EP0169935A2 - Impregnating spray for leather and textiles and use thereof - Google Patents

Impregnating spray for leather and textiles and use thereof Download PDF

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Publication number
EP0169935A2
EP0169935A2 EP84113475A EP84113475A EP0169935A2 EP 0169935 A2 EP0169935 A2 EP 0169935A2 EP 84113475 A EP84113475 A EP 84113475A EP 84113475 A EP84113475 A EP 84113475A EP 0169935 A2 EP0169935 A2 EP 0169935A2
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EP
European Patent Office
Prior art keywords
water
impregnation
leather
active ingredient
solvent
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EP84113475A
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German (de)
French (fr)
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EP0169935B1 (en
EP0169935A3 (en
Inventor
Hans-Joachim Dr. Peter
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Werner and Mertz GmbH
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Werner and Mertz GmbH
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Priority to AT84113475T priority Critical patent/ATE45374T1/en
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C14—SKINS; HIDES; PELTS; LEATHER
    • C14C—CHEMICAL TREATMENT OF HIDES, SKINS OR LEATHER, e.g. TANNING, IMPREGNATING, FINISHING; APPARATUS THEREFOR; COMPOSITIONS FOR TANNING
    • C14C9/00—Impregnating leather for preserving, waterproofing, making resistant to heat or similar purposes
    • 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
    • D06M15/277—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acids; Salts or esters thereof containing fluorine
    • 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
    • D06M15/295—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds of unsaturated carboxylic acid amides or imides containing fluorine
    • 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
    • D06M23/06—Processes in which the treating agent is dispersed in a gas, e.g. aerosols

Definitions

  • suede also called suede, suede, nubuck leather
  • impregnation agent only spray articles (aerosols) are available to the end consumer, by means of which impregnation substances and care products can be applied sparingly, evenly and effortlessly to the surface of the leather articles.
  • This application is superior to all other dosage forms offered (e.g. applying impregnation substances in dissolved, liquid form via pump spraying, direct distribution of the liquid from a bottle via a dispenser made of sponge felt or other material).
  • the propellant or propellant mixture is responsible for the application and fine atomization of the actual active ingredient.
  • This active ingredient consists of water repellents such as silicones, fluorocarbon resins, metal soaps, certain complex compounds, waxes - individually or in mixtures - which are dissolved or finely dispersed in solvents such as white spirit, chlorinated hydrocarbons, alcohols, esters, ketones, aromatics.
  • solvents such as white spirit, chlorinated hydrocarbons, alcohols, esters, ketones, aromatics.
  • Liquefied, water-immiscible gases such as chlorofluorocarbons (PFCs), propane, butanes, are used as blowing agents. Compressed gases such as carbon dioxide and nitrous oxide are also used.
  • PFCs chlorofluorocarbons
  • propane propane
  • propane propane
  • Compressed gases such as carbon dioxide and nitrous oxide are also used.
  • the active ingredient and blowing agent phases should result in a homogeneous mixture.
  • the task was to design aerosol impregnating agents for the end user with comparable hydrophobing performance without disadvantageous physiological side effects.
  • hydrophobic substances known per se based on perfluorinated carbon resins which can be diluted with water alone or with water / alcohol mixtures, as aerosol with propellants, such as e.g. Dimethyl ether (DME), can be filled and sprayed. They are suitable for the hydrophobizing of water-sensitive leather without causing physiological damage to the respiratory tract when the spray is inhaled. Health impairments are not to be feared with the composition according to the invention, as studies on inhalation toxicology have shown.
  • a water-miscible blowing agent (B) present according to the invention is preferably a liquefied blowing agent, such as e.g. Dimethyl ether (DME). If this blowing agent (DME) is present in combination with a solvent system (LA) made of water and / or a water-miscible alcohol, in particular ethanol or isopropanol, then a binary or ternary system of DNE, water and / / or alcohol from within the known quantity ranges in the form of a uniform phase
  • a solvent system LA
  • a binary or ternary system of DNE water and / / or alcohol from within the known quantity ranges in the form of a uniform phase
  • a liquefied (water-immiscible but) emulsifiable blowing agent such as e.g. Propane, butane or difluorodichloromethane.
  • blowing agents may also be present as blowing agents (B), e.g. Carbon dioxide; nitrogen and nitrous oxide are further examples of compressed blowing agents.
  • the fluorocarbon resins present in the active ingredient (A) are the usual ones, as are offered by several companies for the hydrophobic finishing of leather and textiles.
  • hydrophobic fluorocarbon resins which can be diluted with water and / or alcohols, in particular those which contain solutions or emulsions which are stable over a long period of time or
  • FC 208 (approx. 30%); FC 214 (20%); FC 228 (27%); FC 229 (20%); FC 390 (10%); FC 453 (20%); FC 461 (30%); Foraperle C 305 (25%); Foraperle P 300 (17%); Foraperle T 140 (30%); Foraperle T 145 (25%); Foraperle T 355 (30%); Foraperle T 344 (31%); Foraperle 1190 (28%); Foraperle T430;
  • Xeroderm DH 471763 (100%); Nuva F (approx. 20%); Nuva FH (approx. 25%).
  • FC 228 and Foraperle P 300 and C 305 are particularly preferred among these products.
  • the solvent or diluent (LA) present according to the invention is selected from the group: water, preferably deionized water; one with water solvent (LW); and mixtures of water with (LW).
  • Solvents (LW), alone or in a mixture with water, have proven to be water-miscible alcohols, in particular mono- or polyhydric aliphatic alcohols; these are preferably C 1 -C 6 alcohols, such as ethanol, n-propanol, isopropanol, butanol; also glycols, such as ethylene glycol, but also water-miscible ketones are suitable as solvents (LW), such as acetone.
  • the resulting dilute solution of fluorocarbon resin in the solvent (LA), i.e. the active ingredient (A) with the propellant (B), e.g. Dimethyl ether, clear or finely dispersible can be mixed in pressure-resistant containers.
  • a solvent (LA) consisting of the combination of water / alcohol has proven to be particularly suitable here. But also alcohol alone (e.g. in combination with the blowing agents DME, propane or butane) or water alone have proven themselves as solvents (LA) (see also the explanations above for avoiding the known mixture gap of DME / water).
  • the active substances (A) may also contain the auxiliaries customary in sprays of this type.
  • auxiliaries are common anti-corrosion agents (corrosion inhibitors) for tinplate and aluminum cans.
  • corrosion inhibitors common anti-corrosion agents
  • the following are just a few examples: sodium benzoate; Disodium hydrogen phosphate; Vircopet 20, 30 and 40; Deriphat 151 C, Rewo B 3010; Sarcosyl NL 97; Dehyquart SP.
  • fragrances of the type customary in this field are also to be mentioned, such as perfume oils which are resistant to water, solvents and propellants, in particular DME.
  • the active ingredient (A) advantageously has the following composition, the amount of the components in each case being given in percent by weight, based on the active ingredient formulation:
  • the amount of active ingredient (A) in the impregnating spray according to the invention can vary depending on its type and the type of blowing agent present. In general, there are 35 to 65% by weight of active ingredient (A) (based on the finished filling formulation). An amount of active ingredient of 40 to 60% by weight has proven particularly useful.
  • the amount of blowing agent (B) according to the invention can also vary. It is usually 30 to 70% by weight, preferably 35 to 55% by weight of liquefied propellant and 0 to 7% by weight, preferably 0 to 5% by weight of compressed propellant.
  • the impregnating spray according to the invention is applied in the same way as in the known aerosol impregnating agents to the surfaces of leather to be treated, e.g. Shoes, leather clothing, leather furniture, etc., or of textiles, e.g. Clothing, tents, tarpaulins, umbrellas etc. Paper surfaces intended for impregnation can also be treated according to the invention.
  • composition according to the invention showed no acutely toxic effect in the test animals, even at very high concentrations (up to 44 g / m 3 ). No mortality was found at this exposure; LC 50 values could not be determined.
  • the numerical data given represent percentages by weight, based on the active ingredient formulation or on the filling formulation.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Textile Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Dispersion Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Treatment And Processing Of Natural Fur Or Leather (AREA)
  • Medicinal Preparation (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)
  • Cosmetics (AREA)

