EP0210656A2 - Impregnating spray with increased water-proofing for leather and textiles, and its use - Google Patents

Abstract

1. Impregnating spray for leather and textiles based on (A) an active substance consisting of (a) fluorocarbon resins, (b) a solvent selected from ethanol, n-propanol and isopropanol, and optionally (c) adjuvants, and (B) one or more propellants which are miscible or emulsifiable with water, the active substance (A) containing as an obligatory component a hydrophobic agent based on polyacrylate.

Description

European application 84113475.2 relates to a novel impregnation spray for leather and textiles, which is primarily intended for the treatment of water-sensitive materials. Due to its new composition, this impregnation spray is physiologically harmless; Damage to the respiratory tract, as was found in previously known compositions, can no longer occur in the impregnation spray according to this application. It is therefore particularly suitable for the end user who treats the leather and textiles himself.

The impregnation sprays according to registration 84113475.2 have proven themselves to be tried and tested products and in most cases meet the requirements set in a satisfactory manner. However, with the large number of types of leather occurring in practice with the most varied properties, there are sometimes some types of leather whose treatment with the impregnation spray according to the main application is not completely satisfactory.

It was therefore an object of the present invention to provide an improved impregnation spray which has an enhanced hydraphobing effect, without otherwise Having to accept disadvantages. At the same time, it had to be taken into account that the desired strengthening of the hydrophobizing effect does not go hand in hand with a deterioration in the properties associated with inhalation toxicology.

To achieve this goal, one could have thought of increasing the concentrations of the impregnating constituents in the impregnating spray of the earlier application mentioned above beyond the usual level. However, this has some significant disadvantages: The surfaces of smooth leather can become unsightly; shiny surfaces can become matt; polishing is often not possible because the covering becomes sticky. In certain cases, greasy residues can arise which, in addition to reducing gloss, also result in increased dirt adherence; further disadvantages that occur are accumulations of the solids, especially on the leather surface (and here again in the folds of the shoes), which are particularly evident when walking. With suede leather (suede leather, nubuck leather), the surfaces can harden and become rough with such unsuitable compositions; the desired soft, velvety handle is lost. The conceivable measure to increase the hydrophobizing effect of the impregnating spray according to application 84113475.2 by means of larger amounts of impregnating constituents had to be ruled out. Subject of the invention Surprisingly, the applicant has now found that with a type of products known per se, the task at hand - enhancing the hydrophobic effect - can be achieved without the disadvantages mentioned above occurring: When using polyacrylates, as the applicant has determined, Together act with the fluorocarbon resins a very synergistic hydrophobic reinforcement.

This reinforcement mechanism already occurs when relatively low polyacrylate concentrations are present. In this way, only a few solids are added to the leather, which do not entail the disadvantages mentioned above.

This finding of the synergistic interaction of polyacrylates and fluorocarbon resins in the sense of an increased hydrophobic effect is completely unexpected and can be proven by tests.

• (A) einen Wirkstoff, der aus
  • (a) Fluorcarbonharzen,
  • (b) einem Lösungsmittel (LA) aus der Gruppe Wasser und/oder einem mit Wasser mischbaren Lösemittel (LW) sowie gegebenenfalls
  • (c) Hilfsstoffen besteht, und
• (B) ein oder mehrere mit Wasser mischbare oder emulgierbare Treibmittel, das dadurch gekennzeichnet ist, daß der Wirkstoff (A) als obligatorische Komponente noch ein Hydrophobiermittel auf Polyacrylatbasis enthält.

The present application thus relates to an embodiment of the impregnation spray according to application 84113475.2 with the aim of giving it an increased hydrophobic effect. The subject of the present application is therefore an impregnating spray for leather and textiles

• (A) an active ingredient that consists of
  • (a) fluorocarbon resins,
  • (b) a solvent (LA) from the group water and / or a water-miscible solvent (LW) and optionally
  • (c) excipients, and
• (B) one or more water-miscible or emulsifiable blowing agents, which is characterized in that the active ingredient (A) also contains a hydrophobizing agent based on polyacrylate as an obligatory component.

