EP2475816A2 - Apprêts rechargeables pour textiles et formulations pour le chargement de tels apprêts - Google Patents

Apprêts rechargeables pour textiles et formulations pour le chargement de tels apprêts

Info

Publication number
EP2475816A2
EP2475816A2 EP10747028A EP10747028A EP2475816A2 EP 2475816 A2 EP2475816 A2 EP 2475816A2 EP 10747028 A EP10747028 A EP 10747028A EP 10747028 A EP10747028 A EP 10747028A EP 2475816 A2 EP2475816 A2 EP 2475816A2
Authority
EP
European Patent Office
Prior art keywords
emulsion
solution
polymer
water
methacrylate
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.)
Withdrawn
Application number
EP10747028A
Other languages
German (de)
English (en)
Inventor
Uwe HOLZDÖRFER
Theo Gaupp
Roland Lottenbach
Hans-Jürgen HÜBNER
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Schoeller Textil AG
Original Assignee
Schoeller Textil AG
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Schoeller Textil AG filed Critical Schoeller Textil AG
Priority to DK12161487T priority Critical patent/DK2481762T3/en
Priority to EP20120161487 priority patent/EP2481762B1/fr
Publication of EP2475816A2 publication Critical patent/EP2475816A2/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61F—FILTERS IMPLANTABLE INTO BLOOD VESSELS; PROSTHESES; DEVICES PROVIDING PATENCY TO, OR PREVENTING COLLAPSING OF, TUBULAR STRUCTURES OF THE BODY, e.g. STENTS; ORTHOPAEDIC, NURSING OR CONTRACEPTIVE DEVICES; FOMENTATION; TREATMENT OR PROTECTION OF EYES OR EARS; BANDAGES, DRESSINGS OR ABSORBENT PADS; FIRST-AID KITS
    • A61F13/00—Bandages or dressings; Absorbent pads
    • A—HUMAN NECESSITIES
    • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
    • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
    • A61K9/00—Medicinal preparations characterised by special physical form
    • A61K9/10—Dispersions; Emulsions
    • A61K9/107—Emulsions ; Emulsion preconcentrates; Micelles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/285—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety
    • C08F220/286—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing a polyether chain in the alcohol moiety and containing polyethylene oxide in the alcohol moiety, e.g. methoxy polyethylene glycol (meth)acrylate
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M13/00—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment
    • D06M13/322—Treating fibres, threads, yarns, fabrics or fibrous goods made from such materials, with non-macromolecular organic compounds; Such treatment combined with mechanical treatment with compounds containing nitrogen
    • D06M13/46—Compounds containing quaternary nitrogen atoms
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/263—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof
    • D06M15/27—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof of alkylpolyalkylene glycol esters of unsaturated carboxylic acids
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M15/00—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment
    • D06M15/19—Treating fibres, threads, yarns, fabrics, or fibrous goods made from such materials, with macromolecular compounds; Such treatment combined with mechanical treatment with synthetic macromolecular compounds
    • D06M15/21—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • D06M15/285—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides
    • D06M15/29—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing a N-methylol group or an etherified N-methylol group; containing a N-aminomethylene group; containing a N-sulfidomethylene group
    • D—TEXTILES; PAPER
    • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
    • D06M—TREATMENT, NOT PROVIDED FOR ELSEWHERE IN CLASS D06, OF FIBRES, THREADS, YARNS, FABRICS, FEATHERS OR FIBROUS GOODS MADE FROM SUCH MATERIALS
    • D06M23/00—Treatment of fibres, threads, yarns, fabrics or fibrous goods made from such materials, characterised by the process
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/20—Esters of polyhydric alcohols or phenols, e.g. 2-hydroxyethyl (meth)acrylate or glycerol mono-(meth)acrylate
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F220/00—Copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and only one being terminated by only one carboxyl radical or a salt, anhydride ester, amide, imide or nitrile thereof
    • C08F220/02—Monocarboxylic acids having less than ten carbon atoms; Derivatives thereof
    • C08F220/10—Esters
    • C08F220/26—Esters containing oxygen in addition to the carboxy oxygen
    • C08F220/28—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety
    • C08F220/281—Esters containing oxygen in addition to the carboxy oxygen containing no aromatic rings in the alcohol moiety and containing only one oxygen, e.g. furfuryl (meth)acrylate or 2-methoxyethyl (meth)acrylate
    • D—TEXTILES; PAPER
    • D10—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B—INDEXING SCHEME ASSOCIATED WITH SUBLASSES OF SECTION D, RELATING TO TEXTILES
    • D10B2401/00—Physical properties
    • D10B2401/13—Physical properties anti-allergenic or anti-bacterial
    • 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

Definitions

  • the invention relates to polymer compounds and finishing formulations for finishing textile products, the corresponding finishing layers and textile products, emulsions for loading the finishing layer with active ingredients, and methods for loading finished textiles with low molecular weight compounds.
  • textiles are understood to mean in particular both fibers and finished textile products (for example woven, knitted or nonwoven fabrics, etc.), for example as a fabric or as already processed product (eg garment).
  • the textiles may consist of any known materials, in particular natural and / or synthetic materials, in particular cotton, linen, silk, hemp, jute, wool, sisal, viscose, polyamide, polyester, etc., as well as mixtures thereof.
  • wound dressings for example of wound dressings (patches), as well as dressing materials.
  • textiles can be loaded with substances and active ingredients.
  • textiles can be equipped with cyclodextrins as active substance carriers and low-molecular active substances can be incorporated into these cyclodextrins, from where they are subsequently liberated.
  • active ingredients can migrate from a textile product to the skin of the wearer, where they can develop a certain desired effect.
  • cosmetic and / or medicinal agents can be absorbed transdermally in this way.
  • textiles may be loaded, for example, with antibacterial or fungicidal substances, for example to prevent odor, or with UV-absorbing substances to increase the UV absorption of the tissue. Also conceivable are substances which keep insects away. With textiles loaded with low-molecular-weight active substances, part of the active substances is inevitably lost with each wash. It is therefore desirable in such functionally modified textiles to be able to load them again in a simple manner with active ingredients.
  • microcapsules containing low molecular weight active ingredients, as well as the individual loading of textiles with such microcapsules.
  • Microcapsules have the disadvantage that upon mechanical action and destruction of the microcapsules, the active ingredients are released abruptly. Such equipment is therefore unsuitable for controlled delivery over a long period of time.
  • the object of the invention is to provide an advantageous equipment formulation which does not have the above-mentioned and other disadvantages of the prior art.
  • the loading can be done several times.
  • the droplets of the microemulsion may in particular contain active substances and other active substances.
  • the active ingredients of the finishing layer should be able to be released with a defined desorption rate.
  • Yet another object of the invention is to provide polymer compounds for such a finish formulation or equipment.
  • a loading can take place in high dilution of the emulsion, for example during a washing process.
  • a polymer compound according to the invention a finishing formulation with such a polymer compound, a finishing layer with such a polymer compound, a finished textile product or a coated wound dressing, an emulsion according to the invention for loading the finishing layer with active ingredients, and a erfindungsdorfes Process according to the independent claims. Further preferred embodiments and variants are given in the dependent claims. Presentation of the invention
  • a polymer compound according to the invention comprises an acrylic acid copolymer of acrylic acid derivatives and / or methacrylic acid derivatives which comprises: a) at least one acrylic acid derivative and / or methacrylic acid derivative substituted with a sulfonic acid group; b) at least one hydrophilic substituted acrylic acid derivative and / or methacrylic acid derivative; c) at least one lipophilic substituted acrylic acid derivative and / or methacrylic acid derivative; and d) at least one acrylic acid derivative and / or methacrylic acid derivative which acts as a crosslinker.
  • a possible acrylic acid or methacrylic acid derivative monomer having a sulfonic acid group is, for example, 2-acryloyl-2-methylpropanesulfonic acid.
  • the sulfonic acid groups of the polymer compound of the invention provide negative charge sites in the polymer matrix, analogous to an ion exchange polymer. Due to the very low pK value of the sulfonic acid groups, the charge sites are deprotonated at the pH values customary during washing. Due to the negative charge sites of the polymer matrix results in a negative surface charge, which is naturally compensated by cations.
  • the effect of the polymer compound according to the invention lies in the fact that dispersed particles of a microemulsion charged with a positive surface charge or positively charged active substances such as, for example, hydrochlorides of heterocyclic compounds or other cationic compounds, are incorporated into the matrix can store the inventive polymer compound.
  • the polymer matrix has a negative surface charge due to the negative charge sites. In this way, the dispersed phase of a corresponding emulsion or the cationic compounds can be stored efficiently in a finishing layer according to the invention.
  • the dispersed phase of such an emulsion low molecular weight compounds are included, which should develop some effect.
  • the compounds mentioned can be separated from the finish layer in a controlled manner, i. continuously over a longer period of time, be returned, or remain in place.
  • active ingredients can pass from the latter onto the skin of the wearer, be absorbed there transdermally, and fully develop their specific action.
  • the desorption behavior can be tailored by controlling the hydrophilic / lipophilic ratio, ie by adjusting the amphiphilic properties of the donor layer. For example, it is easily possible to set the desorption time to 1 6 h, which corresponds to a realistic wearing time of textiles on the body, or optionally to adapt to any desired period of time.
