EP2262944B1 - Method for finishing fibres and textile fabrics with absorbent microspheres - Google Patents

Description

Field of the invention

The invention relates to a method for equipping fibers and textile fabrics with loadable microspheres.

State of the art

The term "comfort" summarizes increased demands of the consumer, who no longer wants to be satisfied with the fact that the laundry he wears directly on the skin, such as lingerie or pantyhose, does not scratch or cause skin redness, but rather expects that it has a positive effect on the condition of his skin. This can be either to remedy fatigue, as well as to convey a fresh scent or to avoid skin roughness. There has therefore been no lack of efforts to equip textiles, for example, women's tights, with cosmetic agents that merge when wearing on the skin and there cause the desired effects.

• Wirkstoffe werden in Mikrokapseln eingebracht und die beladenen Mikrokapseln auf Textilien aufgebracht. Durch mechanische Zerstörung der Mikrokapseln, z.B. durch Reibung auf der Haut, werden die Wirkstoffe freigesetzt. Nachteilig an dieser Lösung ist, dass die Mikrokapseln, also gewissermaßen die "Behälter" der Wirkstoffe, zerstört werden.

An important technical task in this context is to equip textiles with active ingredients; Of particular importance here are:

• Active substances are introduced into microcapsules and the loaded microcapsules are applied to textiles. By mechanical destruction of the microcapsules, eg by friction on the skin, the active ingredients are released. A disadvantage of this solution is that the microcapsules, so to speak, the "container" of the active ingredients are destroyed.

EP 1,600,210 Al describes loaded microspheres. It involves loading microspheres with active ingredients and then applying the loaded microspheres to textile surfaces where they are physically adsorbed without the use of binders. Although a certain resistance to washing is given in this technical solution, but this does not meet the highest requirements.

WO 2006/015718 A1 describes fibers and fabrics which are characterized by being blended with mixtures of (a) hydrophobic actives and (b) binders. Here, drugs without the mediation of microcapsules or the like are applied to textile surfaces, but not directly, but by means of film-forming polymers (binders). This technical solution lacks a controlled release of the active ingredients.

EP-A-0 388 718 discloses a process for finishing fibers and textiles with porous microspheres loaded with active ingredients.

Description of the invention

It was the task of the present Erdindung to provide a technical solution that ensures that textiles can be loaded by the user with any active ingredients and recharged (reload). In this case, a controlled release of the active ingredients should be given. Furthermore, there should be given an improved compared to the prior art Waschpennanenz. By wash permanence is to be understood that the above-mentioned desirable properties of the textiles are lessened by washing only to a limited extent.
In particular, it was in this context to provide a method that allows a reliable application of active ingredients on textiles.

1. (1) eine wässrige Dispersion der Mikrosphären (a) unter Verwendung von Alkali - und/oder Erdalkaliseifen von Fettsäuren mit 6 bis 24 C-Atomen als Dispergatoren herstellt, wobei man diese Fettsäureseifen entweder als solche einsetzt oder in situ aus Fettsäuren und Alkalihydroxiden herstellt,
2. (2) in die so hergestellten Dispersionen Fasern oder textile Flächengebilde einbringt, wobei gewünschtenfalls eine weitere Verdünnung mit Wasser erfolgt,
3. (3) den pH-Wert der wässrigen Flotte durch Zugabe von organischen und/oder anorganischen Säuren langsam in der Weise absenkt, dass dass die in der Flotte vorhandenen Alkali- und/oder Erdalkaliseifen in die entsprechenden Fettsäuren umgewandelt werden, und
4. (4) Bindemittel (b) zugibt, die im sauren pH-Bereich auf das sphärenbeladene Textil aufziehen.

The invention relates to a process for finishing fibers and textile fabrics with (a) absorbent microspheres and (b) film-forming polymers (binder), wherein component (a) is fixed on the textile surface by means of component (b)

1. (1) preparing an aqueous dispersion of the microspheres (a) using alkali and / or alkaline earth metal soaps of fatty acids having 6 to 24 carbon atoms as dispersants, these fatty acid soaps being used either as such or prepared in situ from fatty acids and alkali hydroxides,
2. (2) incorporating fibers or fabrics into the dispersions so prepared, if desired, further diluting with water,
3. (3) slowly lowering the pH of the aqueous liquor by adding organic and / or inorganic acids in such a way that the alkali and / or alkaline earth metal soaps present in the liquor are converted into the corresponding fatty acids, and
4. (4) Adding binder (b), which draw on the spherically loaded textile in the acidic pH range.

