weit überlegen.The loss caused by plasticizers according to the invention % of color strength is therefore considerably less than when used conventional silicone emulsions (Example 1) and in same order of magnitude as when using e.g. B. polyethylene emulsions. The soft grip caused by aminosilicones but is the one obtainable with polyethylene, like any textile specialist common, far superior.
In den bisherigen Beispielen wurde der erfindungsgemäße Weichmacher
über Foulard aufgetragen um einen streng definierten
Weichmachergehalt auf dem Gewebe zu erzielen.
In der industriellen Praxis aber wird der Weichmacher in der
Waschmaschine im Ausziehverfahren appliziert.In the previous examples, the plasticizer according to the invention was applied via padding in order to achieve a strictly defined plasticizer content on the fabric.
In industrial practice, however, the plasticizer is applied in the washing machine using the pull-out method.
5 a) In einer horizontalen Trommelwaschmaschine wurden 35 Paar Jeans (ca. 30 kg) in langer Flotte entschlichtet, gebleicht und gespült. Nach Ablassen wurden 300 1 Frischwasser zugegeben und mit 1,8 kg Weichmacher 8 (siehe Seite 23) entsprechen 0,3 kg Silicon versetzt. Nach 30 Minuten Laufzeit war der Weichmacher zu ca. 45 % ausgezogen.5 a) 35 pairs were in a horizontal drum washing machine Jeans (approx. 30 kg) desized in a long fleet, bleached and rinsed. After draining, 300 l of fresh water were added and with 1.8 kg of plasticizer 8 (see page 23) correspond to 0.3 kg of silicone added. After 30 minutes, the plasticizer was about 45% moved out.
5 b) Um die Ausbeute zu erhöhen, wurde zusätzlich zu den 1,8 kg Weichmacher Nr. 8 im Parallelversuch ein sogenannter Aktivator zugegeben und zwar in einer Menge von 0,04 kg. Durch diese Zugabe stieg die Ausziehrate auf 90 %.5 b) In order to increase the yield, in addition to the 1.8 kg of plasticizer No. 8 in a parallel experiment, a so-called activator added in an amount of 0.04 kg. With this addition, the extraction rate rose to 90%.
Der Aktivator ist ein seit langem bekanntes Produkt zur Förderung des Ausziehvermögens von Weichmacheremulsionen.The activator is a long-known promotional product the pull-out capacity of plasticizer emulsions.
Er besteht aus einer wässrig-alkoholischen Lösung von 40 % Triethanolamintitanat und 11 % Zinkacetat x 2 H2O.It consists of an aqueous alcoholic solution of 40% triethanolamine titanate and 11% zinc acetate x 2 H 2 O.
Claims (5)
- Indigo-dyed fabric characterized in that it comprises at least one organopolysiloxane and at least one alkyl polyglycoside.
- Indigo-dyed fabric according to Claim 1, characterized in that the organopolysiloxane is an amino-functional organopolysiloxane.
- Indigo-dyed fabric according to Claim 1 or 2, characterized in that the weight ratio of organopolysiloxane to the alkyl polyglycoside is 10:1 to 0.5:1.
- Process for the treatment of a fabric dyed with indigo according to one or more of Claims 1 to 3, characterized in that at least one organopolysiloxane and at least one alkyl polyglycoside are applied.
- Process for the treatment of a fabric dyed with indigo, according to Claim 4, characterized in that at least one organopolysiloxane and at least one alkyl polyglycoside are applied in the form of an emulsion.