  • a finishing layer according to the invention also referred to as donor layer, furthermore has the property that the desorption by the salts in the body sweat can be triggered.
  • the sodium ions present in the sweat increase the release of active ingredient from the donor layer to the skin.
  • Correspondingly stressed parts of the body for example during exercise, can thereby be preferably supplied with active ingredients.
  • An inventive finish layer can be unloaded and reloaded as often as desired.
  • the loading of a textile product equipped with a polymer compound according to the invention can also be carried out at a comparatively high dilution of the emulsion.
  • such an emulsion can be added to the rinse water in a final rinse of a washing program of a household washing machine, analogous to a fabric softener.
  • a load can also be done by hand washing or by spraying the textiles, which may be more advantageous depending on the application.
  • the coating is preferably carried out in the sterile environment of the manufacturing plant. For bandages, an analogous reloading is possible as with clothing.
  • the polymer matrix has positive charge sites, for example in the form of quaternary ammonium groups instead of the sulfonic acid groups, so that emulsion particles having a negative surface charge adsorb thereto.
  • positive charge sites for example in the form of quaternary ammonium groups instead of the sulfonic acid groups, so that emulsion particles having a negative surface charge adsorb thereto.
  • anionic surfactants can attach to the positive charge sites, so these charge points are shielded and no longer accessible.
  • finishing layer In order for the loading capacity of a finishing layer to be optimal, as many charge points as possible should be accessible to the emulsion particles. For this purpose, it is therefore advantageous if the finishing layer on the textile has a certain swelling, since in this way the accessible surface of the polymer matrix increases, and thus also the accessible surface charge.
  • the polymer compound according to the invention contains hydrophilic substituted acrylic acid or methacrylic acid derivative monomers, such as, for example, ethyltriglycol methacrylate, 2-hydroxyethyl methacrylate (H EMA), and / or mPEC-methacrylates , in particular mPEG-I OOO-methacrylate and mPEC-350-methacrylate.
  • HEMA has the added effect of acting as a docking point for crosslinker monomers when fixing the finishing layer to fabric, resulting in internal polymer crosslinking.
  • finishing layers with HEMA tend to behave more brittle when not hydrated, while finishing layers with mPEC methacrylates remain more elastic in the dry state.
  • Lipophilic substituted acrylic acid or methacrylic acid derivative monomers such as, for example, 2-ethylhexyl-acrylate, ensure a certain lipophilicity of the matrix of a finishing layer according to the invention.
  • the ratio of the proportions of hydrophilic and lipophilic monomers determines, inter alia, the sorption and desorption properties of a finishing layer according to the invention.
  • lipophilic compounds within the adsorbed emulsion particles may migrate into the lipophilic domains of the polymer matrix, increasing the loading capacity of the finish layer.
  • the finishing layer In order to achieve sufficient permanence of the finishing layer on the textile product, the finishing layer must be fixed on the fibers.
  • the inventive polymer compound is crosslinked with the textile fibers.
  • Crosslinking agents for textile equipment are known from the prior art.
  • a possible crosslinker monomer for a polymer compound according to the invention is, for example, N- (butoxymethyl) -acrylamide. In a thermal and / or acid-catalyzed fixation, the corresponding monomer is covalently linked to OH and NH 2 groups of the fibers.
  • the crosslinker monomers of the acrylic acid copolymer are selected from a group consisting of N- (butoxymethyl) acrylamide, N- (methylol) -acrylamide, glycidyl methacrylate, p-EMKO-TDI-o-HEMA and EMKO-2.
  • a polymer compound according to the invention may comprise further polymer compounds, for example polyether sulfones, polyurethanes, polyester urethanes, polyether urethanes, polyamides or mixtures thereof.
  • a polymer compound of the invention may be a blend of such various polymer compounds which are advantageously crosslinkable.
  • a finishing formulation is applied to the textile product or the wound dressing, for example in an aqueous liquor.
  • the finishing formulation contains a polymer compound according to the invention in dissolved form and / or in the form of a microemulsion. After a first drying step, the polymer compound is thermally and / or acid-catalytically fixed on the fiber substrate.
  • a finishing formulation according to the invention may contain, in addition to novel polymer compounds, further polymers such as PES, PU, PUE, PA and crosslinker systems, etc., and / or mixtures thereof. Because of their amphiphilic structure, the polymer compounds according to the invention are miscible and / or crosslinkable with many polymers, or can be processed into blends.
  • the sorption of emulsion particles in a finishing layer according to the invention is shown schematically in FIG. By absorbing water from the environment, for example, atmospheric moisture or rinse water from the loading process, the finish layer 3 fixed on the fiber support 1 is hydrated and swollen. The negative charge sites of the polymer matrix become accessible.
  • finishing layer 3 is then brought together with an emulsion whose emulsion particles 2 have a positive surface charge, these particles 2 can migrate into the pores and gaps of the polymer matrix (FIG. 1 (a)), where they are incorporated into the polymer matrix (FIG. b)).
  • a textile product is provided with a finishing layer whose accessible surface has a negative charge; b) bringing the textile product together with an emulsion, for example by immersing the textile product in the emulsion or by spraying the emulsion onto the textile product.
  • At least one low molecular weight compound is contained in the dispersed phase of the emulsion.
  • the dispersed phase interface has a positive charge.
  • a solution may also be used if the low molecular weight compound dissolved therein is cationic.
  • step b) is carried out several times, at arbitrary time intervals. In this way, the finished materials can be loaded again and again with the desired low molecular weight compounds.
  • the emulsion having the low molecular weight compound is preferably an emulsion according to the invention, as described below.
  • An emulsion according to the invention contains at least one low molecular weight compound with which the textiles are to be loaded, in the dispersed phase of the emulsion.
  • the surface of the dispersed phase particles has a positive charge. This is of course balanced by negatively charged counterions.
  • the surface charge of the particles of the dispersed phase of the emulsion is at least 1 5 mC / g of emulsion, more preferably at least 90 mC / g of emulsion.
  • the positive surface charge of the emulsion particles is achieved by emulsifiers or interface-active compounds which have a positive charge at their polar end. These positive charges are then at the surface of the particles in an oil-in-water emulsion.
  • Suitable surface-active compounds are, for example, lecithin, in particular phosphatidylcholine lecithins, and / or quaternary ammonium compounds having one or two long-chain lipophilic radicals, in particular behenyltrimethylammonium, or ethyl-N al ha -lauroyl-L-arginate / HCl.
  • the diameter of the particles should not exceed a certain size.
  • at least 90% vol. the particles of the dispersed phase of the emulsion have a hydrodynamic diameter of less than 1000 nm, more preferably less than 700 nm.
  • the emulsion may be an oil-in-water emulsion wherein at least one low molecular weight compound is in the lipophilic dispersed phase. This variant is particularly suitable for lipophilic low molecular weight compounds.
  • hydrophilic low molecular weight compounds for example, water-in-oil-in-water emulsions are suitable wherein at least one low molecular weight compound is in the aqueous dispersed phase within the lipophilic dispersed phase. Also suitable are emulsions containing liposomes, in which case the hydrophilic low molecular weight compounds are in the aqueous phase within the liposomes.
  • both lipophilic and hydrophilic compounds are to be loaded onto the textile, then the different types of emulsion can also be combined. Alternatively, different emulsions can be applied sequentially.
  • an inventive emulsion for loading a textile product or a wound dressing with lipophilic and / or hydrophilic low molecular weight compounds, wherein preferably the textile product or the wound dressing has a finishing layer according to the invention, and / or equipped with an inventive finish formulation has been.
  • a finishing layer according to the invention can also be combined with the applicant's 3XDry® technology disclosed in WO 2002/075038 Al.
  • the hydrophilic finish according to the invention can be provided on the outside with a hydrophobic coating.
  • a textile according to the invention can not only be rendered water-repellent on an outer surface, while it is furthermore hydrophilic on the inner side, but the hydrophobic layer simultaneously serves as an active substance barrier to the outside.
  • barrier layers are common, for example, in transdermal patches, where agents should desorb only in a defined direction.
  • a finishing layer according to the invention also has the property of being able to bind cationic heavy metal ions such as cadmium, lead or other toxic substances. This is especially This is important, for example, in countries with high arsenic levels in drinking water, as drinking water can be made edible in this way.
  • the regeneration of the textile treated with the polymer layer can be effected by salt, seawater, soap or washing powder.
  • a finishing layer according to the invention can bind organic impurities in water, for example diesel or gasoline, since organic impurities can adsorb to the lipophilic structures of the amphiphilic polymer compounds according to the invention.
  • a textile according to the invention can be used for the treatment of drinking water.
  • the polymer compound P-002 is an acrylic acid copolymer, namely, poly (acrylic acid-stat-2-ethylhexyl-acrylate-stat-N- (butoxymethyl) -acrylamide).
  • the latter serves to crosslink the polymer with OH and NH 2 groups of the textile fibers.
  • the synthesis is carried out by means of free-radical emulsion polymerization.
  • Initiator solution (corresponds to 1% by weight V-501 based on monomers and crosslinkers):
  • Apparatus 1 l four-necked round bottom flask with stirrer, reflux condenser, septum and temperature probe. An outlet with tap on the reflux condenser serves to evacuate and aerate with nitrogen.
  • Prehomogenization The educt solution is pumped five times at 600 bar through the high pressure homogenizer, resulting in a bluish shimmering emulsion. 1 g of homogenized educt solution is diluted with 39 g of water (1:40). Viscosity: 1 .01 mPa ⁇ s.