Examples of suitable polyacrylate hydrophobizing agents are homopolymers and copolymers of acrylic acid esters and to name methacrylic acid esters. A large number of different types of acrylic resin are available for this purpose.

Such polyacrylate hydrophobizing agents can be solvent-free or solvent-containing; they can also be in the form of aqueous dispersions.

Examples of polyacrylate additives for the impregnation spray according to the invention with enhanced hydrophobicity are: solid thermoplastic acrylic resins and thermoplastic acrylate solvent polymers; in particular methyl methac-butyl methacrylate, ethyl methacrylate, and isobutyl methacrylate, which • can each be present as homo- or copolymers. Such polymers are commercially available; they can be solvent-free or solvent-based. Examples of commercially available products are Plexigum N 742 (ethyl methacrylate, solid); Plexigum P 28 (i-butyl methacrylate, solid); Plexigum N 80 (ethyl methacrylate, solid); Plexisol P 550 (butyl methacrylate, dissolved in petrol); Plex 8681 F (ethyl methacrylate, solid); Synthacryl SC 124 (methacrylic acid ester copolymer, dissolved in petrol); Neocryl B 700 (i-butyl methacrylate, solid); Neocryl B 705 (i-butyl methacrylate copolymer, solid); Neocryl B 722 (ethyl acrylate / methyl methacrylate, solid); Neocryl B 731 (i-butyl methacrylate copolymer, solid); Neocryl B 811 (methyl methacrylate, solid); Neocryl V 700-50 (i-butyl methacrylate, in gasoline); Neocryl V 731-50 (i-butyl methacrylate copolymer, in petrol).

The aforementioned solid thermoplastic acrylic resins and thermoplastic acrylate solvent polymers are particularly suitable for anhydrous impregnation spray formulations.

In the case of water-containing impregnation spray formulations, use is made above all of aqueous acrylate dispersions as polyacrylate additives in order to increase the hydrophobizing effect. Such aqueous acrylate dispersions are also widely available on the market. Examples of aqueous acrylate dispersions which can be used according to the invention are: Acrym 02 (acrylic copolymer, aqueous dispersion); Acrym 32 (acrylic copolymer, aqueous dispersion); Acrym 37 (acrylic polymer, aqueous dispersion); Neocryl A 26-.C (acrylic polymer, aqueous dispersion); Neocryl A 401 (acrylic polymer, aqueous dispersion); Neocryl A 349 (acrylic polymer, aqueous dispersion); Neocryl NH 20 (acrylic polymer, aqueous dispersion).

The amounts of the polyacrylates which are used in the impregnation spray according to the invention as water repellant boosters are relatively small. Amounts of acrylic polymer from 0.1 to 2.0% by weight, based on the active ingredient formulation (A), have proven successful. Amounts of acrylic polymer of 0.2 to 1.5% by weight, based on active ingredient (A), have proven particularly useful.

The other constituents of the impregnation spray according to the invention essentially correspond to the components as described in the above-mentioned application 84113475.2.

The fluorocarbon resins (a) present in the active ingredient (A) are the usual ones, as are offered by several companies for the hydrophobizing finish 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 have solutions with water and / or alcohols or over a prolonged period form stable emulsions or dispersions. The term "stable over a longer period" in this area generally means the usual service life of these products, for example up to 3 years. 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 should 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 , DE-AS 10 72 612 and EP-A-102 690). Representatives of commercially available products (mostly as dispersions or solutions) are to be mentioned, with the solids content in percent by weight being given in brackets: FC 208 (approx. 30%); FC 213 (20%); FC 214 (20%); FC 217 (20%); FC 218 (36%); FC 228 (27%); FC 229 (20%); FC 232 (30%); FC 247 (30%); FC 270 (18%); FC 310 (15%); FC 326 (40%); FC 390 (10%); FC 453 (20%); FC 461 (30%); FC 3000 (3%); 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 T 430; Foraperle B 244; Foraperle B 208; Foraperle 333; Xeroderm DH 471763 (100%); Nuva F (approx. 20%); Nuva FH (approx. 25%). FC 228, FC 3000 and Foraperle P 300 and C 305 are particularly preferred among these products.

