DE3428023A1 - IMPREGNATION SPRAY FOR LEATHER AND TEXTILES AND THEIR USE - Google Patents

Description

WERNER & HERTZ G.m.b.H., D-6500 Mainz

Impregnation spray for leather and textiles as well as its

use

description

Technical background

Modern shoes have a high standard in terms of comfort and fit. Most of those available today Shoes do not have to "go in", i.e. the slow adaptation of the relatively hard leather to the individual foot shape with all its annoying complaints. Pressing shoes and aching feet when wearing new shoes are largely a thing of the past.

This progress was achieved, among other things, by processing soft, flexible and elastic types of smooth leather, the are quickly adaptable and hardly cause any pressure or chafing points on the foot. However, this benefit went to Loads of another important leather property, water resistance. By incorporating softening substances, such as emulsified fats (fat liquor), the hydrophobicity in the leather was in some cases significantly worsened. In order to meet the requirements of daily use of this footwear prepared in this way, it is It is imperative to additionally impregnate these shoes before they are used for the first time and also in between while they are being worn. Treatment with normal care products remains unaffected.

The same applies analogously to what has been said for shoes for leather clothing.

Furthermore, it is necessary to also use fiber-open leather, so-called rough leather (also suede, suede, nubuck leather called), to effectively impregnate the water resistance of which is insufficient for general use.

Prior art leather impregnants

The only impregnating agent available to the end user is spray articles (aerosols), by means of the impregnating substances and care products are applied sparingly, evenly and effortlessly to the surface of the leather article get applied. This application is superior to all other forms of administration offered (e.g. application of impregnating 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). It's in the aerosol can Propellant or propellant mixture for the application and fine atomization of the actual active ingredient responsible. This active ingredient consists of water repellants, such as silicones, fluorocarbon resins, metal soaps, certain complex compounds, waxes - individually or in Mixtures - those in solvents such as white spirit, chlorinated hydrocarbons, alcohols, esters, ketones, aromatics, are dissolved or finely dispersed. Liquefied, water-immiscible gases such as Chlorofluorocarbons (HFCs), propane, butanes are used. Furthermore, compressed gases, such as carbon dioxide, nitrous oxide, are used. Active ingredient and propellant phase should result in a homogeneous mixture. None of the known impregnating agents is based on aqueous or e.g. aqueous / alcoholic solvent systems;

they contain purely organic solvents. The ingredients are filled in pressure-resistant tinplate or Aluminum cans with standard valves and spray heads.

These impregnating agents produced in this way fulfill their purpose of rendering leather and textiles hydrophobic very well.

The unrestricted use of the above-mentioned aerosol products is now facing the one that has appeared in recent years counteracts undesirable physiological effects. These waterproofing sprays have been published in several publications on the basis of known active ingredient / propellant combinations for the occurrence of poisoning in the area of the Respiratory tract blamed. Severe coughing, dyspnoea, and pulmonary edema have been reported. These toxic phenomena mainly occurred when using waterproofing sprays in closed, mostly unventilated small rooms. For this reason are therefore used on all impregnation sprays available in the Federal Republic of Germany in coordination with the authorities with the impregnation spray-producing industry warning notices printed on the labels. Impregnation sprays were also used withdrawn from the market by individual manufacturers in agreement with the responsible authorities.

Subject matter of the invention

The task was to produce aerosol impregnating agents with comparable water repellency for the end user without conceiving of adverse physiological side effects.

The solution to this problem turned out to be so difficult because it is not known according to the current state of knowledge is which of the raw materials described above or which raw material combination for the occurrence of the health

impairments of health are to be blamed.

Surprisingly, it has now been found that water repellants known per se based on perfluorinated carbon resins (Fluorocarbon resins), which can be diluted with water alone or with water / alcohol mixtures, as an aerosol Propellants, such as dimethyl ether (DME), can be filled and sprayed. They are used to make them hydrophobic Finishing of water-sensitive leather suitable without physiological damage when inhaling the spray mist the airways arise. Health impairments are not to be dealt with with the composition according to the invention. fear, as inhalation toxicological studies have shown.

The present invention now relates to an impregnation spray for leather and textiles containing

(A) an active ingredient consisting of fluorocarbon resins, solvents (LA) and, if appropriate, auxiliaries and

(B) one or more propellants,

which is characterized in that (B) is a propellant which can be mixed or emulsified with water and the solvent (LA) is water and / or a water-miscible solvent (LW).