Abstract

1. Impregnating spray for leather and textiles based on (A) an active substance consisting of fluorocarbon resins, a solvent and optionally adjuvants and (B) one or more propellants which are miscible or emulsifiable with water, characterised in that the solvent (in the active substance A) is only ethanol, n-propanol and/or isopropanol.

Description

Technischer HintergrundTechnical background

Moderne Schuhe haben einen hohen Standard im Hinblick auf Tragekomfort und Paßform. Beim größten Teil der heute erhältlichen Schuhe entfällt das früher übliche "Eingehen", d.h. das langsame Anpassen der relativ harten Leder an die individuelle Fußform mit all seinen lästigen Beschwerden. Drückende Schuhe, schmerzende Füße beim Tragen neuer Schuhe gehören weitgehend der Vergangenheit an.Modern shoes have a high standard in terms of comfort and fit. Most of the shoes available today do not have the usual "shrink", i.e. the slow adjustment of the relatively hard leather to the individual foot shape with all its annoying complaints. Squeezing shoes, aching feet when wearing new shoes are largely a thing of the past.

Erreicht wurde dieser Fortschritt u.a. durch Verarbeitung weicher, flexibler und dehnfähiger Glattledersorten, die schnell anpassungsfähig sind und kaum Druck- und Scheuerstellen am Fuß verursachen. Dieser Vorteil ging jedoch zu Lasten einer anderen wichtigen Ledereigenschaft, der Wasserfestigkeit. Durch Einarbeitung von weichmachenden Substanzen, wie emulgierte Fette (Fettlicker), in die Leder wurde die Hydrophobierung zum Teil bedeutend verschlechtert. Um den Erfordernissen beim täglichen Gebrauch dieses so zugerichteten Schuhwerks Rechnung zu tragen, ist es dringend geboten, diese Schuhe vor dem ersten Gebrauch und auch zwischendurch während des Tragens zusätzlich zu imprägnieren. Die Behandlung mit üblichen Pflegemitteln bleibt unberührt.This progress has been achieved by processing soft, flexible and stretchable smooth leather types that are quickly adaptable and hardly cause pressure and abrasion points on the foot. However, this advantage was at the expense of another important leather property, water resistance. The incorporation of softening substances, such as emulsified fats (fat licker), into the leather made the water repellency in some cases significantly worse. In order to take into account the requirements for the daily use of this type of footwear, it is imperative to additionally impregnate these shoes before they are used for the first time and also in between. Treatment with usual care products remains unaffected.