In one embodiment, the dispersion prepared in step (1) is diluted with water in step (2).

The inventive method has several steps, but these are not isolated, but to understand their interaction. Step (1) has the purpose of producing an aqueous dispersion of the microspheres (a), it being understood that it is a solid dispersion. In step (2), textile is introduced into the dispersion thus prepared. In step (3) is achieved by lowering the pH, that the dispersants are converted into the acidic form; as a result, they lose their dispersing activity with the result that the microspheres (a) virtually "precipitate", which they do in such a way that they deposit on the textile. Step (4) has the purpose of making the microspheres (a) applied to the fabric in step (3) wash-permanently bond to the textile.

• Herstellung einer Dispersion von Mikrosphären (a), die feste Teilchen darstellen, in Schritt (1) unter Verwendung von preisgünstigen, gut verfügbaren und ökologisch vorteilhaften Fettsäureseifen;
• einfache Prozessführung durch Steuerung der Aufziehrate über den pH-Wert in Schritt (3);
• sehr hohe Aufziehraten der Mikrosphären (a) auf die damit auszurüstenden Textilien, da die als Dispergatoren eingesetzten Seifen nach Absenkung des pH-Wertes in nicht emulgierende Fettsäure gespalten wird;
• und schließlich eine deutliche Verbesserung der Waschpermanenz, indem in Schritt (4) die Mikrosphären (a) an das textil gebunden werden.

As essential advantages of the invention described are:

• Preparing a dispersion of microspheres (a) constituting solid particles in step (1) using inexpensive, readily available and ecologically advantageous fatty acid soaps;
• simple process control by controlling the Aufziehrate on the pH in step (3);
• very high rates of uptake of the microspheres (a) on the textiles to be equipped therewith, since the soaps used as dispersants are split into non-emulsifying fatty acids after lowering the pH;
• and finally a significant improvement in wash permanence by bonding the microspheres (a) to the textile in step (4).

In one embodiment, the alkali and / or alkaline earth metal soaps of fatty acids having 6 to 24 carbon atoms used in step (1) are selected to have an HLB value in the range of 8 to 25.

In a preferred embodiment, in step (1), the alkali and / or alkaline earth metal soaps of fatty acids having 6 to 24 carbon atoms are prepared in situ by reacting the desired microspheres (a) with one or more fatty acids having 6 to 24 carbon atoms. Mixed atoms, then adds water and the fatty acids by addition of alkali and / or alkaline earth metal hydroxides in the corresponding soaps transferred.

In one embodiment, the dispersion prepared in step (1) contains 1 to 90% by weight, based on the total dispersion, of microspheres (a). The dispersion prepared in step (1) preferably contains from 10 to 70% by weight and in particular from 30 to 60% by weight, in each case based on the total dispersion, of microspheres (a).

The liquor ratios set in step (2) are not critical per se. In a preferred embodiment, liquor ratios in the range of 1:10 and 1:15 are set in step (2). The term liquor ratio is known to the person skilled in the art.

This is understood to mean the ratio of the amount of textile to the volume of water in the machine used for the equipment.

The invention is not subject to any particular limitations with regard to the acids to be used in step 3, provided that it is ensured that these acids are capable of converting the alkali and / or alkaline earth metal soaps of said fatty acids used as dispersants into the free fatty acids. In a preferred embodiment, the acid from the group acetic acid, lactic acid and glycolic acid is selected in step (3).

The lowering of the pH in step (3) is preferably carried out slowly. This ensures that the microspheres (a) are applied to the textile in very high quantities. Preferably, the lowering of the pH in step (3) takes place at a rate such that the microspheres (a) are applied to the textile in amounts of at least 70% and in particular of at least 80%, based on the total amount in the liquor existing microspheres (a) - takes place.

To the absorbent microspheres (a)

The microspheres (a) may be unloaded or partially loaded with drugs or fully loaded. They fulfill the function that they can be loaded by the user as desired and, after release of the active ingredients, can also be reloaded as desired.