The (b) solvent or diluent (LA) which is also present is selected from the group: water, preferably deionized water; a water-miscible solvent (LW); and mixtures of water with (LW) .. As a solvent (LW), alone or in a mixture with water, water-miscible alcohols, in particular mono- or polyhydric aliphatic alcohols, have proven successful; 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.

In addition to the components (a) and (b) mentioned, the active ingredients (A) may also contain the auxiliaries (c) customary in such impregnation sprays, as described in the second older EP application 85113333.9. Such auxiliaries are initially conventional leather care additives, such as those used to give the impregnation spray a care effect. Examples of such care components are: waxes (e.g. natural waxes, modified montan waxes, PE waxes, paraffins); Silicones (e.g. dimethylpolysiloxanes, amino functional polysiloxanes and the like); Oils and fats (tears, wool fat, mink oil, lanolin); Dyes (dissolved dyes, organic and inorganic pigment fine doughs, inorganic and organic color pigments).

Such additives for leather care are expediently dispersed or emulsified in water and / or alcohol in the customary manner (since they are usually not themselves water- or alcohol-soluble). Examples of suitable emulsifiers are: nonionic emulsifiers, such as follyglycol ether of fatty alcohols and _/ or alkylphenols (eg emulsifier 2106); anionic emulsifiers, such as amine salts of higher fatty acids (eg morpholine stearate); cationic emulsifiers, such as quaternary alkylammonium salts (for example alkyldimethylbenzylammonium chloride).

• 1. Emulsionen mit Naturwachsen anionisch
  
• 2. Emulsionen mit modifizierten Montanwachsen anionisch nichtionogen
  
• 3. Emulsionen mit Polyäthylenwachsen
  

In principle, the wax emulsions can be prepared from conventional natural waxes, modified montan waxes, oxidized polyethylene waxes or paraffins in a manner known per se with emulsifiers (nonionic, anionic, cationic). The wax is selected in the usual way according to the application requirements, such as gloss, hardness and flexibility of the Wax film in connection with the other ingredients. Many wax manufacturers' company publications provide comprehensive information about waxes and their emulsions, their production and properties. There are also some manufacturers who offer ready-made wax emulsions. Examples include:

• 1. Emulsions with natural waxes anionic
  
• 2. Emulsions with modified montan waxes anionically nonionic
  
• 3. Emulsions with polyethylene waxes
  

The various types of emulsion can of course also be combined with one another, provided that there is compatibility due to the ionic character of all the constituents used.

With the use of silicones as leather care additives, as mentioned above, if necessary, it becomes common Silicone oils are used to improve water repellency, make polishing easier, optimize the flexibility of the care film and give the leather surface a deeper shine. Polymethylsiloxanes of low, medium and higher viscosity (e.g. Baysilon M 100, M 500, M 10,000) and polymethylsiloxane derivatives with, for example, amino-functional groups (e.g. Baysilone OF 4061; silicone oil SLM 50349) are common and customary. These products are water-insoluble and must be emulsified in water in the usual way for use in aqueous formulations. For this, silicone surfactants such as Dow Corning Q 2 3225 C can be used. Several manufacturers also offer aqueous silicone oil emulsions based on polymethylsiloxanes and various derivatives. Some silicone emulsion types are listed below by way of example: LE-467 HS Union Carbide, E 22 Wacker-Chemie, AN 2553 Goldschmidt (anionic); 347 Dow Corning, 7274 Dow Corning - amino functional -, E 10 Wacker-Chemie (non-ionic); 929 Dow Corning - amino functional -, VP 1019 Wacker-Chemie - amino functional - (cationic).

Reactive silicone types can be used for water-free formulations, e.g. Tegosivin LHZ from Goldschmidt.

Other care additives can be cleaned and stabilized wool fat derivatives (lanolins), which improve the surface of the treated leather and are used to adjust the properties in care products. If water-soluble lanolins are required, ethoxylated types (e.g. aqualose types from the Golden Dawn Company) are available. Also recently refined mink oil has been used in care products, which must be made water-miscible with the usual emulsifiers.