Sinngemäß gilt das für Schuhe ausgeführte auch für Lederbekleidung.The same applies to shoes as to leather clothing.

Weiterhin ist es notwendig, auch faseroffene Leder, sogenannte Rauhleder (auch Wildleder, Veloursleder, Nubukleder genannt), wirksam zu imprägnieren, deren Wasserfestigkeit für den allgemeinen Gebrauch nicht ausreicht.Furthermore, it is also necessary to effectively impregnate fiber-open leather, so-called suede (also called suede, suede, nubuck leather), whose water resistance is not sufficient for general use.

Lederimprägniermittel des Stands der TechnikState of the art leather impregnation agent

.Als Imprägnierungsmittel stehen dem Endverbraucher ausschließlich Sprühartikel (Aerosole) zur Verfügung, mittels der sich Imprägniersubstanzen und Pflegemittel sparsam, gleichmäßig und mühelos auf die Oberfläche der Lederartikel aufbringen lassen. Diese Applikation ist allen anderen angebotenen Darreichungsformen überlegen (z.B. Aufbringen von Imprägniersubstanzen in gelöster, flüssiger Form über Pumpenversprühung, direkter Verteilung der Flüssigkeit aus einer Flasche über einen Dispenser aus Schwamm-Filz oder anderem Material). In der Aerosoldose ist das Treibmittel bzw. die Treibmittelmischung für das Ausbringen und das feine Zerstäuben des eigentlichen Wirkstoffes verantwortlich. Dieser Wirkstoff besteht aus Hydrophobiermitteln, wie Siliconen, Fluorcarbonharzen, Metallseifen, bestimmten Komplexverbindungen, Wachsen - einzeln oder in Mischungen - die in Lösemitteln, wie Testbenzin, chlorierten Kohlenwasserstoffen, Alkoholen, Estern, Ketonen, Aromaten, gelöst oder fein dispergiert sind. Als Treibmittel werden verflüssigte, mit Wasser nicht mischbare Gase, wie Fluorchlorkohlenwasserstoffe (FKW), Propan, Butane, eingesetzt. Ferner werden auch komprimierte Gase, wie Kohlendioxid, Distickoxid, verwendet. Wirkstoff- und Treibmittelphase sollen eine homogene Mischung ergeben. Keines der bekannten Imprägniermittel basiert auf wäßrigen oder z.B. wäßrig/alkoholischen Lösungsmittelsystemen; sondern sie enthalten rein organische Lösemittel. Abgefüllt werden die Inhaltsstoffe in druckfesten Weißblech-oder Aluminiumdosen, die mit handelsüblichen Ventilen und Sprühköpfen versehen sind.As an impregnation agent, only spray articles (aerosols) are available to the end consumer, by means of which impregnation substances and care products can be applied sparingly, evenly and effortlessly to the surface of the leather articles. This application is superior to all other dosage forms offered (e.g. applying impregnation substances in dissolved, liquid form via pump spraying, direct distribution of the liquid from a bottle via a dispenser made of sponge felt or other material). In the aerosol can, the propellant or propellant mixture is responsible for the application and fine atomization of the actual active ingredient. This active ingredient consists of water repellents such as silicones, fluorocarbon resins, metal soaps, certain complex compounds, waxes - individually or in mixtures - which are dissolved or finely dispersed in solvents such as white spirit, chlorinated hydrocarbons, alcohols, esters, ketones, aromatics. Liquefied, water-immiscible gases, such as chlorofluorocarbons (PFCs), propane, butanes, are used as blowing agents. Compressed gases such as carbon dioxide and nitrous oxide are also used. The active ingredient and blowing agent phases should result in a homogeneous mixture. None of the known impregnating agents is based on aqueous or, for example, aqueous / alcoholic solvent systems; they contain purely organic solvents. The ingredients are filled in flameproof tinplate or aluminum cans, which are equipped with standard valves and spray heads.

Diese so hergestellten Imprägniermittel erfüllen ihren Zweck, Leder und Textilien zu hydrophobieren, sehr gut.These impregnating agents thus produced fulfill their purpose of making leather and textiles hydrophobic very well.