Absorbent microspheres are structures that have a largely homogeneous structure. The absorbent microspheres used in the context of the present invention have the property of being able to take up active substances and also release them again, with both occurring several times can, ie agents can be absorbed by loading or reloading and released over time again. Because of this property, these microspheres are referred to as absorbent microspheres. For the sake of simplicity, however, at numerous points in the description of the present application, the addition "absorbent" (= capable of taking active ingredients) is omitted and simply spoken of microspheres. The active substances can be adsorbed on the surface of the microspheres and / or dissolved in the microspheres and / or incorporated in the microspheres, for example in fine channels. Microspheres are dimensionally stable, ie they are not destroyed in the release of the active ingredients.
It should be expressly stated that microcapsules, which are indeed destroyed in the release of the active ingredients, are not covered by the definition of microspheres.

• Die Mikrosphären wirken als Container für Wirkstoffe.
• Die Mikrosphären sind formstabil und werden durch Freisetzung der Wirkstoffe nicht zerstört.
• Die Mikrosphären können mehrfach - auch mit unterschiedlichen Wirkstoffen - nachbeladen werden (reload).

Die Mikrosphären werden durch - ein oder mehrere - filmbildende Polymere auf der Textiloberfläche fixiert, wodurch sich eine im Vergleich zum Stand der Technik relative Verbesserung der Waschpermanenz ergibt.The central point of the technical solution proposed by the present invention is a combination of several factors:

• The microspheres act as containers for active ingredients.
• The microspheres are dimensionally stable and are not destroyed by release of the active ingredients.
• The microspheres can be reloaded several times - even with different active ingredients - (reload).

The microspheres are fixed by - one or more - film-forming polymers on the textile surface, resulting in a relative to the prior art, relative improvement of the washing permanence.

The microspheres are preferably spherical in shape, but are not limited in geometry to spheroidal shape, but may have other spatial shapes, for example, they may represent rotatiosellipsoids or have a rod shape.

The microspheres preferably have an average particle size in the range of 1 to 15 microns, and more preferably 5 to 10 microns.

In one embodiment, microsphere based on polymethylmethacrylate (PMMA) is used. Examples are, for example, Covabead LH 85 or LH 170 from the company LCW or Cosmedia PMMA V8, Cosmedia PMMA V 12 or Cosmedia SILC from Cognis.

In one embodiment, silicone-based or SiO ₂ -based microspheres are used. Examples are "Dow Corning 9509 Silicone Elastomer Suspension" from Dow Corning.

In a preferred embodiment, microspheres based on polymethylmethacrylate (PMMA) are used.

The film-forming polymers (b) (binders)

• Polyurethanen (PU),
• Polyethylvinylacetaten (EVA),
• polymeren Melaminverbindungen,
• polymeren Glyoxalverbindungen,
• polymeren Siliconverbindungen,
• epichlorhydrinvernetzten Polyamidoaminen und
• Poly(meth)acrylaten

The film-forming polymers (b) which are suitable for the purposes of the invention, which can also be referred to as binders, can be of any type per se. Preferably, they are selected from the group formed by

• Polyurethanes (PU),
• Polyethylvinyl acetates (EVA),
• polymeric melamine compounds,
• polymeric glyoxal compounds,
• polymeric silicone compounds,
• epichlorohydrin crosslinked polyamidoamines and
• Poly (meth) acrylates

Suitable polyurethanes (PU) and polyethylvinyl acetates (EVA) are, for example, the commercially available products from the Cognis 3011-A or Cognis 3009-A range from Cognis.

Polymeric melamine compounds: Melamine (synonym: 2,4,6-triamino-1,3,5-triazine) is usually formed by trimerization of dicyandiamide or by cyclization of urea with elimination of carbon dioxide and ammonia. For the purposes of the invention, melamine refers to oligomeric or polymeric condensation products of melamine with formaldehyde, urea, phenol or mixtures thereof. Polymeric Glyoxal Compounds: Glyoxal (synonym: oxaldehyde, ethanedial) results from the vapor phase oxidation of ethylene glycol with air in the presence of silver catalysts. For the purposes of the invention, glyoxals are understood as meaning the self-condensation products of glyoxal ("polyglyoxals").

Silicone compounds: Suitable silicone compounds are, for example, dimethylpolysiloxanes, methylphenylpolysiloxanes, cyclic silicones and amino, fatty acid, alcohol, polyether, epoxy, fluorine, glycoside and / or alkyl-modified silicone compounds which are preferably solid or resin-form at room temperature. Also suitable are simethicones, which are mixtures of dimethicones having an average chain length of from 200 to 300 dimethylsiloxane units and hydrogenated silicates. Particular preference is given to the use of aminosiloxanes, for example Cognis 3001 from Cognis. Their further crosslinking with H-siloxanes, eg Cognis 3002 from Cognis, can further increase the performance as a binder.