For the complete care of leather objects, a color refresh is sometimes necessary. This can be achieved by adding water-soluble or water-dispersing dyes or color pigments to the aerosol active ingredients. It must be taken into account that the dyes, together with the care and impregnation agents, have sufficient fastness to dry and wet rubbing. This requirement is met by finely dispersed organic and / or inorganic pigment preparations, e.g. Melustral colors, Helio real colors or Corial real colors. Most of these color pigments are also commercially available as fine dough preparations. Metal complex dyes can also be used to color the above-mentioned impregnating / care active ingredients, e.g. Irgaderm colors, Levaderm colors, Bayderm colors. Alcoholic ingredients can be colored with Sudan colors.

By appropriately mixing the basic colors, all the color shades that occur can be adjusted.

Other auxiliary substances (c) which may be present in the active ingredient (A) of the impregnating spray according to the invention are customary corrosion inhibitors (corrosion inhibitors) for tinplate and aluminum cans. Examples include: sodium benzoate; Disodium hydrogen phosphate; Vircopet 20, 30 and 40; Deriphate 151 C; Rewo B 3010; Sarcosyl NL 97; Dehyquart SP. In addition, fragrance substances (perfumes) of the type customary in this field may also be present in the active ingredient (A), such as Water, solvent and blowing agent, especially DME-resistant perfume oils. Customary anti-foaming agents may also be mentioned as any auxiliary substances (c) present.

The present in the impregnation spray according to the invention Water-miscible or emulsifiable blowing agents (B) are also explained in the above-mentioned application 84113475.2. (B) is advantageously a liquefied propellant, such as, for example, 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, especially ethanol or isopropanol, then a binary or ternary system of DME, water and / / forms in the impregnation spray. or alcohol, which is present in the form of a uniform phase within the known quantity ranges. 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. A liquefied (water-immiscible but) emulsifiable blowing agent, such as propane, butane or difluorodichloromethane, can also be present as blowing agent (B). However, compressed, water-miscible blowing agents, such as carbon dioxide, may also be present as blowing agents (B); nitrogen and nitrous oxide are further examples of compressed blowing agents.

The amount of active ingredient (A) in the impregnating spray according to the invention can vary depending on its type and on the type of blowing agent (B) present. In general, 30 to 70% by weight of active ingredient (A) (based on the finished filling formulation) is present. An amount of active ingredient of 40 to 65% by weight has proven particularly useful.

The amount of blowing agent (B) present can also vary. It is usually 70 to 30% by weight th blowing agent, such as dimethyl ether, propane or butane. Compressed blowing agents, such as carbon dioxide, can also be used; their amount (in the finished filling recipe) is then 0 to 7% by weight, preferably 0 to 5% by weight.

The amounts of the components (components) (a), (b) and (c) from which the active ingredient (A) is composed can vary within ranges. The active ingredient (A) (i.e. the active ingredient formulation) advantageously has the composition given below, the amount of the components in each case being given in% by weight, again based on the active ingredient formulation:

In the case of an active ingredient without leather care additives

In the case of an active ingredient with care additives

The present invention also relates to the use of the impregnating spray according to the invention described above for the treatment of leather and textiles. 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.

As mentioned above, there is a functional interaction between the fluorocarbon resins and the polyacrylate component additionally present according to the invention in the sense that this combination leads to a surprisingly synergistic hydrophobization enhancement. This synergism already occurs with relatively small amounts of acrylic polymer, as stated above. It is expressed by the fact that with the same amount of fluorocarbon resin the hydrophobizing effect can be increased disproportionately by the addition of acrylate resins; furthermore it is also possible to reduce the amount of fluorocarbon resin and at the same time to compensate or overcompensate for the hydrophobizing effect by adding acrylate resins. Such a functional interlocking of fluorocarbon resin component and acrylate resin component represents a completely unexpected phenomenon. Reference is made in detail to the test report below. In the present case, similar to the application 84113475.2 mentioned, the special advantage of toxicological compatibility should also be pointed out. In the present case, inhalation toxicological investigations of recipes according to the invention, ie acrylate-containing formulations, showed that no LC ₅₀ values could be determined, even with such formulations, the color substances (as auxiliary (c)) contained. The toxicological tests were carried out in accordance with the method described in OECD Protocol 403. This animal experiment allows to obtain acute inhalation toxicological data, which are expressed in the LC ₅₀ value in rats after four hours of exposure (LC lethal in 50% of the test animals, inhalation concentration in 50% of the test animals). Recipes according to the invention showed no mortality rates even at the very high concentration of 50 g / m ³ (higher concentrations are not technically feasible according to the OECD 403 method mentioned).