  • PCS Photon Correlation Spectroscopy
  • Synthesis 455 g of homogenized educt solution are introduced into the apparatus and heated to 90.degree. It is then evacuated three times in each case and aerated with nitrogen in order to remove the atmospheric oxygen (inhibitor). To ensure pressure equalization throughout the polymerization, the apparatus is back-flowed with nitrogen. Now, with good stirring by means of a syringe, 25 g of initiator solution are added through the septum. The reaction starts immediately. Due to the strong exotherm (5 ° C / min) is immediately countercooled with a water bath and the reaction temperature is kept constant at 90 ° C, (no Nachexothermie feststel lbar). When the startexotherm has subsided, the remaining 27 g of initiator solution are again added after 40 minutes by means of a syringe (no post-exotherm can be determined).
  • the polymer compound P-004 poly (2-acryloylamino-2-methylpropane-sodium sulfonate-stat-2-ethylhexyl-acrylate-stat-N- (butoxymethyl) -acrylamide) contains the monomers 2-acryloylamino-2-methylpropane-sodium sulfonate, 2- Ethylhexyl acrylate, and N- (butoxymethyl) acrylamide.
  • the sulfonate groups provide the negative charge sites in the polymer matrix.
  • the polymer compound P-005 poly (2-acryloylamino-2-methylpropane-sodium sulfonate-stat-2-ethylhexyl-acrylate-stat-mPEC-1 OOO-methacrylate-stat-N- (butoxymethyl) -acrylamide) contains, in addition to 2-acryloylamino 2-methylpropane-sodium sulfonate, 2-ethylhexyl-acrylate, and N- (butoxymethyl) -acrylamide as another monomer mPEC-1 000-methacrylate.
  • the mPEC-I OOO methacrylate monomer serves to hydrophilize the polymer layer, which can absorb water so that the negative charge sites in the matrix are more accessible.
  • Polymer compound P-008 poly (2-acryloylamino-2-methylpropane-sodium sulfonate-stat-2-ethylhexyl-acrylate-stat-2-hydroxyethyl-methacrylate-stat-N- (butoxymethyl) -acrylamide) contains the monomers 2-acryloylamino 2-methylpropane sodium sulfonate, 2-hydroxyethyl methacrylate (HEMA), 2-ethylhexyl acrylate, and N- (butoxymethyl) acrylamide.
  • HEMA serves to hydrophilize the polymer layer, which can absorb water so that the negative charge sites in the matrix are more accessible.
  • the educt solution is diluted 1: 4 with 2-propanol and water.
  • the initiator solution is used undiluted in order to maintain the reaction rate without major losses.
  • the polymer compound P-009 is prepared analogously to P-008.
  • the initiator solution is again used undiluted in order to maintain the reaction rate without major losses.
  • the polymer compound P-01 0 - poly (2-acryloylamino-2-methylpropane-sodium sulfonate-stat-2-ethylhexyl acrylate-stat-mPEC-350-methacrylate-stat-N- (butoxymethyl) -acrylamide) - is analogous to P -005, but with mPEC-350 methacrylate instead of mPEC-I OOO methacrylate, to investigate the influence of a shorter-chain mPEC monomer on permanence.
  • 2-Pro anol is additionally added to avoid phase separation of the starting material solution.
  • Prehomogenization The educt solution is homogenized homogenously for two minutes in an ultrasonic bath.
  • the polymer compound P-01 1 is prepared analogously to P-01 0, but with 1 2% N- (butoxymethyl) - acrylamide as a crosslinker instead of only 3% as before, to increase the permanence.
  • P-01 2 is poly (2-acrylamido-2-methylpropane-sodium sulfonate-stat-2-ethylhexyl-acrylate-stat-2-hydroxyethyl-methacrylate-statmPEC-350-methacrylate-stat-N- (butoxymethyl) acrylamide).
  • the composition is analogous to P-01 0, but with only 1 0% mPEC-350-methacrylate, but with 30% 2-hydroxyethyl methacrylate (HEMA). Since a solution polymerization is carried out, working without emulsifiers.
  • P-01 3 is analogous to P-01 2 poly (2-acrylamido-2-methylpropane-natri umsulfonatstat-2-ethylhexyl-acrylate-stat-2-hydroxyethyl-methacrylate statmPEC-350-methacrylate stat N- (butoxymethyl) acrylamide).
  • the crosslinker is increased to 1 2%. Again, swellability and cross-linking are examined. Compared to P-01 2, the emulsifiers are used again.
  • P-01 4 corresponds to P-01 3, but without emulsifiers.
  • Starting material solution Identical to P-01 3, without emulsifiers (Disponil AFX 1 080, sodium dodecylsulfate).
  • Initiator solution apparatus as in P-008.
  • Prehomogenization, synthesis, in-process control as in P-01 0.
  • the reaction solution is im- more viscous. The stirrer stops and it forms a very sticky gel. The reaction is stopped.
  • P-01 5 corresponds to P-01 4.
  • the educt solution is diluted with water 1: 2.
  • the initiator solution is used undiluted in order to maintain the reaction rate without major losses.
  • Synthesis educt solution such as P-01 3, without emulsifiers (Disponil AFX 1080, sodium dodecylsulfate). Initiator solution, apparatus as in P-008. Prehomogenization, synthesis, in-process control as in P-01 0. 1 5 g of homogenized educt solution is placed in the Schlenk tube and diluted 1: 2 by the addition of 1 5 g of water. With the obtained 30 g solution is analogous to P-01 0 continue. Swelling: Some dried polymer is poured over with water, causing the polymer to slowly swell and peel off. The permanence is bad, the polymer falls apart brittle.
  • P-01 6 is based on P-01 5.
  • the AMPS sodium salt is used instead of the sulfonic acid monomer. This makes it possible to dispense with the necessary neutralization of the educt solution with sodium hydroxide.
  • AM PS-Na 2403 monomer 2-acrylamido-2-methylpropane natrium msulfonate (contains approx. 50% water),
  • P-01 7 is a repeat of P-01 6 but with V-50 as the initiator and at a reaction temperature of 70 ° C.
  • V-50 2,2'-azobis (2-amidinopropane) dihydrochloride
  • V-50 is not but also has a lower half-life at a corresponding temperature, which means that the polymerization temperature can be reduced from about 90 ° C. or 80 ° C. to about 70 ° C.
  • the cationic character of V-50 does not appear to be the same negative influence on the polymerization.
  • P-01 8 to P-026 Screening with various mPEG-350 methacrylate and HEMA fractions, and with 0% crosslinker
  • the donor layer In order for the anionic charge of the polymers to be accessible to the cationic emulsion during the loading process, the donor layer must be readily swellable in an aqueous environment. Especially with washing machine application in particular a good short-term swelling capacity is important. This, like the permanence, is influenced by the degree of crosslinking.
  • the composition of the polymers according to the invention was optimized. Based on P-01 7, the polymers have the following basic composition: 30% -Cew. AMPS sodium salt, 30% Cew. 2-ethylhexyl acrylate, variable 0-40% -Cew. mPEC-350 methacrylate and 40-0% -Cew. 2-hydroxyethyl methacrylate (HEMA).
  • the polymerizations are carried out with V-50 as initiator at a reaction temperature of 70 ° C.
  • P-027 to P-035 Screening with various mPEG-350 methacrylate and HEMA moieties, as well as with 5% crosslinker Various variants of poly (2-acrylamido-2-methylpropane-sodium sulfonate-stat-2-ethylhexyl-acrylate-stat-2 ⁇ hydroxyethyl-methacrylate-stat-mPEC-350-methacrylate-stat-N- (butoxymethyl) -acrylamide) - polymer compounds with 5% crosslinkers were tested.
  • the polymers have the following basic composition: 30% -Cew. AMPS sodium salt, 5% Cew. N BMA Crosslinker, 25% Cew. 2-ethylhexyl acrylate, variable 0 to 40% -Cew. mPEC-350 methacrylate and 40 to 0% Cew. 2-hydroxyethyl methacrylate (HEMA).
  • the polymerizations are carried out with V-50 as initiator at a reaction temperature of 70 ° C.
  • the polymers have the following basic composition: 30% wt. AMPS sodium salt, 1 0% wt. N BMA crosslinker, 20% wt. 2-ethylhexyl acrylate, variable 0 to 40% by weight. mPEG-350 methacrylate and 40 to 0% wt. 2-hydroxyethyl methacrylate (HEMA).
  • V-50 as initiator at a reaction temperature of 70 ° C. reactant solution:
  • Apparatus, experimental procedure, synthesis, swelling experiments, etc. are analogous to P-01 8 to P-026.
  • the dry matter is between 1 2.2% and 14.3% for all polymers.
  • the polymers change from slightly golden brownish (P-036) to golden brownish (P-044).
  • the brittleness of the polymers changed from slightly brittle (P-036) to not brittle (P-044).
  • the stickiness of the polymers does not change from P-036 to P-044. All polymers are not sticky. With regard to the swellability of the polymers, no ambiguous tendency can be visually observed.