Dem unbeschränkten Einsatz obengenannter Aerosolprodukte stellt sich nun aber ihre in den letzten Jahren aufgetretene unerwünschte physiologische Wirkung entgegen. In mehreren Veröffentlichungen wurden diese Imprägniersprays auf der Basis bekannter Wirkstoff/Treibmittel-Kombinationen für das Auftreten von Vergiftungen im Bereich des Atemtraktes verantwortlich gemacht. Es wurde über hochgradigen Hustenreiz, Atemnot und Lungenödeme berichtet. Diese toxischen Erscheinungen traten hauptsächlich bei der Verwendung von Imprägniersprays in geschlossenen, meist unbelüfteten kleinen Räumen auf. Aus diesem Grund werden deshalb auf allen in der Bundesrepublik Deutschland erhältlichen Imprägniersprays in Abstimmung der Behörden mit der Imprägnierspray herstellenden Industrie Warnhinweise auf die Etiketten gedruckt. Auch wurden Imprägniersprays von einzelnen Herstellern in Übereinkunft mit den zuständigen Behörden vom Markt zurückgenommen.However, the unlimited use of the above-mentioned aerosol products is now being countered by their undesirable physiological effects which have occurred in recent years. In several publications, these impregnation sprays were made responsible for the occurrence of poisoning in the area of the respiratory tract on the basis of known active ingredient / propellant combinations. Severe coughing, shortness of breath and pulmonary edema have been reported. These toxic effects mainly occurred when using waterproofing sprays in closed, mostly unventilated, small rooms. For this reason, warning notices are printed on the labels on all impregnation sprays available in the Federal Republic of Germany in coordination with the authorities and the industry that produces the impregnation spray. Impregnation sprays were also withdrawn from the market by individual manufacturers in agreement with the responsible authorities.

ErfindungsgegenstandSubject of the invention

Es stellte sich die Aufgabe, Aerosol-Imprägniermittel für den Endverbraucher mit vergleichbarer Hydrophobierleistung ohne nachteilige physiologische Nebenwirkungen zu konzipieren.The task was to design aerosol impregnating agents for the end user with comparable hydrophobing performance without disadvantageous physiological side effects.

Die Lösung dieses Problems gestaltete sich deshalb so schwierig, da nach gegenwärtigem Wissensstand nicht bekannt ist, welcher der oben beschriebenen Rohstoffe bzw. welche Rohstoffkombination für das Auftreten der Gesundheitsbeeinträchtigungen verantwortlich zu machen sind.The solution to this problem turned out to be so difficult, because according to the current state of knowledge it is not known which of the raw materials described above or which raw material combination for the appearance of the healthy impairments are to be held responsible.

Überraschenderweise wurde nun gefunden, daß an sich bekannte Hydrophobierstoffe auf Basis perfluorierter Carbonharze (Fluorcarbonharze), die mit Wasser allein oder mit Wasser/Alkohol-Mischungen verdünnbar sind, als Aerosol mit Treibmitteln, wie z.B. Dimethylether (DME), abgefüllt und versprüht werden können. Sie sind zur hydrophobierenden Ausrüstung wasserempfindlicher Leder geeignet, ohne daß beim Einatmen der Sprühnebel physiologische Schädigungen der Atemwege entstehen. Gesundheitsbeeinträchtigungen sind mit der erfindungsgemäßen Zusammensetzung nicht zu be-_ fürchten, wie inhalationstoxikologische Untersuchungen erbracht haben.Surprisingly, it has now been found that hydrophobic substances known per se based on perfluorinated carbon resins (fluorocarbon resins), which can be diluted with water alone or with water / alcohol mixtures, as aerosol with propellants, such as e.g. Dimethyl ether (DME), can be filled and sprayed. They are suitable for the hydrophobizing of water-sensitive leather without causing physiological damage to the respiratory tract when the spray is inhaled. Health impairments are not to be feared with the composition according to the invention, as studies on inhalation toxicology have shown.

Gegenstand der vorliegenden Erfindung ist nun ein Imprägnierspray für Leder und Textilien, enthaltend

  • (A) einen aus Fluorcarbonharzen, Lösungsmittel (LA) sowie gegebenenfalls Hilfsstoffen bestehenden Wirkstoff und
  • (B) ein oder mehrere Treibmittel,

das dadurch gekennzeichnet ist, daß (B) ein mit Wasser misch-oder emulgierbares Treibmittel ist und das Lösungsmittel (LA) Wasser und/oder ein mit Wasser mischbares Lösemittel (LW) ist.The present invention now relates to an impregnating spray for leather and textiles
  • (A) an active ingredient consisting of fluorocarbon resins, solvents (LA) and optionally auxiliary substances and
  • (B) one or more blowing agents,

which is characterized in that (B) is a water-miscible or emulsifiable blowing agent and the solvent (LA) is water and / or a water-miscible solvent (LW).

Bei einem erfindungsgemäß vorhandenen, mit Wasser mischbaren Treibmittel (B) handelt es sich bevorzugt um ein verflüssigtes Treibmittel, wie z.B. Dimethylether (DME). Ist dieses Treibmittel (DME) in Kombination mit einem Lösungsmittelsystem (LA) aus Wasser und/oder einem mit Wasser mischbaren Alkohol, insbesondere Äthanol oder Isopropanol, vorhanden, dann bildet sich in dem Imprägnierspray ein binäres bzw. ternäres System aus DNE, Wasser und/oder Alkohol aus, das innerhalb der bekannten Mengenbereiche in Form einer einheitlichen PhaseA water-miscible blowing agent (B) present according to the invention is preferably a liquefied blowing agent, such as e.g. Dimethyl ether (DME). If this blowing agent (DME) is present in combination with a solvent system (LA) made of water and / or a water-miscible alcohol, in particular ethanol or isopropanol, then a binary or ternary system of DNE, water and / / or alcohol from within the known quantity ranges in the form of a uniform phase

vorliegt. Im Falle einer Kombination von DME mit Wasser und/oder Alkohol (z.B. Äthanol oder Isopropanol) ist daher das Mengenverhältnis dieser Stoffe bevorzugt derart, daß die bekannte Mischungslücke zwischen DME und Wasser (vgl. Seite 18 des Prospekts der Aerofako B.V., Holland, "DME Pure, NEW AEROSOL PROPELLANT", September 1983) vermieden wird.is present. In the case of a combination of DME with water and / or alcohol (for example ethanol or isopropanol), the quantitative ratio of these substances is therefore preferably such that the known mixing gap between DME and water (cf. page 18 of the prospectus of Aerofako BV, Holland, "DME Pure, NEW AEROSOL PROPELLANT ", September 1983) is avoided.