1. i) Polyaminoamide werden (a) zunächst mit einer Menge von 5 bis 30 Mol-% - bezogen auf den zur Quaternierung zur Verfügung stehenden Stickstoff - eines Quaternierungsmittels umgesetzt, und (b) anschließend die resultierenden quatemierten Polyaminoamide mit einer dem Gehalt an nicht quaterniertern Stickstoff entsprechenden molaren Menge Epichlorhydrin vernetzt, oder
2. ii) Polyaminoamide werden (a) zunächst bei 10 bis 35°C mit einer Menge von 5 bis 40 Mol-% - bezogen auf den für die Vernetzung zur Verfügung stehenden Stickstoff - Epichlorhydrin umgesetzt, und (b) das Zwischenprodukt auf einen pH-Wert im Bereich von 8 bis 11 einstellt und bei einer Temperatur im Bereich von 20 bis 45°C mit einer weiteren Menge Epichlorhydrin vernetzt, so dass das molare Einsatzverhältnis in Summe 90 bis 125 Mol-% - bezogen auf den für die Vernetzung zur Verfügung stehenden Stickstoff - beträgt.

Epichlorohydrin Crosslinked Polyamidoamine: Epichlorohydrin Crosslinked Polyamidoamines, also referred to as " fibrabones " or " wet strength resins, " are well known in textile and paper technology. Their preparation is preferably based on two methods:

1. i) Polyaminoamides are (a) first reacted with an amount of 5 to 30 mol% based on the available for quaternization nitrogen of a quaternizing agent, and (b) then the resulting quaternized polyaminoamides having a content of non-quaternized nitrogen corresponding molar amount of epichlorohydrin crosslinked, or
2. ii) Polyaminoamides are (a) reacted first at 10 to 35 ° C in an amount of 5 to 40 mol% based on the nitrogen available for the crosslinking of epichlorohydrin, and (b) the intermediate product to a pH in the range from 8 to 11 and cross-linked at a temperature in the range of 20 to 45 ° C with a further amount of epichlorohydrin, so that the molar use ratio in total from 90 to 125 mol% - based on the nitrogen available for the crosslinking - is.

Poly (meth) acrylates: The term poly (meth) acrylates are homo- and copolymerization products of acrylic acid, methacrylic acid and optionally their esters, especially their esters with lower alcohols, such as methanol, ethanol, isopropyl alcohol, the isomeric butanols, cyclohexanol and the like to understand which are obtained in a conventional manner, for example by free-radical polymerization under UV irradiation. Typically, the average molecular weight of the polymers is between 100 and 10,000, preferably 200 and 5,000 and especially 400 to 2,000 daltons.

Usually, the binders (b) - based on the component (a) - in amounts of 0.5 to 15, preferably 1 to 10 and especially 1 to 5 wt .-% applied to the fibers. Component (a) is to be understood as meaning the microspheres in unloaded form.

drugs

The choice of active ingredients that are intended to load the microspheres is not critical per se and depends exclusively on which effect is to be effected on the skin. For the textile equipment, but also for cosmetic applications, such active ingredients are preferred which have moisturizing properties or counteract cellulite. Typical examples are tocopherol, tocopherol acetate, tocopherol palmitate, carotenes, caffeine, ascorbic acid, (deoxy) ribonucleic acid and their fragmentation products, β-glucans, retinol, bisabolol, allantoin, phytantriol, panthenol, AHA acids, amino acids, ceramides, pseudoceramides, chitosan, dihydroxyacetone , Menthol, squalane, essential oils (eg lavender oil, lemon oil, eucalyptus oil or peppermint oil), vegetable oils (eg Monoi de Tahiti, shea butter, almond oil, passion fruit oil, rosehip seed oil or apricot oil), vegetable proteins and their hydrolysis products, plant extracts, such as Extracts of Ginkgo biloba, Camellia sinensis, Trifolium pratensis, Oleacea europensis, Litchi sinensis, Valeriana oficinalis, Medicago sativa, Vitis vinifera, Passiflora incarnata and the like as well as vitamin complexes.