  • P-045 to P-053 Screening with various mPEG-350 methacrylate and HEMA moieties, as well as with 1 5% crosslinker
  • the polymers have the following basic composition: 30% wt. AMPS sodium salt, 1 5% wt. N BMA crosslinker, 1.5% wt. 2-ethylhexyl acrylate, variable 0 to 40% wt. mPEG-350 methacrylate and 40 to 0% wt. 2-hydroxyethyl methacrylate (HEMA).
  • the polymerizations are carried out with V-50 as initiator at a reaction temperature of 70 ° C.
  • the polymerization was repeated with only 1% N BMA crosslinker.
  • Preliminary tests showed that dilution (1: 2) of the educt solution with water leads to phase separation, which can not be eliminated by using 3.0% Disponil AFX 1 080 and 0.5% sodium dodecyl sulfate (SDS). Therefore, the polymerization is carried out undiluted.
  • NMA crosslinker monomer N- (methylol) -acrylamide
  • NBMA butoxymethyl) -acrylamide
  • CMA crosslinking monomer (cyclyl methacrylate) was used as a crosslinking agent instead of N- (butoxymethyl) acrylamide (N BMA) as a crosslinking agent to test the elasticity. did enhance the donor layer on swelling, which should increase the layer permanence due to decreasing stress fractions. In order to be able to assess the actual permanences, the crosslinking monomer is used equimolar with respect to NBMA (P-042).
  • p-EMKO-TDI-o-HEMA crosslinker monomer was tentatively used in place of N- (butoxymethyl) -acrylamide (NBMA).
  • p-EMKO-TDI-o-HEMA is longer chain than the crosslinkers NBMA, NMA and GMA.
  • the resulting greater distance of the polymer chains after crosslinking increases the elasticity of the donor layer when swelling.
  • the stress fractures in the polymer should decrease when swelling and thus increase the layer permanence.
  • the crosslinking monomer is used equimolar with respect to N BMA (P-042). Preliminary tests showed that gelation occurs during undiluted polymerization. To avoid this and still obtain a single-phase educt solution, this is not diluted with water but with 2-propanol 1: 2.
  • the initiator solution is used undiluted in order to maintain the reaction rate without major losses.
  • the stress fractures in the polymer should decrease when swelling and thus increase the layer permanence.
  • the crosslinking monomer is used equimolar with respect to NBMA (P-042).
  • NBMA NBMA
  • Preliminary experiments showed that the undiluted polymerization cellob tion occurs. To avoid this and still obtain a single-phase educt solution, this is not diluted with water but with 2-propanol 1: 2.
  • the initiator solution is used undiluted in order to maintain the reaction rate without major losses.
  • the protected isocyanate is deblocked only on condensation and released for the crosslinking reaction.
  • the use of a catalyst can be dispensed with in this synthesis, since amines (N- (tert-butylamino) ethyl methacrylate) are about 4000 times more nucleophilic than OH-groups (see 2nd stage in p-EMKO-TDI). o-HEMA synthesis). This generally increases the storage stability of the later, aqueous polymer dispersion, since traces of catalyst can be avoided.
  • the reaction also takes place in substance, ie solvent-free, which additionally simplifies the entire synthesis and work-up.
  • ETMA ethyltriglycol methacrylate
  • Ethyl triglycol methacrylate has the advantage over methyltriglycol methacrylate that it is commercially available in large quantities.
  • Literature source Kumakura, M., Kaetsu, I., Physical characterization and molecular structure of hydrophilic polymers obtained by radiation cast-polymerization of methoxypolyethyleneglycols, Methacrylates monomers for biomedical applications, Journal of Materials Science (18), 1, 983, 2430 to 2436.
  • Educt solution such as P-059, with 4.96 g AMPS ammonium solution instead of the AMPS lithium solution.
  • Apparatus, experimental procedure, synthesis, swelling experiments, etc. are analogous to P-054.
  • Initiator solution as in P-01 7.
  • Swelling behavior Some dried polymer is poured over with water, causing the polymer to swell and peel off within minutes. Although the polymer decomposes into rough pieces, the permanence still seems to be bad.
  • Educt solution such as P-059, with 4.96 g of AMPS triethylammonium solution instead of the AMPS lithium solution.
  • Apparatus, experimental procedure, synthesis, swelling experiments, etc. are analogous to P-054.
  • Initiator solution as in P-01 7.
  • Swelling behavior Some dried polymer is poured over with water, causing the polymer to swell and peel off within minutes. Although the polymer decomposes into rough pieces, the permanence still seems to be bad.
  • Educt solution such as P-059, with 4.96 g of AMPS-1-methylimidazolium solution instead of the AMPS lithium solution.
  • Apparatus, experimental procedure, synthesis, swelling experiments, etc. are analogous to P-054.
  • Initiator solution as in P-01 7.
  • Swelling behavior Some dried polymer is poured over with water, causing the polymer to swell and peel off within minutes. Although the polymer breaks down into coarse pieces, the permeance still seems to be poor.
  • Educt solution such as P-059, with 4.96 g AMPS-4-methylmorpholine solution instead of the AMPS lithium solution.
  • Apparatus, experimental procedure, synthesis, swelling experiments, etc. are analogous to P-054.
  • Initiator solution as in P-01. 7.
  • Swelling slightly dried polymer is poured over with water to give the polymer swells within minutes and peels off. Although the polymer decomposes into rough pieces, the permanence still seems to be bad.
  • the polymerization is repeated in place of the N BMA crosslinker with 1% N, N'-methylene-bis-acrylamide (MBAm).
  • MMBAm N, N'-methylene-bis-acrylamide
  • the polymerization is repeated with 9% N BMA crosslinker and 1% N, N'-methylene-bis-acrylamide (MBAm).
  • the aim is to investigate whether the brittleness of the polymers decreases when swelling with water, which should positively influence the washing permanence.
  • the polymerization is carried out undiluted.
  • the polymerization is carried out as compared to the experiment P-042 not as 1 2% solution polymerization, but as a 30% free radical emulsion polymerization in a 1 I Clasapparatur with V-50 as initiator at a reaction temperature of 70 ° C.
  • Disponil AFX and sodium dodecyl Benzenesulfonate added as an additional emulsifier.
  • the aim is to investigate whether P-042 can easily be prepared as a 0.5 kg scale-up by means of emulsion polymerization.
  • Initiator solution as in P-01 7.
  • Apparatus 1 l four-necked round bottom flask with stirrer, reflux condenser, septum and temperature probe. An outlet with tap on the reflux condenser serves to evacuate and aerate with nitrogen.
  • Synthesis 455 g of homogenized educt solution are initially charged in the apparatus and heated to 70 ° C. by means of a heated mushroom. When reaching about 60 ° C is evacuated three times in each case and aerated with nitrogen to remove the atmospheric oxygen (inhibitor). To ensure pressure equalization throughout the polymerization, the apparatus is back-flowed with nitrogen. Now, with good stirring by means of a syringe, 25 g of initiator solution are added through the septum. Only a slight exotherm can be detected. The reaction temperature is kept constant at 70.degree.
  • reaction mixture becomes highly viscous and then completely polymerises completely, with all the water in the batch being absorbed by the polymer formed and thus leaving behind a solid, gel-like polymer block in the reactor.
  • the 30% free radical emulsion polymerization is too concentrated.
  • Cylink NBMA monomer N- (butoxymethyl) -acrylamide, 81%, Cytec Industries
  • Synthesis 455 g of homogenized educt solution are initially charged in the apparatus and heated to 70 ° C. by means of a heated mushroom. When reaching about 60 ° C is evacuated three times in each case and aerated with nitrogen to remove the atmospheric oxygen (inhibitor). To ensure pressure equalization throughout the polymerization, the apparatus is back-flowed with nitrogen. Now, with good stirring by means of a syringe, 25 g of initiator solution are added through the septum. Only a slight exotherm can be detected. The reaction temperature is kept constant at 70.degree. After 30 minutes, the remaining 27 g of initiator solution are again added by syringe (no post-exothermic detection).
  • the educt solution is a versatile monomer system with hydrophilic and hydrophobic as well as nonionic and ionic monomers, which so far in the unstirred system after about 1 0 Minutes a phase separation occurred. This can cause problems in cross-reactor polymerization because the upper buoyant monomer phase could go through bulk polymerization. Therefore, preliminary tests were carried out with the following nonionic emulsifiers: Marlipal 01 3/30, Marlipal 01 3/50, Mulsifan RT1 10, Hostapur OS Liquid, Marlosol OL7 and Marlowet R 40. The most stable was obtained with 3-5% Marlowet R 40 Emulsion.
  • Marlowet R 40 is used as the sole emulsifier. However, this forms only a stable emulsion, when first the monomers are presented in the apparatus, Marlowet R 40 added and only at the end of water is added. If, however, first the water and then the emulsifier is added, an unstable emulsion is formed.
  • SDS sodium dodecyl sulfate
  • sodium dodecylbenzenesulfonate leads to renewed phase separation. Therefore, only Marlowet R 40 is used as the sole emulsifier. However, this forms only a stable emulsion, when first the monomers are presented in the apparatus, Marlowet R 40 added and only at the end of water is added. If, however, first the water and then the emulsifier is added, an unstable emulsion is formed.
  • the polymerization is based on P-042 Scale-up No. 2 but is carried out with only 1% V-50 as initiator (instead of 2% as in Scale-up P-042 No. 2) at a reaction temperature of 70 ° C.
  • the monomer AMPS-Na 2405 is used instead of AMPS-Na 2403 for production.