Als Treibmittel (B) kann auch ein verflüssigtes (mit Wasser nicht mischbares aber) emulgierbares Treibmittel, wie z.B. Propan, Butan oder Difluordichlormethan, vorliegen.A liquefied (water-immiscible but) emulsifiable blowing agent, such as e.g. Propane, butane or difluorodichloromethane.

Als Treibmittel (B) können aber auch komprimierte, mit Wasser mischbare Treibmittel vorhanden sein, wie z.B. Kohlendioxid; als weitere Beispiele komprimierter Treibmittel sind Stickstoff und Distickoxid zu nennen.Compressed, water-miscible blowing agents may also be present as blowing agents (B), e.g. Carbon dioxide; nitrogen and nitrous oxide are further examples of compressed blowing agents.

Die in dem Wirkstoff (A) vorhandenen Fluorcarbonharze sind die üblichen, wie sie von mehreren Firmen zur hydrophobierenden Ausrüstung von Leder und Textilien angeboten werden. Insbesondere sind solche hydrophobierenden Fluorcarbonharze zu nennen, die mit Wasser und/oder Alkoholen verdünnbar sind, insbesondere solche, die mit Wasser und/oder Alkoholen Lösungen oder über längere Zeit stabile Emulsionen bzw.The fluorocarbon resins present in the active ingredient (A) are the usual ones, as are offered by several companies for the hydrophobic finishing of leather and textiles. In particular, mention should be made of those hydrophobic fluorocarbon resins which can be diluted with water and / or alcohols, in particular those which contain solutions or emulsions which are stable over a long period of time or

Dispersionen bilden. Dabei versteht man auf diesem Gebiet unter "längere Zeit stabil" im allgemeinen übliche Standzeiten dieser Produkte, von z.B. bis zu 3 Jahren.Form dispersions. In this area, "long-term stability" is generally understood to mean the usual service life of these products, e.g. up to 3 years.

Im Zusammenhang mit solchen bekannten hydrophobierenden Perfluorverbindungen sind zu nennen-langkettige Perfluorcarbonsäuren, Perfluoralkansulfonsäuren, Perfluoralkansulfonsäurefluoride bzw. davon abgeleitete Polymerisate auf der Basis fluorhaltiger (Meth)-acrylsäureester, ferner Produkte auf Basis fluoraliphatischer Verbindungen mit salzbildenden Aminogruppen (vgl. z.B. DE-AS 11 96 183, DE-AS 10 72 612 sowie EP-A-102 690). Als Vertreter von im Handel befindlichen Produkten (meistens als Dispersionen) sind zu nennen, wobei in Klammern jeweils der Feststoffgehalt in Gewichtsprozent angegeben ist: FC 208 (ca. 30 %); FC 214 (20 %); FC 228 (27 %); FC 229 (20 %); FC 390 (10 %); FC 453 (20 %); FC 461 (30 %); Foraperle C 305 (25 %); Foraperle P 300 (17 %); Foraperle T 140 (30 %); Foraperle T 145 (25 %); Foraperle T 355 (30 %); Foraperle T 344 (31 %); Foraperle 1190 (28 %);Foraperle T430;Long-chain perfluorocarboxylic acids, perfluoroalkanesulfonic acids, perfluoroalkanesulfonic acid fluorides or polymers derived therefrom on the basis of fluorine-containing (meth) acrylic acid esters and also products based on fluoroaliphatic compounds with salt-forming amino groups are to be mentioned in connection with such known hydrophobicizing perfluoro compounds, and also products based on fluoroaliphatic compounds with salt-forming amino groups (cf., for example, DE-AS 11 96) 183, DE-AS 10 72 612 and EP-A-102 690). Representatives of commercially available products (mostly as dispersions) are to be mentioned, with the solid content in percent by weight being given in brackets: FC 208 (approx. 30%); FC 214 (20%); FC 228 (27%); FC 229 (20%); FC 390 (10%); FC 453 (20%); FC 461 (30%); Foraperle C 305 (25%); Foraperle P 300 (17%); Foraperle T 140 (30%); Foraperle T 145 (25%); Foraperle T 355 (30%); Foraperle T 344 (31%); Foraperle 1190 (28%); Foraperle T430;

Xeroderm DH 471763 (100 %); Nuva F (ca. 20 %); Nuva FH (ca. 25 %). Besonders bevorzugt unter diesen Produkten sind FC 228 sowie Foraperle P 300 und C 305.Xeroderm DH 471763 (100%); Nuva F (approx. 20%); Nuva FH (approx. 25%). FC 228 and Foraperle P 300 and C 305 are particularly preferred among these products.