It is particularly preferable to select the active compounds from the group formed by essential oils, vegetable oils, squalane, chitosan, menthol, retinol (or vitamin A), caffeine, vegetable or animal proteins and their hydrolysis products, carotenes and jojoba oil. These have a very broad property profile and contribute individually or in combination to the balance of the cutaneous hydrolipid layer, prevent the loss of water and thus wrinkles, refresh the skin and counteract fatigue, give the skin a soft and elastic feeling, improve skin drainage , the supply of nutrients and blood circulation, work against oxidative stress, environmental toxins, skin aging and free radicals, compensate for the loss of fats caused by water and sun, improve the water resistance of UV filters, ensure a homogeneous tanning and finally also have antimicrobial properties.

Usually, the weight ratio between the component (a) - such as the finely divided PMMA - and the active ingredients is 10: 90 to 99: 1, preferably 3: 1 to 1: 1 and more preferably about 2: 1.

Examples Substances used

• Phenonip : preservative in dispersion
• Cutina GMS-V : additional emulsifier in dispersion
• Cosmedia SP : thickener to stabilize the dispersion
• Edenor PK 1805 : oleic acid, Cognis
• Cosmedia PMMA V8 : microspheres based on polymethylmethacrylate (Cognis)
• Cognis 6003-A : wetting agent in the application process
• Cognis 6006-A : Extraction aid in the application process (cat chitosan "drops" the anionic soap)
• Cognis 3001-A : binder in the application process
• Cognis 3002-A : Crosslinker for binders in the application process

Example 1: Preparation of a Microsphere Dispersion

705 g of demineralized water, 10 g of phenonip, 15 g of Cutina GMS-V and 66 g of Edenor PK 1805 were placed in a stirred tank and mixed. Subsequently, 100 g of Cosmedia PMMA V8 were stirred in and the mixture was homogenized. Now 100 g of a 10% i-potassium hydroxide solution were stirred in, followed by 4 g of Cosmedia SP. The batch was heated to 80 ° C. After 30 minutes was cooled to a temperature below 40 ° C and finally filled at 25 ° C on 250μ sieve. The pH of the dispersion was 8.7. The resulting dispersion was used in Example 2 below.

Example 2: Application

1 kg compression stockings (Venotrain Micro, compression stockings made of 55% / 45% polyamide / elastane, manufactured by Bauerfeind) were placed in a drum dyeing machine. Then the machine was filled with 10 1 of soft water and 10 g of Cognis 6003-A plus 10 g of acetic acid 60%, added. The machine was heated to 50 ° C, the drum speed was set to 25-30 revolutions per minute. Subsequently, 200 g of the microspheres dispersion obtained in Example 1 above were weighed, pre-dissolved in soft water and added. Thereafter, it was treated at 50 ° C for 2 minutes. The pH was controlled; he was 4.6. Subsequently, 20 g of Cognis 6006-A were weighed, pre-dissolved in soft water, and added. Thereafter, it was treated at 50 ° C for 10 minutes. Subsequently, 20 g of Cognis 3001-A were weighed, pre-dissolved in soft water and added. Thereafter, it was treated at 50 ° C for 5 minutes. Subsequently, 1 g of Cognis 3002-A was weighed, pre-dissolved in soft water and added. Then it was 5 min. treated at 50 ° C. After that, the fleet was drained and it was thrown off. Finally, drying / condensing at 120 ° C.

Claims (2)

1. Process for endowing fibres and textile fabrics with (a) absorbent microspheres and (b) filming polymers (binders), wherein component (b) serves to fix component (a) on the textile surface, characterized in that

   (1) an aqueous dispersion of microspheres (a) is produced by using alkali and/or alkaline earth metal soaps of fatty acids having 6 to 24 carbon atoms as dispersants, wherein these fatty acid soaps are either used as such or produced in situ from fatty acids and alkali metal hydroxides,

   (2) the dispersions thus produced are entered with fibres or textile fabrics, wherein a further dilution with water is effected if desired,

   (3) the pH of the aqueous liquor is gradually lowered by addition of organic and/or inorganic acids such that the alkali and/or alkaline earth metal soaps present in the liquor are converted into the corresponding fatty acids, and

   (4) binders (b) are added to exhaust on the sphere-loaded textile in the acidic pH range,

   with the proviso that microcapsules do not fall within the definition of absorbent microspheres (a).
2. Process according to Claim 1, wherein the dispersions produced in step (1) are diluted with water in step (2).