  • AMPS-Na 2405 is approved for both food and skin applications as the acrylamide and acrolynitrile levels are below 0.05%.
  • the polymerization is carried out without pre-homogenization and the basis of the recipe of P-044 (without HEMA) is used, as this showed the best results in the finishing trials.
  • the aim is to investigate whether P-044 can easily be prepared as a 0.5 kg scale-up by means of emulsion polymerization.
  • Synthesis The apparatus is charged with 97.5 g of monomers and 2.3 g of Marlowet R 40 and 5.0 g of dipropylene glycol. Then, with vigorous stirring, 375.2 g of water are slowly added dropwise, whereby the system is emulsified (white emulsion). While stirring, the monomer emulsion is heated to 70 ° C by means of a heater. When reaching about 60 ° C is evacuated three times in each case and aerated with nitrogen to remove the atmospheric oxygen (inhibitor). To ensure pressure equalization throughout the polymerization, the apparatus is back-flowed with nitrogen. N and 5 g of initiator solution are metered through the septum with good stirring by means of a syringe.
  • the polymer P-067 thus has the following basic composition: 30% -Cew. AMPS sodium salt, 20% -Cew. mPEC-350 methacrylate, 40% Cew. 2-ethylhexyl acrylate, 10% wt. N BMA crosslinker.
  • the desorption rate of the active substances can be investigated as a function of the amphiphilic character of the polymeric donor layer. If the drugs release too fast to the skin, the donor layer must be made more lipophilic, and conversely more hydrophilic if the drug desorption is too low.
  • the polymerization is carried out in a 6 l four-necked round bottom flask with V-50 as initiator at a reaction temperature of 70 ° C. Since in the emulsion polymerization of scale-up P-067 without pre-homogenization visually coarse particles could be detected in the diluted sample, this polymerization is pre-homogenized. In order to save time, however, the educt solution is only pumped three times at 600 bar through the high-pressure homogenizer. It will be investigated whether P-044 can be easily prepared as 4.5 kg scale-up by emulsion polymerization.
  • Initiator solution as in P-01 7.
  • Apparatus 6 l four-necked round bottomed flask with stirrer, reflux condenser, 250 ml feed funnel with pressure equalization and temperature sensor. An outlet with tap on the reflux condenser serves to evacuate and aerate with nitrogen.
  • a finish of 100% polyamide (PA) was used for the finish trials (Charmeuse pre-fixed, weight per unit area 1 35 g / m 2 , Fussenegger Textilveredelung GmbH, AT-6850 Dornbirn, Trikot combination: Huber Tricot GmbH, AT-6841 Gurder, Prod. No. 1 1 065).
  • the liquor mixtures consisted of 200 g polymer / kg aqueous liquor. Added to this were optionally 1 00 g of crosslinking catalyst stock solution / kg liquor.
  • Said catalyst stock solution consisted of 50 g of MgCl 2 x 6 H 2 0 / kg of stock solution and 20 g of L - (+) - tartaric acid / kg stock solution.
  • the equipment was made by padding the PA fabric with the polymer dispersion liquor (roller pressure 1 5 bar, product speed 2 m / min), followed by drying (circulating air temperature 1 00 ° C, 3 min), and condensing / fixing the equipment (circulating air temperature 1 50 ° C, 5 min).
  • Permanence of the equipment The permanence of the equipment was determined by Soxleth extraction. For this purpose, in each case two samples of textile fabric a 2.5 g were extracted with methanol for 3 hours. The results for the different equipment variants examined showed: Table: Permanence of the equipment
  • the surface charge of the finished ceweb pattern is determined by charge titration with a batch analysis system (CAS) (AFC Analytic GmbH, Leipzig, DE, model no. B390 / B422 / B490).
  • Sample preparation 0.5 g of fabric sample are ground with a 20 mm tungsten carbide grinding ball in a screw-fixable 25 ml grinding bowl made of hardened special steel at -1 96 ° C (liquid nitrogen) for 2 x 2 min at 30 Hz (Retsch MM400 ball mill).
  • A-003, A-004 Immediately after equipping the fabric samples, the analytically detectable surface charge is only 3.7 ⁇ / g goods, of theoretically possible 33 ⁇ / g goods. However, this already increases after a storage period of one week to 25 ⁇ / g goods and is essentially completely accessible after four weeks with 34 ⁇ / g goods.
  • the negative sulfonate groups of polymer P-004 promote the swellability of the finish layer. However, this should be swellable faster.
  • the permanence of the finish layer is sufficient, and as expected, the use of the catalyst for acid catalyzed fixation improves permanence.
  • A-007 Due to its fast swelling capacity, the polymer ensures immediate accessibility of the load carriers after the equipment. On the other hand, the permanence of the equipment is insufficient, which may be related to the bulky mPEG-I OOO methacrylate monomers. Hereby, through a suitable optimization with respect to the crosslinker and the fixing parameters, the permanence can be improved.
  • A-008, A-009 The surface charges are not yet fully accessible after finishing the textile product, but in A-009 the permanence is improved over A-007.
  • a finish of 100% polyamide (PA) was used for the finish trials (Charmeuse pre-fixed, basis weight 1 35 g / m 2 , Fussenegger Textilveredelung GmbH, AT-6850 Dornbirn, Trikot combination: Huber Tricot GmbH, AT-6841 Gurder, Prod. No. 1 1 065).
  • Equipment liquor The aqueous liquor consisted respectively of 1 3.2 g of polymer solution and 1 0.8 g of catalyst solution.
  • the polymer solution corresponds to the reaction solutions of the polymerization experiments, diluted with water to a polymer concentration of 1 2.0% (see Section A).
  • the reaction solution (diluted to 1 2.0% polymer content) is diluted in a bowl with stirring with catalyst solution.
  • six fabric samples (punched to 1 ⁇ 1 cm) are immersed by hand for a few minutes in each impregnation solution and pressed once in the padder (roller pressure 1 5 bar, product speed 2 m / min).
  • the liquor pick-up based on the dry weight was between 57% and 64% -Cew., Which corresponds to an order quantity of on average 4% -Cew. Polymer corresponds. This was followed by drying (circulating air temperature 1 00 ° C, 3 min), and condensation / fixing of the equipment (circulating air temperature 1 50 ° C, 5 min).
  • Persistence of the equipment To check the washing machine permanence of the equipment, in each case a finished PA fabric sample was halved and subjected to machine washing (MW). A commercial European household washing machine is filled with a laundry bag containing the finished fabric samples and a polyester and polyamide (total 2 kg) load. For the main rinse, about 1 5 g of washing powder (Perwoll wool & fine) are used. After 1 wash at 60 ° C (for underwear) for 50-55 minutes, the washed fabric samples are air dried at room temperature and stored for at least 24 hours under standard conditions (20 ⁇ 2 ° C, 65 ⁇ 5% relative humidity).
  • the polyelectrolyte consumptions of the screening series A-054 to A-059 with different crosslinkers exhibit different charge accesses in the unwashed state.
  • the polyDADMAC consumptions of the washed fabric samples (1 MW at 60 ° C for 50-55 minutes) are in the range of 1 ml of 0.001 N PolyDADMAC for all layers.
  • the polyelectrolyte consumptions of the A-060 to A-064 screening series with different AMPS counterions have consumptions of between 2 ml and 5 ml with AMPS lithium, which in the unwashed state consumes approximately 8.5 ml of 0.001 N PolyDADMAC Add 4 ml of 0.001 N PolyDADMAC. Due to the lower swellability of the donor layers, the values of relative charge permanence increase.
  • the polyDADMAC consumptions of the washed fabric samples (1 and 5 MW at 60 ° C for 50-55 min) are in the same range as the screening series A-027 to A-053, thus also found no significant improvement in the charge accessibility can be.
  • finishing formulations according to the invention were tested together with a polyurethane dispersion (Lamethan N KS-AF) in combination with an alkyl-modified melamine / formaldehyde derivative (Knittex CHN) as the binder system.
  • Lamethan N KS-AF polyurethane dispersion
  • Knittex CHN alkyl-modified melamine / formaldehyde derivative
  • Equipment Fleet A-065, A-066 as in Run Series 2.
  • Equipment Fleet A-068 The aqueous liquor consisted of 1 3.2 g polymer solution, 3.3 g Lamethane N KS-AF (48%, CHT R.
  • the polymer solution corresponds to the reaction solutions of the polymerization experiments, diluted with water to a polymer concentration of 1 2.0% (see Section A). Catalyst solution as in test series 2.
  • the polyelectrolyte consumptions of Runs A-065 to A-068 are unwashed to approximately 5 ml of 0.001 N PolyDADMAC.
  • the polyDADMAC consumption of the washed fabric sample A-065 (1 MW at 60 ° C. for 50-55 min) with N, N'-methylene-bis-acrylamide (MBAm) as crosslinker is approximately 0.4 ml 0.001 N PolyDADMAC in the Screening series A-01 8 to A-026.
  • the previous N BMA crosslinker is combined with MBAm (A-066), the polyDADMAC consumption of the washed textile increases for the first time to just under 3.5 ml 0.001 N PolyDADMAC.
  • the relative charge permanence is also good at 69%. However, this drops to 27% after 5 MW.
  • the relative charge permanence can be obtained even after five washes.
  • Equipment Fleet A-070 The aqueous liquor consisted of 1 3.2 g of polymer solution, 3.3 g of Nethane-AFA Lamethane (48%, CHT R.