A water-miscible propellant (B) present according to the invention is preferably a liquefied one Propellants such as dimethyl ether (DME). Is this propellant (DME) in combination with a solvent system (LA) from water and / or a water-miscible alcohol, in particular ethanol or isopropanol, is present, then a binary or ternary system of DME, water and / or alcohol is formed in the impregnation spray from that within the known quantity ranges in the form of a uniform phase

is present. In the case of a combination of DME with water and / or alcohol (e.g. ethanol or isopropanol) the proportions of these substances are preferably such that the known miscibility gap between DME and water (See page 8 of the prospectus from Aerofako B.V., Holland, "DME Pure, NEW AEROSOL PROPELLANT", September 1983) will.

A liquefied (water-immiscible but) emulsifiable propellant, such as e.g. propane, butane or difluorodichloromethane.

However, compressed, water-miscible blowing agents, such as carbon dioxide, for example, can also be present as blowing agents (B); further examples of compressed propellants are nitrogen and nitrous oxide.

The fluorocarbon resins present in the active ingredient (A) are the usual ones, as offered by several companies for the hydrophobic finishing of leather and textiles. Such hydrophobic fluorocarbon resins are in particular mention that can be diluted with water and / or alcohols, in particular those that can be diluted with water and / or Alcohol solutions or long-term stable emulsions or

Form dispersions. In this field, “stable for a long time” is generally understood to mean the usual standing times of these products, for example up to 3 years.

In connection with such known hydrophobic perfluorocompounds, mention should be made of long-chain perfluorocarboxylic acids, perfluoroalkanesulfonic acids, perfluoroalkanesulfonic acid fluorides and / or polymers derived therefrom based on fluorine-containing (meth) acrylic acid esters, and also products based on fluoroaliphatic compounds with salt-forming amino groups (cf. e.g. DE-AS 1196 , DE-AS 10 72 612 and EP-A-102 690). Representatives of commercially available products (mostly as dispersions) should be mentioned, the solids content in each case being given in percentages by weight in brackets: PC 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 (3I%); Foraperle II90 (28%); Foraperle T430;

Xeroderm DH 471763 (100%); Nuva F (ca 20%); Nuva FH (approx. 25%). Particularly preferred among these products are FC 228 as well as Foraperle P 300 and C 305.

The solvent or diluent present according to the invention (LA) is selected from the group: water, preferably deionized water; one mixed with water

available solvents (LV); and mixtures of water with '(LW). ' As solvents (LW), alone or in a mixture with water, water-miscible alcohols, in particular or polyhydric aliphatic alcohols, proven; these are preferably C.-Cg alcohols, such as ethanol, n-propanol, isopropanol, butanol; also glycols, such as e.g. Ethylene glycol, but also water-miscible ketones Suitable as a solvent (LW), such as acetone.

It is preferred in the subject matter 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. dirnethyl ether, clear or finely dispersed in pressure-resistant containers is miscible. A solvent (LA) consisting of a combination of has proven to be particularly suitable here Water / alcohol, proven. But also alcohol alone (e.g. in Combination with the propellants DME, propane or butane) or water alone have proven themselves as solvents (LA) (cf. also the above explanations for avoiding the known miscibility gap of DME / water).

In the active ingredient (A), in addition to the fluorocarbon resin and the Solvents (LA) possibly also those in such Sprays usual auxiliaries be present. One of these optional ones Auxiliary materials are common corrosion protection agents (corrosion inhibitors) for tinplate and aluminum cans. To be mentioned only by way of example: sodium benzoate; Disodium hydrogen phosphate; Vircopet 20, 30 and 40; Deriphat C, Rewo B 3010; Sarcosyl NL 97; Dehyquart SP.

With regard to those which may be present in the active ingredient (A) Auxiliaries are also fragrances in this field the usual type, such as water, solvent and propellant, especially DME-resistant perfume oils.

Customary antifoam agents should also be mentioned as further auxiliary substances which may be present.