Das erfindungsgemäß vorhandene Lösungs- oder VerdünnungsMittel (LA) ist ausgewählt aus der Gruppe:Wasser, bevorzugt deionisiertes Wasser; einem mit Wasser mischbaren Lösemittel (LW); und Mischungen von Wasser mit (LW). Als Lösemittel (LW), allein oder in Mischung mit Wasser, haben sich mit Wasser mischbare Alkohole, insbesondere ein-oder mehrwertige aliphatische Alkohole, bewährt; bevorzugt handelt es sich dabei um C1-C6-Alkohole, wie z.B. Ethanol, n-Propanol, Isopropanol, Butanol; ferner Glykole, wie z.B. Ethylenglykol, aber auch mit Wasser mischbare Ketone sind als Lösemittel (LW) geeignet, wie z.B. Aceton.The solvent or diluent (LA) present according to the invention is selected from the group: water, preferably deionized water; one with water solvent (LW); and mixtures of water with (LW). Solvents (LW), alone or in a mixture with water, have proven to be water-miscible alcohols, in particular mono- or polyhydric aliphatic alcohols; these are preferably C 1 -C 6 alcohols, such as ethanol, n-propanol, isopropanol, butanol; also glycols, such as ethylene glycol, but also water-miscible ketones are suitable as solvents (LW), such as acetone.

Bevorzugt ist es beim Anmeldungsgegenstand, wenn die resultierende verdünnte Lösung von Fluorcarbonharz im Lösungsmittel (LA), d.h. der Wirkstoff (A), mit dem Treibmittel (B), z.B. Dimethylether, klar oder fein dispers in druckfesten Behältern mischbar ist. Hier hat sich als besonders geeignet ein Lösungsmittel (LA), bestehend aus der Kombination von Wasser/Alkohol, erwiesen. Aber auch Alkohol allein (z.B. in Kombination mit den Treibmitteln DME, Propan oder Butan) oder Wasser allein haben sich als Lösungsmittel (LA) bewährt (vgl. auch obige Ausführungen für die Vermeidung der bekannten Mischungslücke von DME/Wasser).It is preferred in the subject of the application if the resulting dilute solution of fluorocarbon resin in the solvent (LA), i.e. the active ingredient (A) with the propellant (B), e.g. Dimethyl ether, clear or finely dispersible, can be mixed in pressure-resistant containers. A solvent (LA) consisting of the combination of water / alcohol has proven to be particularly suitable here. But also alcohol alone (e.g. in combination with the blowing agents DME, propane or butane) or water alone have proven themselves as solvents (LA) (see also the explanations above for avoiding the known mixture gap of DME / water).

In dem Wirkstoff (A) können außer dem Fluorcarbonharz und dem Lösungsmittel (LA) gegebenenfalls noch die bei derartigen Sprays üblichen Hilfsstoffe vorhanden sein. Einer dieser fakultativen Hilfsstoffe sind übliche Korrosionsschutzmittel (Korrosionsinhibitoren) für Weißblech- und Aluminiumdosen. Nur beispielsweise sind,zu nennen: Natriumbenzoat; Dinatriumhydrogenphosphat; Vircopet 20, 30 und 40; Deriphat 151 C, Rewo B 3010; Sarcosyl NL 97; Dehyquart SP.In addition to the fluorocarbon resin and the solvent (LA), the active substances (A) may also contain the auxiliaries customary in sprays of this type. One of these optional auxiliaries are common anti-corrosion agents (corrosion inhibitors) for tinplate and aluminum cans. The following are just a few examples: sodium benzoate; Disodium hydrogen phosphate; Vircopet 20, 30 and 40; Deriphat 151 C, Rewo B 3010; Sarcosyl NL 97; Dehyquart SP.

Bezüglich der im Wirkstoff (A) gegebenenfalls vorhandenen Hilfsstoffe sind außerdem noch Riechstoffe der auf diesem Gebiet üblichen Art zu nennen, wie wasser-, lösemittel- und treibmittel-, insbesondere DME-beständige Parfümöle.With regard to the excipients which may be present in the active ingredient (A), fragrances of the type customary in this field are also to be mentioned, such as perfume oils which are resistant to water, solvents and propellants, in particular DME.

Als weitere gegebenenfalls vorhandene Hilfsstoffe sind noch übliche Antischaummittel zu erwähnen.Conventional anti-foaming agents are also to be mentioned as further auxiliary substances which may be present.