  • A-071 The aqueous liquor consisted of 79.2 g of polymer solution, 7.8 g of Dicrylan PCS (7753), 1 .2 g of Phobol XAN and 55.8 g of catalyst solution.
  • A-072 The aqueous liquor consisted of 79.2 g of polymer solution, 9.9 g of lamethane NKS-AF, 1 .2 g of Phobol XAN, 53.3 g of catalyst solution, 0.4 g of p-toluenesulfonic acid monohydrate.
  • A-071 The aqueous liquor consisted of 1 3.2 g of polymer solution, 0.7 g of Dicrylan PCS (7753), 0.2 g of Phobol XAN and 9.9 g of catalyst solution.
  • A-074 The aqueous liquor consisted of 1 3.2 g of polymer solution, 0.8 g of Nethane-AF Lamethane, 0.2 g of Phobol XAN, 9.7 g of catalyst solution, 0.1 g of p-toluenesulfonic acid monohydrate.
  • A-075 The aqueous liquor consisted of 1 3.2 g of polymer solution, 0.2 g of Phobol XAN, 1 0.6 g of catalyst solution.
  • Equipment Number MW equipment overlay calculated from Relative Charge Percentage in%, nor Fleet Content before Drying /% - wt. 4% weight. Edition before MW
  • the content of lamethane NKS-AF was also obtained and, as a result, comparable to A-071 permanence. Reduction of Dicrylan PCS at A-073 to one quarter of the original amount used does not provide any significant improvement in the particular layer parameters.
  • the content of lamethane NKS-AF was also reduced to a quarter of the original amount used, and as a result, a permanence comparable to A-072 was obtained.
  • Equipment liquor The aqueous liquor consisted in each case of 1 3.2 g of polymer solution, 1 .7 g of lamethane NKS-AF, 0.2 g of Phobol XAN, 8.8 g of catalyst solution, 0.1 g of p-toluenesulfonic acid monohydrate. Table: Relative charge permanence
  • A-077 is thus the best equipment formulation so far, as it has a high swelling capacity as well as a high relative charge permanence.
  • A-078 also based on A-072, the content of the incorporated in the polymer N BMA crosslinker was reduced to 5%, whereby, however, the permanence against A-072 particularly reduced to 25 and 50 MW.
  • the polymer P-024 contains no N BMA, but like P-042 1 0% HEMA, with which the oximblock Arthur polyisocyanate Phobol XAN can also crosslink and the permanence should thus be guaranteed.
  • Equipment liquor The aqueous liquor consisted in each case of 1 3.2 g of polymer solution, 1 .7 g of Lamethane N KS-AF, and 0.2 g (A-080), 0.1 g (A-081), 0.0 g (A-082), 0.7 g (A-083) Phobol XAN, 8.7 g (A-080), 8.9 g (A-081), 9.0 g (A-082), 8.3 g (A-083) catalyst solution, 0.1 g of p-toluenesulfonic acid monohydrate. Table: Relative charge permanence
  • Catalyst stock solution 1 25 g of magnesium chloride x 6 H 2 O,> 98.0%, Fluka; 50 g of L - (+) - tartaric acid> 99.5%, Fl uka; 2325 g of water (deionized).
  • Tissue impregnation batch 1 320 g Scale-up P-044 No. 2 Reaction solution; 21.0 g Lamethane NKS-AF, CHT R. Beitlich GmbH, 1 l 70 g water (not deionized); 300 g of catalyst stock solution. The catalyst is added just before padding.
  • the average swatches of the swatches are 55% for PA (A-084), 72% for PES (A-085), 52% for PES / PUE (A-086) and 83% for CO (A -087).
  • different runs are achieved, namely about 3.7% polymer on the PA fabrics, about 4.8% polymer overlay on the PES fabric, about 3.5% polymer overlay on the PES / PUE fabric, and about 5.6% polymer overlay the CO tissue.
  • the production trial A-084 has both excellent charge accessibility and relative charge permanence, allowing for high drug loading capacity.
  • Polyelectrolyte consumption for the unwashed swatches is 7 ml 0.001 N PolyDADMAC.
  • the PolyDADMAC consumption of the washed fabric sample (1 MW at 60 ° C for 50-55 min) is 5.5 ml 0.001 N PolyDADMAC.
  • the 5, 25, 50, and 100 MW consumptions increase to almost 8 ml of 0.001 N PolyDADMAC, which is sometimes caused by the washing out of uncrosslinked polymer moieties.
  • the relative charge permanence increases to more than 1 00%.
  • Production trial A-085 is also 10000 times washable. However, due to the lack of anchor groups of the polyester, significantly less donor layer can be deposited, as evidenced by polyelectrolyte consumption of the washed fabric samples in the range of 2 ml of 0.001 N PolyDADMAC. The relative charge permanence is around 45%. The production trial A-086 is also over 100 times wash resistant. Polyelectrolyte consumption for the unwashed swatches (1, 5 and 25 MW at 60 ° C for 50-55 min) is 4 ml of 0.001 N PolyDADMAC. Thereafter, after 50 and 1 00 MW, the PolyDADMAC consumptions increase to 5 ml and 7 ml, respectively.
  • the elasticity of the donor layer increases over time, which also increases the analytically detectable surface charge.
  • the production test A-087 is more than 100 times washable.
  • the charge accessibility increases here as the number of source cycles increases.
  • the PolyDADMAC consumption with 1 1 .4 ml reaches the maximum, theoretically possible consumption of 1 1 .6 ml 0.001 N PolyDADMAC.
  • the relative charge permanence of 1 74% after 1 00 MW for CO corresponds to the absolute layer permanence since nothing is lost from the donor layer during washing.
  • Washing machine permanence Same as in test series 2.
  • Charge titration Sample preparation and charge titration with Charge Analyzing System (CAS) as in test series 1 and 2.
  • CAS Charge Analyzing System
  • the average liquor pick-up of the fabric samples is in the range of 49%, resulting in a circulation of about 3.4% polymer on the PA fabrics.
  • Production trial A-088, like A-084, has excellent charge accessibility. Due to the lipophilic nature of the amphiphilic donor layer, the polyelectrolyte consumptions of the washed fabric samples (1, 5, 25, 50 and 100 MW at 60 ° C for 50-55 minutes) are somewhat lower than A-084 with approximately 6 ml 0.001 N PolyDADMAC , The relative charge permanence is in the range of 70%.
  • tissue sample was subjected to a cytotoxicity test in accordance with DI N EN ISO 1 0993-5 ("Biological Evaluation of Medical Devices - Part 5: Tests for In Vitro Cytotoxicity")
  • DI N EN ISO 1 0993-5 Biological Evaluation of Medical Devices - Part 5: Tests for In Vitro Cytotoxicity
  • the tissue sample was previously washed once (60 ° C for 50-55 min.)
  • the fabric was not with any emulsion (s) loaded.
  • the cytotoxicity test according to DIN EN ISO 1 0993-5 is recognized and required as the basis for all medical devices.
  • the use of cell cultures makes it possible to detect toxic substances that can be released from the tested products.
  • the release of toxic substances from a textile product with skin contact is a prerequisite for the development of a skin irritation.
  • the cytotoxicity test allows the assessment of a hazard potential for skin irritation. This is recorded as a sum parameter.
  • Cell line L 929 cells (ATCC No. CCL1, NCTC clone 929 L (DSMZ)), Passenger count: 31.
  • Culture medium DMEM with 10% FCS.
  • Extraction method Incubation of the sample with acidic Welding solution according to standard DI N EN ISO 1 05-E04 for 24 h with gentle shaking at 37 ° C; The welding solution is adjusted to pH 7.3-7.4 and filtered steri ll. Incubation of cell culture: 68-72 h with sweat solution in dilution steps of 33, 3% to 9, 9%. Examination of cytotoxicity: After incubation of the cells, the protein content is compared with that of the controls as a measure of cell growth (Biol.
  • Toxicol. 1 984, 1 (1), 55-65.
  • a positive and a negative control are included in the experiment to confirm the validity of the test system.
  • In the presence of cytotoxic substances, altered proliferation and division rates of the cells are shown (growth inhibition test).
  • Test material Concentrations of the test material in culture medium: 9.9%, 14.8%, 22.2% and 33.3%.
  • a growth inhibition of more than 30% is considered to be a cytotoxic effect compared to the solvent control.
  • the sweat extract of the sample showed a growth inhibition of 1 8% in the cytotoxicity test.
  • a dose-dependent growth inhibition of L929 cells was observed, but the significance limit of 30% was not exceeded.
  • the sample shows no biological activity. From this it can be concluded that under the specified conditions no cytotoxic substances are released from the examination material, which can cause irritations on contact with the skin.
  • an emulsifier which has corresponding positive charges. This results in active ingredient emulsions containing active-ingredient-containing oil phase droplets which, due to the positive surface charge present, deposit well into the matrix of the finishing layer of the invention provided with negative charge sites.
  • the active ingredient after loading the finishing layer with the emulsion, can diffuse from the emulsified oil droplets into the lipophilic areas of the polymer matrix. From the oil phase of the adsorbed emulsion particles and / or the lipophilic phases of the polymer matrix, the active ingredient can subsequently be dispensed.
  • phosphatidylcholine lecithins for example 1-palmityl-2-oleyl-sn-glycero-3-phosphatidylcholine (POPC, palmityloleylphosphatidylcholine).