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19722680 | 1997-05-30 | ||
DE19722680A DE19722680A1 (en) | 1997-05-30 | 1997-05-30 | Silicone softener for jeans |
Publications (2)
Publication Number | Publication Date |
---|---|
EP0881325A1 EP0881325A1 (en) | 1998-12-02 |
EP0881325B1 true EP0881325B1 (en) | 1999-09-29 |
Family
ID=7830941
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP98109267A Expired - Lifetime EP0881325B1 (en) | 1997-05-30 | 1998-05-22 | Silicone softening agents for jeans |
Country Status (6)
Country | Link |
---|---|
US (1) | US6042615A (en) |
EP (1) | EP0881325B1 (en) |
JP (1) | JP2868763B2 (en) |
BR (1) | BR9801560A (en) |
DE (2) | DE19722680A1 (en) |
ES (1) | ES2139467T3 (en) |
Families Citing this family (8)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE19915439A1 (en) * | 1999-04-07 | 2000-10-12 | Cognis Deutschland Gmbh | Process for stabilizing dyed textile against yellowing |
DE10005855A1 (en) * | 2000-02-10 | 2001-08-23 | Wacker Chemie Gmbh | Polyester containing sheet, useful for the production of clothing, table cloths, coverings, tents, awnings, bags and rucksacks, contains an organopolysiloxane and an alkyl polyglycoside |
DE10034831A1 (en) * | 2000-07-18 | 2002-01-31 | Ciba Sc Pfersee Gmbh | Mixtures of polysiloxane emulsions |
DE10040631A1 (en) * | 2000-08-16 | 2002-03-07 | Wolfram Koch | Yellowing inhibitor for blue denim textiles |
US6632385B2 (en) | 2001-03-23 | 2003-10-14 | First Quality Nonwovens, Inc. | Condrapable hydrophobic nonwoven web and method of making same |
ES2496966T3 (en) * | 2005-12-16 | 2014-09-22 | Southern Mills, Inc. | Protective clothing that provides thermal protection |
US9725680B2 (en) * | 2014-08-27 | 2017-08-08 | The Procter & Gamble Company | Method of preparing a detergent composition comprising a cationic polymer with a silicone/surfactant mixture |
CN110698691A (en) * | 2019-11-06 | 2020-01-17 | 常州市宁河新材料科技有限公司 | Preparation method of hydrophobic amino silicone oil emulsion |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US5114426A (en) * | 1988-12-28 | 1992-05-19 | Atochem North America, Inc. | Chemical stonewash methods for treating fabrics |
DE3925846A1 (en) * | 1989-08-04 | 1991-02-14 | Huels Chemische Werke Ag | EMULSIFIERS FOR THE PRODUCTION OF STABLE, AQUEOUS POLYSILOXANE OR POLYSILOXANE PARAFFINOEL EMULSIONS |
DE4131551A1 (en) * | 1991-09-21 | 1993-03-25 | Pfersee Chem Fab | Aq. dispersions of amino- or amido-polysiloxane(s) - contain alkyl-poly:glycoside(s) as dispersants, and are useful for treatment of fibre materials, esp. textiles |
US5254269A (en) * | 1991-11-26 | 1993-10-19 | Lever Brothers Company, Division Of Conopco, Inc. | Fabric conditioning composition containing an emulsified silicone mixture |
DE4306796A1 (en) * | 1993-03-04 | 1994-09-08 | Wacker Chemie Gmbh | Emulsions of organopolysiloxanes containing polar groups with alkylpolyglycosides as emulsifiers |
US5480567A (en) * | 1994-01-14 | 1996-01-02 | Lever Brothers Company, Division Of Conopco, Inc. | Surfactant mixtures for fabric conditioning compositions |
DE19603401A1 (en) * | 1996-01-31 | 1997-08-07 | Basf Ag | Preventing yellowing of ready-made textile goods dyed with vat dye |
-
1997
- 1997-05-30 DE DE19722680A patent/DE19722680A1/en not_active Withdrawn
-
1998
- 1998-05-22 DE DE59800032T patent/DE59800032D1/en not_active Expired - Fee Related
- 1998-05-22 EP EP98109267A patent/EP0881325B1/en not_active Expired - Lifetime
- 1998-05-22 ES ES98109267T patent/ES2139467T3/en not_active Expired - Lifetime
- 1998-05-27 US US09/085,744 patent/US6042615A/en not_active Expired - Fee Related
- 1998-05-28 JP JP10147251A patent/JP2868763B2/en not_active Expired - Fee Related
- 1998-05-29 BR BR9801560-5A patent/BR9801560A/en not_active Application Discontinuation
Also Published As
Publication number | Publication date |
---|---|
JP2868763B2 (en) | 1999-03-10 |
DE19722680A1 (en) | 1998-12-03 |
JPH10331074A (en) | 1998-12-15 |
DE59800032D1 (en) | 1999-11-04 |
BR9801560A (en) | 1999-12-14 |
EP0881325A1 (en) | 1998-12-02 |
US6042615A (en) | 2000-03-28 |
ES2139467T3 (en) | 2000-02-01 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
DE667744C (en) | Process for the preparation of condensation products which are soluble or easily dispersible in water | |
EP0622397B1 (en) | Emulsions of polar groups-containing organopolysiloxanes with alkylpolyglycosides as emulsifiers | |
DE3519601C2 (en) | ||
EP0881325B1 (en) | Silicone softening agents for jeans | |
EP0628655B1 (en) | Bleaching aids | |
DE2641263A1 (en) | DETACHING MEANS AND METHODS FOR CLEANING AND, IF NECESSARY, COLORING TEXTILE MATERIALS | |
DE102016218163A1 (en) | Improved coloring of textiles with synthetic materials in the washing machine due to modified silicones | |
DE3932276C2 (en) | Textile treatment agent and its use | |
CH689150B5 (en) | Finishing agent. | |
DE4407801A1 (en) | Treatment of textiles | |
CN107858843B (en) | A kind of textile color fixing agent of chitosan-containing quaternary ammonium salt and preparation method thereof | |
DE10259291B4 (en) | Highly concentrated, self-emulsifying preparations containing organopolysiloxanes and alkylammonium compounds and their use in aqueous systems | |
KR20000077318A (en) | Siloxane emulsions | |
DE19652524C2 (en) | Emulsions containing organopolysiloxanes, their preparation and use in aqueous systems | |