Die Mengen der Komponenten des wie oben beschriebenen Wirkstoffs (A) können in weiten Bereichen variieren. Vorteilhaft besitzt jedoch der Wirkstoff (A) (Wirkstoffrezeptur) folgende Zusammensetzung, wobei die Menge der Komponenten jeweils in Gewichtsprozent, bezogen auf die Wirkstoffrezeptur, angegeben ist:

Figure imgb0001
The amounts of the components of the active ingredient (A) as described above can vary within wide limits. However, the active ingredient (A) (active ingredient formulation) advantageously has the following composition, the amount of the components in each case being given in percent by weight, based on the active ingredient formulation:
Figure imgb0001

Die Menge des Wirkstoffs (A) im erfindungsgemäßen Imprägnierspray kann je nach seiner Art und der Art des vorhandenen Treibmittels variieren. Im allgemeinen liegen 35 bis 65 Gew.-% an Wirkstoff (A) (bezogen auf die fertige Abfüllrezeptur) vor. Besonders bewährt hat sich eine Wirkstoffmenge von40 bis 60 Gew.-%. Die Menge des erfindungsgemäßen Treibmittels (B) kann ebenfalls variieren. Sie liegt gewöhnlich bei 30 bis.70 Gew.-%, bevorzugt 35 bis 55 Gew.-% verflüssigtem Treibmittel und bei 0 bis 7 Gew.-%, bevorzugt 0 bis 5 Gew.-% komprimiertem Treibmittel.The amount of active ingredient (A) in the impregnating spray according to the invention can vary depending on its type and the type of blowing agent present. In general, there are 35 to 65% by weight of active ingredient (A) (based on the finished filling formulation). An amount of active ingredient of 40 to 60% by weight has proven particularly useful. The amount of blowing agent (B) according to the invention can also vary. It is usually 30 to 70% by weight, preferably 35 to 55% by weight of liquefied propellant and 0 to 7% by weight, preferably 0 to 5% by weight of compressed propellant.

Die Anwendung des erfindungsgemäßen Imprägniersprays erfolgt in gleicher Weise wie bei den bekannten Aerosol-Imprägniermitteln auf die zu behandelnden Oberflächen von Leder, z.B. Schuhen, Lederbekleidung, Ledermöbeln usw., oder von Textilien, z.B. Bekleidung, Zelten, Planen, Schirmen etc. Auch zur Imprägnierung vorgesehene Papierflächen lassen sich erfindungsgemäß behandeln.The impregnating spray according to the invention is applied in the same way as in the known aerosol impregnating agents to the surfaces of leather to be treated, e.g. Shoes, leather clothing, leather furniture, etc., or of textiles, e.g. Clothing, tents, tarpaulins, umbrellas etc. Paper surfaces intended for impregnation can also be treated according to the invention.

Ein Vergleich des erfindungsgemäßen Imprägniersprays hinsichtlich Toxikologie mit bekannten Produkten ergab überraschend vorteilhafte Resultate. Die toxikologischen Prüfungen wurden gemäß der im OECD-Protokoll 403 beschriebenen Methode durchgeführt. Diese tierexperimentelle Untersuchung gestattet es, akute inhalationstoxikologische Daten zu erhalten, die sich im LC 50-Wert an Ratten bei vierstündiger Exposition ausdrücken (LC-letale Inhalationskonzentration).. Während bei den herkömmlichen Imprägniersprays LC 50-Werte zwischen ca. 0,7 und 12 g/m3 A comparison of the impregnation spray according to the invention Visible toxicology with known products gave surprisingly beneficial results. The toxicological tests were carried out in accordance with the method described in OECD Protocol 403. This animal experiment allows acute inhalation toxicological data to be obtained, which are expressed in the LC 50 value in rats after four hours of exposure (LC lethal inhalation concentration). While the conventional impregnation sprays have LC 50 values between approx. 0.7 and 12 g / m 3

ermittelt wurden, zeigte die erfindungsgemäße Zusammensetzung keinerlei akut toxische Wirkung bei den Versuchstieren, selbst bei sehr hohen Konzentrationen (bis 44 g/m3). Bei dieser Exposition wurde keine Mortalität festgestellt; LC 50-Werte konnten nicht ermittelt werden.were determined, the composition according to the invention showed no acutely toxic effect in the test animals, even at very high concentrations (up to 44 g / m 3 ). No mortality was found at this exposure; LC 50 values could not be determined.

Die folgenden Beispiele erläutern die Erfindung, ohne ihre Anwendung zu beschränken.The following examples illustrate the invention without restricting its application.

In den folgenden Beispielen stellen die genannten Zahlenangaben jeweils Gewichtsprozent, bezogen auf die Wirkstoffrezeptur bzw. auf die Abfüllrezeptur, dar.In the following examples, the numerical data given represent percentages by weight, based on the active ingredient formulation or on the filling formulation.

B e i s p i e 1 eExample: 1 e

Figure imgb0002
Figure imgb0002
Figure imgb0003
Figure imgb0003

Claims (8)