  • POPC palmityloleylphosphatidylcholine
  • Lecithin-containing oil / water microemulsions are known.
  • a macroemulsion is converted by high-pressure homogenization into a microemulsion or miniemulsion.
  • microemulsions for example, behenyltrimethylammonium methosulfate:
  • ethyl-N al ha -Lauroyl-L-arginate / HCl has been found (hereinafter Lauroylarginat).
  • Lauroyl arginate is a white, hygroscopic solid which is water dispersible up to 247 g / kg. The melting point is 50 ° C to 58 ° C.
  • Lauroylarginate is used as an antimicrobial preservative, its antimicrobial properties being based on its properties as a cationic surfactant. Lauroylarginate is effective against a wide range of Gram-negative and -positive bacteria as well as yeasts and molds. It suppresses the growth of bacterial colonies but does not lysine cells.
  • WO 02/087328 A2 discloses the use of lauroylarginate in combination with sorbic acid, quinisor sorbate or sodium sorbate.
  • WO 2008/014824 AI postulates the antiviral activity of lauroylarginate.
  • WO 2007/01 4580 A1 discloses other similar antimicrobial surfactants. The disclosure of the aforementioned documents is hereby incorporated as part of this description.
  • lauroyl arginate As an emulsifier.
  • the use of lauroylarginate for this purpose has, on the one hand, the advantage that no further preservatives are necessary for a corresponding emulsion. On the other hand, at the same time the health safety of such an emulsion is given.
  • evening primrose oil is used as an example of a carrier medium or active substance, with which a finishing layer according to the invention can be loaded.
  • the seeds of the common evening primrose (Oenothera biennis) contain about 7-1 0% wt. Linolenic acid.
  • the corresponding oil of the evening primrose for example, relieves pain in premenstrual syndrome, and has a healing effect on skin diseases such as psoriasis (psoriasis) and atopic dermatitis.
  • Evening primrose oil consists of 71% -gew. Linoleic acid, 10% wt. gamma-linolenic acid, 7% wt. Oleic acid, 2% wt. Stearic acid, 7% wt. Palmitic acid and 3% wt. other substances.
  • the active ingredient is gamma-linolenic acid.
  • lipophilic media for example based on paraffin or paraffin oil
  • hydrophilic active substances can be loaded in the interior of water-in-oil-in-water emulsions or liposomes onto finishing layers according to the invention.
  • WO 2007/050580 A2 and US 5474783 disclose a number of active compounds which are suitable for transdermal uptake. The disclosure of these references forms an integral part of this specification.
  • adjuvants can also be provided which, for example, improve the absorption of the active substance into the skin (so-called “penetration enhancers") or contain, for example, osmophoric or chromophoric groups which take into account the sensory consumer needs as fragrances or dyes wear.
  • all substances which are suitable e.g. prevent the emulsion from freezing or generally provide emulsion stability over a wide temperature range and period of time by increasing both the chemical and physical and biological stability thereof.
  • the emulsion may contain bittering agents to prevent uncontrolled ingestion by children.
  • Preparation 50.0 g of evening primrose oil are placed in a 250 ml Erlenmeyer flask. Then, with stirring, 4.0 g of lecithin are added. The mixture is stirred on the magnetic stirrer, and after the lecithin is evenly swollen, slowly add 1 3.0 g of propylene glycol and 1 33.0 g of water are added dropwise with vigorous stirring and stirred for 3 h (difficult to mix). Determination of homogeneity: 1 g of emulsion solution is diluted with 1 9 g of water (1:20).
  • Viscosity 1 .04 mPa ⁇ s (All viscosity measurements: viscometer CBC Materials Co., Ldt, Tokyo, Japan. Model: Visco Mate VM-1 0A-L, probe: PR-1 0-L).
  • Preparation 50.0 g of evening primrose oil are placed in a 250 ml Erlenmeyer flask. Then 4.0 g Lipoid S 40 (Lipoid GmbH) are added with stirring. The mixture is stirred on the magnetic stirrer and after the lecithin is evenly swollen, slowly add 1 3.0 g of propylene glycol and 1 33.0 g of water are added dropwise with vigorous stirring and further stirred for 2 h (easy to mix). This results in 200 g of low-viscosity, white-yellowish emulsion. Determination of homogeneity: 1 g of emulsion solution is diluted with 1 9 g of water (1:20).
  • Viscosity 1 .03 mPa ⁇ s.
  • Emulsion E-020 Emulsion E-020
  • Preparation 50.0 g of evening primrose oil are placed in a 250 ml Erlenmeyer flask. 6.7 g of Phosal 50 PC (Phospholipid GmbH) are then added with stirring. The mixture is slowly added dropwise with vigorous stirring on the magnetic stirrer 1 0.3 g of propylene glycol and 1 33.0 g of water and stirred for 2 h (contains oil drops). Determination of homogeneity: 1 g of emulsion solution is diluted with 1 9 g of water (1:20). Viscosity: 0.98 mPa ⁇ s.
  • Emulsion E-021 Preparation 25.0 g of evening primrose oil are placed in a 250 ml Erlenmeyer flask. Then 2.0 g of Varisoft BTMS Flake are added with stirring. The mixture is heated in an oil bath to 75 ° C and stirred for 2 h. The result is a viscous, white mixture. In a second 250 ml Erlenmeyer flask 66.5 g of water are introduced and added 6.5 g of propylene glycol. The mixture is heated to 60 ° C and then added dropwise with vigorous stirring in the warm oil phase (27 g). While stirring, the emulsion solution is allowed to cool to room temperature.
  • Preparation 25.0 g of evening primrose oil are placed in a 250 ml Erlenmeyer flask. Then 2.0 g of Varisoft BTMS Flake are added with stirring. The mixture is heated in an oil bath to 75 ° C and stirred for 2 h. Add 1 .5 g of lecithin and continue stirring for 1 0 min. The result is a viscous, white-yellow mixture. In a second 250 ml Erlenmeyer flask 65.0 g of water are introduced and added 6.5 g of propylene glycol. The mixture is heated to 60 ° C and then added dropwise with vigorous stirring in the warm oil phase (28.5 g). While stirring, the emulsion solution is allowed to cool to room temperature.
  • lecithin reduces, as expected, the surface charge of emulsion drops compared to E-021.
  • the particle size distribution gives a monodisperse emulsion drop size with a hydrodynamic diameter of 755 nm. This means that both the lecithin and the behenyltrimethylammonium methosulfate are incorporated in the same emulsion droplets.
  • the lecithin emulsion is mixed with a calcium chloride solution to check whether the phosphate groups of two lecithin molecules with CaCl 2 form the sparingly soluble calcium phosphate.
  • the released chloride ions are then available to the trialkylammonium groups of lecithin as cegenions.
  • the lecithin emulsion should receive a cationic surface charge.
  • M ammonium
  • 4.0 g of lecithin correspond to 5.3 mmol. This means that half as much calcium chloride has to be used to screen off the entire phosphate groups of the lecithin used. As a result, a salt excess is also avoided, which would destabilize the emulsion.
  • Preparation 50.0 g of evening primrose oil are placed in a 250 ml Erlenmeyer flask. Then, with stirring, 4.0 g of lecithin are added. The mixture is stirred on the magnetic stirrer, and after the lecithin is evenly swollen, slowly add 1 3.0 g of propylene glycol and 1 33.0 g of calcium chloride solution (0.3 g of CaCl 2 in 1 of 32.7 g of water) while stirring vigorously for 4 h further stirred. It forms a low-viscosity, white-yellowish, two-phase mixture. Upon standing, an upper, white-yellowish suspension phase immediately forms and a lower, clear, aqueous phase immediately forms.
  • the electrolyte addition in E-01 8 and E-023 caused in the region of the zero charge point an unstable emulsion, causing them breaks.
  • the lecithin is converted in the nonaqueous system. charged to then produce the emulsion with the then cationic emulsifier.
  • the charge zero point of the emulsion solution does not have to be passed through, since the emulsion is only subsequently produced with the already cationic lecithin.
  • the lecithin is transhipped by means of an aluminum chloride-cosolvent solution and a coemulsifier suitable for emulsion stabilization in the nonaqueous system in order to prepare the emulsion with the cationic lecithin.
  • lecithin molecular weight of M approx. 760 g / mol
  • 4.0 g of lecithin correspond to 5.3 mmol. That One-third of aluminum chloride must be used to shield the entire phosphate groups of the lecithin used. As a result, a salt excess is avoided, which would destabilize the emulsion.
  • lecithin oil phase 400 g of evening primrose oil are placed in a 250 ml Erlenmeyer flask. Then, with stirring, 32 g of lecithin are added. The mixture is stirred on the magnetic stirrer until the lecithin is evenly swollen. This gives 432 g of yellow lecithin oil phase.
  • Aluminum chloride in ethylene glycol 54 g of lecithin oil phase are introduced into a 250 ml Erlenmeyer flask and then, while stirring vigorously, 1 7.0 g of aluminum chloride cosolvent co-emulsifier solution (0.29 g of aluminum chloride in 1.7 g of ethylene glycol and 4 g of Marlipal 01 3 / 30) drops. Again, with vigorous stirring, 1 29 g of water (including 400 ⁇ 37% formaldehyde solution for preservation) are slowly added dropwise and stirring is continued for 4 h. This results in 200 g of white-yellowish mixture (no phase separation).