The amounts of the components of the as described above Active ingredient (A) can vary within wide limits. However, the active ingredient (A) (active ingredient formulation) advantageously has the following composition, the amount of the components in percent by weight, based on the Active ingredient formulation, indicated is:

Fluorocarbon resin (solids) 0.1 to 1.5%, preferably 0.2 to 1.0% Solvent (LW) 6 to 98%, preferably 12 to 98%, Water 0 to 98%, preferably ο to 65%

possibly corrosion inhibitor 0 to 0.5%, preferably 0.1 to 0.4% optionally perfume 0 to 0.5%, preferably 0 to 0.3%

The amount of the active ingredient (A) in the impregnation spray according to the invention can depend on its type and the type of substance present Propellant vary. In general, there is 35 "to 65% by weight of active ingredient (A) (based on the finished filling recipe) before. An amount of active ingredient of 40 to 60% by weight has proven particularly useful. The amount of the invention Propellant (B) can also vary. It is usually from 30 to. 70% by weight, preferably 35 to 55% by weight, liquefied Propellant and at 0 to 7 wt .-%, preferably 0 to 5 wt .-% compressed propellant.

The impregnation spray according to the invention is used in the same way as with the known aerosol impregnating agents on the surfaces to be treated Leather, e.g. shoes, leather clothing, leather furniture, etc., or of textiles, e.g. clothing, tents, tarpaulins, Umbrellas, etc. Paper surfaces provided for impregnation can also be treated according to the invention.

A comparison of the impregnation spray according to the invention

Visibly toxicology with known products gave surprisingly beneficial results. The toxicological Tests were carried out according to the method described in OECD protocol 403 ". These animal experiments Investigation permits acute inhalation toxicological Obtain data that is reflected in the LC 50 value in rats four hours of exposure (LC lethal inhalation concentration). While conventional impregnation sprays have LC 50 values between approx. 0.7 and 12 g / no were determined, the composition according to the invention showed no acute toxic effect in the Test animals, even at very high concentrations (up to 44 g / nr). There was no mortality at this exposure established; LC 50 values could not be determined.

The following examples illustrate the invention without limit their application.

In the following examples, the figures given represent percentages by weight, based on the active ingredient formulation or on the filling recipe.

Examples

1. Active ingredient formulations I II III (Active ingredient (A))

Foraperle P 300 2.9 - -

FC 228 _ 1.85 -

Foraperle C 305 N ethanol, denatured isopropanol distilled water.

Na benzoate B 3010

Perfume

- - 2.0 6.6 - 92.7 - 35.00 - - 62.95 5.0 - 0.20 0.3 0.3 - - 0.2 -

2. Filling recipes

Active ingredient I 60.0

Active ingredient II - 50.0

Active ingredient III - - 60.0

Propane / butane 2.7 bar 40.0

ME - 50.0 35.0

Carbon dioxide - - 5 »0

Claims (1)

Dr. F. Zumsteir sen. - Dr. E. Assmann 34 28 Dipl.-Ing. F. Klingseisen - Dr. F. Zumstein jun. patent attorneys Authorized representatives at the European Patent Office representatives before the european p at en t office 90 / Si Claims 1. Impregnation spray for leather and textiles, containing (A) an active ingredient consisting of fluorocarbon resins, solvents (LA) and, if appropriate, auxiliaries and (B) one or more propellants, characterized in that (B) is a water-miscible or emulsifiable propellant and the solvent (LA) is water and / or a water-miscible solvent (LW). 2. Impregnation spray according to claim 1, characterized in that (B) is a liquefied one Propellant, e.g., dimethyl ether. 5. Impregnation spray according to claim 1, characterized in that that (B) is a liquefied propellant, e.g. propane or butane, and the solvent (LA) is one Is a water-miscible solvent (LW). 4-, impregnation spray according to claim 1, characterized in, that (B) is a compressed propellant such as carbon dioxide. "™ C- ™ * 5. Impregnation spray according to one of the preceding claims, characterized in that the with water miscible solvent (LV) is an alcohol. 6. Impregnation spray according to claim 5i, characterized in that that the water-miscible alcohol is a monohydric or polyhydric aliphatic alcohol. 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): Fluorocarbon resin (pesticide) solvent (LW) water optionally corrosion inhibitor, optionally perfume and that the ready-to-use spray (filling formulation) contains (in each case percent by weight, based on the filling recipe): 35 to 65 % active ingredient (A) 30 to 70 % liquefied propellant and
0 to 7 % compressed propellant. 8. Use of a spray characterized in the preceding claims for the impregnation of leather and Textiles. ο, 1 to 1.5 6th until 98 0 until 98 0 until 0.5 0 until 0.5