The following examples illustrate the invention without restricting its application. The stated numerical figures each represent percentages by weight, based on the active ingredient formulation or based on the filling formulation.

Example 1

This example explains impregnation sprays according to the invention, the active ingredients (A) (active ingredient formulations) of which contain no leather care additives.

Example: 1 2

Die in den vorstehenden Beispielen genannten Wirkstoffrezepturen können jeweils auch in eingefärbter Form vorliegen, d.h. Farbstoffe enthalten. Nur beispielsweise seien einige Einfärberezepturen genannt:This example explains impregnation sprays according to the invention, the active ingredients (A) (active ingredient formulations) of which contain leather care additives.

The active ingredient formulations mentioned in the examples above can also be in colored form, ie they contain dyes. Some coloring recipes are just a few examples:

Versuchsbericht (Beleg des synergistischen Hydrophobiereffekts)

Test report (evidence of the synergistic water repellent effect)

The tests for determining the hydrophobizing effect were carried out in accordance with DIN 53 338 "Determination of the Behavior towards Water under Dynamic Stress in a Penetrometer". This standard has been specially developed for testing leather.

The test pieces cut out of the leather (according to DIN 53 302 Part 1) were each with 30 g of the test formulations A 1, A 2, A 3; B 1, B 2, B 3 and C 1, C 2, C 3 sprayed and allowed to dry overnight in an air-conditioned room. The water penetration times were then determined in the penetrometer in accordance with DIN 53 338.

The test formulations and the water penetration times according to DIN 53 338 of the individual tests on different types of leather can be found in the following tables. The water penetration times given are mean values from four measurements, with the highest and lowest values being deleted.

Tables A a), B a) and C a): In the experiments listed, the numbers A 1, B 1 and C 1 are fillings that contain only fluorocarbon resins in increasing amounts (dissolved in isopropanol) and (with propane / Butane) are filled in aerosol cans. The bottlings A 2, B 2 and C 2 contain only acrylates as impregnating agents; Solvents and propellants are analogous to A 1, B 1 and C 1. A 3, B 3 and C 3 list the fillings that contain both FC resin and acrylates - in the same proportions as before - at the same time.

In Tables A b), B b) and C b) the times are on given that the water needs to penetrate the corresponding leather according to DIN 53 338; A 3, B 3 and C 3 each show the penetration times of the combination of fluorocarbon resin and acrylate. These clearly exceed the values of the individual measurements.

From these values it can be seen that the water penetration times which can be achieved with formulations based exclusively on fluorochemicals or acrylic polymers are clearly exceeded (compared to the values to be expected additively) in the case of the combination of fluorochemical and acrylic polymer. Depending on the recipes and the leathers used, this results in water penetration times that are 1.4 to 3.5 times cheaper. This disproportionate improvement in the waterproofing performance of the compositions according to the invention is surprising and was not to be expected.

Claims (5)

1. Impregnation spray for leather and textiles, containing (A) an active ingredient that consists of (a) fluorocarbon resins, (b) a solvent (LA) from the group water and _/ or a water-miscible solvent (LW) and optionally (c) excipients, and (B) one or more water-miscible or emulsifiable blowing agents, characterized in that the active ingredient (A) also contains a hydrophobicizing agent based on polyacrylate as an obligatory component. 2. Impregnation spray according to claim 1, characterized in that the polyacrylate hydrophobizing agent is present in the active ingredient (A) in an amount of 0.1 to 2.0% by weight, based on the active ingredient formulation. 3. Impregnation spray according to one of the preceding claims, characterized in that the polyacrylate hydrophobizing agent is a homo- or copolymer of acrylic acid esters or methacrylic acid esters. 4. Impregnation spray according to one of the preceding claims, characterized in that the polyacrylate hydrophobizing agent is solvent-free, solvent-containing or an aqueous dispersion. 5. Use of a spray characterized in the preceding claims for the treatment of leather and textiles.