1. Imprägnierspray für Leder und Textilien, enthaltend (A) einen aus Fluorcarbonharzen, Lösungsmittel (LA) sowie gegebenenfalls Hilfsstoffen bestehenden Wirkstoff und (B) ein oder mehrere Treibmittel,
dadurch gekennzeichnet , daß (B) ein mit Wasser misch- oder emulgierbares Treibmittel ist und das Lösungsmittel (LA) Wasser und/oder ein mit Wasser mischbares Lösemittel (LW) ist.1. Impregnation spray for leather and textiles, containing (A) an active ingredient consisting of fluorocarbon resins, solvents (LA) and optionally auxiliary substances and (B) one or more blowing agents,
characterized in that (B) is a water-miscible or emulsifiable blowing agent and the solvent (LA) is water and / or a water-miscible solvent (LW). 2. Imprägnierspray nach Anspruch 1, dadurch gekennzeichnet, daß (B) ein verflüssigtes Treibmittel, z.B. Dimethylether, ist.2. Impregnation spray according to claim 1, characterized in that (B) a liquefied propellant, e.g. Dimethyl ether. 3. Imprägnierspray nach Anspruch 1, dadurch gekennzeichnet, daß (B) ein verflüssigtes Treibmittel, z.B. Propan oder Butan, ist und das Lösungsmittel (LA) ein mit Wasser mischbares Lösemittel (LW) ist.3. Impregnation spray according to claim 1, characterized in that (B) a liquefied propellant, e.g. Propane or butane, and the solvent (LA) is a water-miscible solvent (LW). 4. Imprägnierspray nach Anspruch 1, dadurch gekennzeichnet, daß (B) ein komprimiertes Treibmittel, z.B. Kohlendioxid, ist.4. Impregnation spray according to claim 1, characterized in that (B) a compressed blowing agent, e.g. Carbon dioxide. 5. Imprägnierspray nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß das mit Wasser mischbare Lösemittel (LW) ein Alkohol ist. -5. Impregnation spray according to one of the preceding claims, characterized in that the water-miscible solvent (LW) is an alcohol. - 6. Imprägnierspray nach Anspruch 5, dadurch gekennzeichnet, daß der mit Wasser mischbare Alkohol ein ein- oder mehrwertiger aliphatischer Alkohol ist.6. Impregnation spray according to claim 5, characterized in that the water-miscible alcohol is a mono- or polyhydric aliphatic alcohol. 7. Imprägnierspray nach einem der vorhergehenden Ansprüche, dadurch gekennzeichnet, daß der Wirkstoff (A) besteht aus (jeweils Gewichtsprozent, bezogen auf Wirkstoffrezeptur):
Figure imgb0004
und daß das gebrauchsfertige Spray (Abfüllrezeptur) enthält (jeweils Gewichtsprozent, bezogen auf Abfüllrezeptur): 35 bis 65 % Wirkstoff (A) 30 bis 70 % verflüssigtes Treibmittel und 0 bis 7 % komprimiertes Treibmittel.7. Impregnation spray according to one of the preceding claims, characterized in that the active ingredient (A) consists of (in each case percent by weight, based on the active ingredient formulation):
Figure imgb0004
and that the ready-to-use spray (filling formulation) contains (in each case percent by weight, based on filling formulation): 35 to 65% active ingredient (A) 30 to 70% liquefied propellant and 0 to 7% compressed propellant. 8. Verwendung eines in den vorstehenden Ansprüchen gekennzeichneten Sprays zur Imprägnierung von Leder und Textilien.8. Use of a spray characterized in the preceding claims for the impregnation of leather and textiles.
EP84113475A 1984-07-30 1984-11-08 Impregnating spray for leather and textiles and use thereof Expired EP0169935B1 (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84113475T ATE45374T1 (en) 1984-07-30 1984-11-08 IMPREGNATION SPRAY FOR LEATHER AND TEXTILES AND THEIR USE.

Applications Claiming Priority (3)

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DE3428023 1984-07-30
DE19843428023 DE3428023A1 (en) 1984-07-30 1984-07-30 IMPREGNATION SPRAY FOR LEATHER AND TEXTILES AND THEIR USE
DE19853527299 DE3527299A1 (en) 1984-07-30 1985-07-30 IMPREGNATION SPRAY WITH HYDROPHOBIC REINFORCEMENT FOR LEATHER AND TEXTILES AND THEIR USE

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EP86110532A Expired - Lifetime EP0210656B1 (en) 1984-07-30 1986-07-30 Impregnating spray with increased water-proofing for leather and textiles, and its use

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DE3728162A1 (en) * 1987-08-24 1989-03-09 Hoechst Ag METHOD FOR THE HYDROPHOBICATION AND OLEPHOBICATION OF LEATHER BY IMPREGNATION WITH FLUORCHEMICALS
DE4406863A1 (en) * 1994-03-02 1995-09-07 Gruenzweig & Hartmann Treatment of mineral fibres e.g. for insulation
US5902637A (en) * 1997-11-10 1999-05-11 W. L. Gore & Associates, Inc. Water repellent restorative and process of use
US7094743B2 (en) * 2003-07-29 2006-08-22 3M Innovative Properties Company Composition, wipe and method for cleaning, protecting and imparting gloss to a substrate

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FR2202515A5 (en) * 1972-10-09 1974-05-03 Asahi Glass Co Ltd Oil-and water-repellent agents for textiles - from copolymerising of monomers contg. fluoroalkyl gps., vinyl chloride and maleate or fumarate esters
EP0032779A2 (en) * 1980-01-21 1981-07-29 Pfw (Nederland) B.V. Novel method for preparation of homogeneous dimethylether-propelled water-based aerosols

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EP0210656A2 (en) 1987-02-04
DE3428023C2 (en) 1990-06-13
DK539084D0 (en) 1984-11-13
EP0210656B1 (en) 1990-10-24
DE3527299A1 (en) 1987-02-05
EP0210656A3 (en) 1987-10-14
EP0169935B1 (en) 1989-08-09
DE3428023A1 (en) 1986-02-06
EP0169935A3 (en) 1986-05-07

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