GB2492641A (en) | Process for inkjet printing of textiles | |
EP1498541A2 (en) | Process for manufacturing cotton warp yarns with an "inverse denim " effect. | |
DE3137044A1 (en) | IMIDAZOLINDERVATE | |
EP0978586A2 (en) | Aqueous microemulsions containing organopolysiloxanes | |
DE60127117T2 (en) | COLOR RECOVERY FUNDS | |
EP1127975A1 (en) | Polyester fabric | |
DE349655C (en) | Process to remove all types of textile fibers from their starchy, rubbery, gelatinous and fat, from the finishing or stiffening and the like. Like. To rid originating substances with the help of bacteria | |
MXPA98004314A (en) | Silicon softener for je | |
DE19614628A1 (en) | Pretreatment of textiles | |
JP2004218180A (en) | Method for continuous enzymic refining of cotton fiber | |
DE1149687B (en) | Process for the treatment, in particular antistatic finishing, of textile materials |
Legal Events
Date | Code | Title | Description |
---|---|---|---|
PUAI | Public reference made under article 153(3) epc to a published international application that has entered the european phase |
Free format text: ORIGINAL CODE: 0009012 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
17P | Request for examination filed |
Effective date: 19980522 |
|
AK | Designated contracting states |
Kind code of ref document: A1 Designated state(s): BE CH DE ES FR GB IT LI NL |
|
AX | Request for extension of the european patent |
Free format text: AL;LT;LV;MK;RO;SI |
|
17Q | First examination report despatched |
Effective date: 19981204 |
|
GRAG | Despatch of communication of intention to grant |
Free format text: ORIGINAL CODE: EPIDOS AGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
GRAH | Despatch of communication of intention to grant a patent |
Free format text: ORIGINAL CODE: EPIDOS IGRA |
|
AKX | Designation fees paid |
Free format text: BE CH DE ES FR GB IT LI NL |
|
GRAA | (expected) grant |
Free format text: ORIGINAL CODE: 0009210 |
|
AK | Designated contracting states |
Kind code of ref document: B1 Designated state(s): BE CH DE ES FR GB IT LI NL |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: EP |
|
REF | Corresponds to: |
Ref document number: 59800032 Country of ref document: DE Date of ref document: 19991104 |
|
GBT | Gb: translation of ep patent filed (gb section 77(6)(a)/1977) |
Effective date: 19991108 |
|
ITF | It: translation for a ep patent filed |
Owner name: JACOBACCI & PERANI S.P.A. |
|
ET | Fr: translation filed | ||
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FG2A Ref document number: 2139467 Country of ref document: ES Kind code of ref document: T3 |
|
PLBE | No opposition filed within time limit |
Free format text: ORIGINAL CODE: 0009261 |
|
STAA | Information on the status of an ep patent application or granted ep patent |
Free format text: STATUS: NO OPPOSITION FILED WITHIN TIME LIMIT |
|
26N | No opposition filed | ||
REG | Reference to a national code |
Ref country code: GB Ref legal event code: IF02 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: NL Payment date: 20050429 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: FR Payment date: 20050517 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: GB Payment date: 20050518 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: CH Payment date: 20050520 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: ES Payment date: 20050609 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: BE Payment date: 20050624 Year of fee payment: 8 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: DE Payment date: 20050630 Year of fee payment: 8 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: GB Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060522 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: ES Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060523 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: LI Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060531 Ref country code: CH Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060531 Ref country code: BE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060531 |
|
PGFP | Annual fee paid to national office [announced via postgrant information from national office to epo] |
Ref country code: IT Payment date: 20060531 Year of fee payment: 9 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: NL Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061201 Ref country code: DE Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20061201 |
|
REG | Reference to a national code |
Ref country code: CH Ref legal event code: PL |
|
GBPC | Gb: european patent ceased through non-payment of renewal fee |
Effective date: 20060522 |
|
NLV4 | Nl: lapsed or anulled due to non-payment of the annual fee |
Effective date: 20061201 |
|
REG | Reference to a national code |
Ref country code: FR Ref legal event code: ST Effective date: 20070131 |
|
REG | Reference to a national code |
Ref country code: ES Ref legal event code: FD2A Effective date: 20060523 |
|
BERE | Be: lapsed |
Owner name: *WACKER-CHEMIE G.M.B.H. Effective date: 20060531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: FR Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20060531 |
|
PG25 | Lapsed in a contracting state [announced via postgrant information from national office to epo] |
Ref country code: IT Free format text: LAPSE BECAUSE OF NON-PAYMENT OF DUE FEES Effective date: 20070522 |