  • pH Titration with Charge Analyzing System For the CAS-pH-titration 0.1 N HCl titration solution was used. For the preparation, ie cleaning of the PTFE measuring cell of the CAS, it is rinsed in sequence with deionized water, 2-propanol, deionized water and acetone (spray bottles) before each measurement and then blown out with compressed air. From time to time, the PTFE measuring cell is additionally cleaned with 65% nitric acid. 1 .0 g of emulsion solution is weighed into the PTFE measuring cell of the CAS and filled up with 9.0 g of water (dilution 1: 1 0). Then the volumetric flask is inserted into the measuring cell and the CAS pH titration is started at the CAS. Table: Surface charge
  • the maximum conductivity of the 1: 1 0 diluted samples is 590 S / cm for E-026-C (2.0 eq AICI 3 ). Furthermore, CAS-pH-titrations with different diluted samples were carried out. So remains E-026-C with 2.0 eq. AICI 3 undiluted, 1: 1 0 and 1: 50 diluted always cationic.
  • LAE lauroyl L-arginine ethyl ester monohydrochloride
  • N a lauroyl-L-arginine ethyl ester monohydrochloride (LAE) in maltodextrin shows as a cationic emulsifier, instead of Behenyltrimethylammoni to methosulfate, that a low-viscosity, white-gelbl cozy, stable emulsion can be produced.
  • the particle size distribution gives a monodisperse emulsion droplet size with a hydrodynamic diameter of 228 nm.
  • the CAS-pH titrations show that the flow potential of the emulsion is always greater than +343 mV over the entire pH range of 3.0 to 1.0.
  • N a -Lauroyl-L-arginine ethyl ester monohydrochloride (LAE) in glycerol as a cationic emulsifier.
  • This solution is available as Aminat-G of the Vedeq SA and containing 20% N a lauroyl-L-arginine ethyl ester monohydrochloride (LAE) in 80% glycerol.
  • Cationic emulsifier which, however, does not mix properly with the oil.
  • Homogenization This emulsion solution is pumped five times at 600 bar through the high-pressure homogenizer. This results in 1 50 g of low viscosity, white-yellowish emulsion.
  • LAE in clycerin as a cationic emulsifier instead of LAE in maltodextrin shows that a thin, white-yellowish emulsion can also be produced. However, the emulsion thickens after a few days and forms lumps. By shaking the emulsion but can liquefied again. The particle size distribution gives a monodisperse emulsion droplet size with a hydrodynamic diameter of 248 nm. The CAS-pH titrations show that the flow potential of the emulsion is always greater than +386 mV over the entire pH range of 3.0 to 1.0.
  • the result is a low-viscosity, white-yellow, stable emulsion.
  • the particle size distribution gives a monodisperse emulsion droplet size with a hydrodynamic diameter of 233 nm.
  • pH titrations show that the flow potential of the emulsion over the entire pH range of 3.0 to 1 0.0 is always greater than +306 mV.
  • Emulsion E-031 Kilo batch of cationic emulsion with LAE / glycerol, lecithin and ß-carotene as pseudo-active substance
  • the particle size distribution gives emulsion droplets with hydrodynamic diameters of 82 nm (4.9% v / v) and 631 nm (95.1% v / v).
  • LAE inin-ethyl ester monohydrochloride
  • Emulsion E-032 Kilo batch of cationic emulsion with LAE / glycerol, lecithin and ß-carotene as pseudo-active substance Based on recipe E-031, but with 0.8% LAE as a cationic emulsifier rather than just 0.4%. 0.8% is the maximum allowable concentration of LAE in soaps and anti-dandruff shampoos (does not apply to products used as a spray).
  • the emulsion thus has no isoelectric point in this pH range. 0.8% N a lauroyl-L-arginine ethyl ester monohydrochloride (LAE) as a cationic emulsifier thus is sufficient to provide the lecithin emulsion over the pH range mentioned cationic.
  • LAE lauroyl-L-arginine ethyl ester monohydrochloride
  • This cationic emulsion is used to load the finished textiles for sorption and desorption studies.
  • This cationic emulsion is used to load the finished textiles for sorption and desorption studies.
  • the production of the active ingredient-free emulsion proceeded successfully, it was possible to produce a low-viscosity, white-yellowish emulsion.
  • the particle size distribution gives a monodisperse emulsion droplet size with a hydrodynamic diameter of 303 nm.
  • the surface charge of the cationic emulsion is 1 2.1 2 mol pos. Charge / g emulsion.
  • the pH Titrations show that the flow potential of the emulsion over the entire pH range of 3.0 to 1 0.0 is always greater than +1 98 mV.
  • 0.2 g of emulsion E-021 are diluted in 6 ml of water and sprayed completely onto 4.4 g of finished fabric sample A-007 (with mPEC-1 000-methacrylate). The sample is extracted after complete drying and methylated. GC analysis gives 423.6 ⁇ g of methyl palmitate / gm of product, which corresponds to 6 mg of evening primrose oil / gm of product.
  • Sorption test 39.2 g of water are introduced into a 1 00 ml Schott bottle and 0.8 g of cationic BTMS emulsion E-021 are added. Subsequently, a 4.0 g fabric sample A-009 placed in the bottle, shaken and allowed to stand for 1 6 h at RT. Thereafter, the fabric sample is dried for 1 h at 50 ° C in a drying oven. Optically, a take off is detectable.
  • emulsion E-021 0.4 g of emulsion E-021 are diluted in 40 ml of water. 4.0 g of finished cloth sample A-009 (with HEMA) are dipped and shaken. The active ingredient emulsion immediately dries on the tissue.
  • E-033 (LAE emulsion) on A-084 (equipment with P-044, with 40% mPEG-350 methacrylate and 20% 2-ethylhexyl acrylate) and on A-088 (equipment with P-067, with 20% mPEG-350 methacrylate and 40% 2-ethylhexyl acrylate) for 30 min to determine loading capacity (sorption capacity).
  • the amounts of skin care products applied to the skin are in the Dermatolo- typically at 2 mg / cm with an active ingredient content between 1 -3% and a contact time of normally 1 6 hours. This is taken into account in the subsequent sorption experiments.
  • A-084 Anionic PA fabric with poly (2-acrylamido-2-methylpropane-sodium sulfonate-stat-2-ethylhexyl-acrylate-stat-N- (butoxymethyl) -acrylamide) with P-044 after machine wash at 60 ° C for 50-55 min.
  • A-088 Anionic PA fabric with poly (2-acrylamido-2-methylpropane-sodium sulfonate-stat-2-ethylhexyl-acrylate-stat-N- (butoxymethyl) -acrylamide) with P-067 after machine wash at 60 ° C during 50-55 min.
  • the finished PA fabric samples after being machine-washed at 60 ° C for 50-55 minutes, are cut to a weight of 5.0 g each (about 20x20 cm).
  • metal bombs are presented in each case 71.O g of water and in each case 4.0 g of cationic LAE emulsion E-033 was added.
  • the fabric samples together with the liquor are centrifuged separately in the spin dryer previously cleaned with spray cleaners, sponge, washcloths and water at 2800 rpm for exactly 1 minute and finally dried in air at RT.
  • the blank value is made in the same way.

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Abstract

L'invention concerne un composé polymère contenant un copolymère d'acide acrylique composé de dérivés d'acide acrylique et de dérivés d'acide méthacrylique. Le copolymère d'acide acrylique contient a) au moins un dérivé d'acide acrylique et/ou un dérivé d'acide méthacrylique substitué avec un groupe d'acide sulfonique; b) au moins un dérivé d'acide acrylique et/ou un dérivé d'acide méthacrylique à substitution hydrophile; c) au moins un dérivé d'acide acrylique et/ou un dérivé d'acide méthacrylique à substitution lipophile; et d) au moins un dérivé d'acide acrylique et/ou un dérivé d'acide méthacrylique agissant comme réticulant. Le procédé de chargement de produits textiles avec un composé de faible poids moléculaire consiste a) à pourvoir un produit textile d'une couche d'apprêt dont la surface accessible présente une charge négative, et b) à mettre le produit textile en contact avec une émulsion ou une solution d'agent actif par exemple par immersion du produit textile dans l'émulsion/solution ou par pulvérisation de l'émulsion/solution sur le produit textile, au moins un composé de faible poids moléculaire étant contenu dans la phase dispersée de l'émulsion, et la surface des particules de la phase dispersée présentant une charge positive.
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ES2531578T3 (es) 2015-03-17
BR112012005118A2 (pt) 2016-05-03
JP2013503985A (ja) 2013-02-04
CH701769A1 (de) 2011-03-15
WO2011029723A2 (fr) 2011-03-17
EP2481762A1 (fr) 2012-08-01
DK2481762T3 (en) 2015-03-09
KR20120091018A (ko) 2012-08-17
WO2011029723A3 (fr) 2011-07-21
CN102575416A (zh) 2012-07-11
JP5938811B2 (ja) 2016-06-22
JP2015132042A (ja) 2015-07-23
EP2481762B1 (fr) 2014-12-31
CN102575416B (zh) 2014-03-12
US20130102943A1 (en) 2013-04-25
CA2772707A1 (fr) 2011-03-17
PT2481762E (pt) 2015-02-18
HK1169664A1 (en) 2013-02-01

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