Additive-Containing Paints

Europaisches Patentamt 449 M European Patent Office m) Publication number: 0190 B1 Office europeen des brevets

EUROPEAN PATENT SPECIFICATION

Date of publication of the patent specification : intci- C09D 7/12 09.08.89 Application number: 85116046.5 Date of filing: 16.12.85

Additive-containing paints.

Priority: 03.01.85 IT 1900885 Proprietor: OECE Industrie Chimiche Spa, via Voltumo 96, 1-41032 Cavezzo (Modena)(IT)

@ Date of publication of application : 13.08.86 Bulletin 86/33 Inventor: Raffaellini, Peppino, via della Liberia 20, 1-41032 Cavezzo (Modena)(IT) Inventor: Benattl, Gastone, via Gavioli 132, Publication of the grant of the patent : 1-41032 Cavezzo (Modena)(IT) Bulletin 89/32 Inventor: Vernizzi, Giorgio, via Carbonieri 47, 09.08.89 1-41100 Modena(IT) Inventor: Trevisan, Luclo, via Galimberti 9, Parma(IT) Designated Contracting States: FR GB IT LI LU NL SE AT BE CH DE Representative: Gervasl, Gemma, Dr. et al, Studio Brevetti e Marchi NOTARBARTOLO & GERVASI 33, Viale Blanca Maria, 1-20122 Milano(IT) References cited: EP-A- 0093 198 CA-A-899782 CH-A-293434 US-A-2103830

Q Note- Within nine months from the publication of the mention of the grant of the European patent, any person may give notice to the European Patent Office of opposition to the European patent granted. Notice of opposition shall be filed in a written reasoned fee has been paid (Art. 99(1) European patent ft statement. It shall not be deemed to have been filed until the opposition M convention). ^ ACTORUM AG EP 0190 449 B1

Description <-

The present invention relates to novel paints showing a lower irritating power on the respiratory and 5 conjunctival mucosae, and improved olfactory characteristics. More precisely, the present invention d relates to paints from natural or synthetic materials, applicable as solutions to any types of surfaces, to which substances suitable to:

a) neutralize the irritating effect on the mucosae of the volatile substances contained in the paints, es- 1 o sentially the volatile monomers and the solvents; and/or to b) prevent the cellular-metabolic damages caused by the volatile components of the paints, as they have been hereinabove defined, on the respiratory and conjunctival mucosae, by increasing the immunologic defenses of the organism itself; and to c) modify the olfactory characteristics of volatile components having an unpleasant smell, so as to ob- 15 tain end products with a pleasant smell, have been added. The additive-containing paints according to the present invention are essentially pertaining to the following classes:

20 A - paints on the basis of natural resins, such as shellac or the most soluble varieties of Manilla co- pals, which are generally applied as solutions in ethyl alcohol, and dried by evaporation of the solvent; B - paints on the basis of cellulose derivatives, which are generally applied as solutions in blends of volatile solvents, easily removable by evaporation at room temperature, or also by suitable heating. The more largely used cellulose derivatives are nitrocellulose and cellulose esters (acetate, butyrate) and 25 cellulose ethers (e.g., ethylcellulose); C - paints on the basis of synthetic resins, and essentially polyurethane resins, polyisocyanates and polyisocyanurates, saturated or unsaturated polyesters, polyacrylates, epoxy, ureic and melamine resins, alkyd, ketonic, coumarone, silicone, polyamide resins, polymers and copolymers from unsaturated hydrocarbons. All these resins are applied in the presence of blends of organic solvents and often, in 30 particular in the case of polyester resins, of polyurethane resins and of polyisocyanates, in the presence of monomers or of oligomers crosslinking under the application conditions, remaining incorporated within the same paints. The monomers most commonly used as solvent/crosslinking agents in the paints are styrene, diisocianates, acrylates, epoxides.

35 From the above, it is clear that the different families of paints, and specifically the single paints, show different problems of toxicity and of intolerability for the user. Whilst indeed in the case of the paints of groups (A) and (B) and of many paints of group (C) the nega- tive effects for the user are only deriving from the use of volatile solvents, for some paints from group (C) a strong influence is due to the presence in the applied solution of monomer substances, which are 40 not completely fixed by the crosslinking reaction, and are evaporated together with the solvent. Moreover for all paints the irritating effect for the mucosae is to be taken into account, which is due to the dusts originated by the sanding, and is caused both by mechanical effect, and by the chemical activity of the same dusts. The prior art in this field proposes in EP-A 0 093 398 to add to polyurethane paints and varnishes a 45 compound consisting of substances possessing hydrogen atoms designed to react with isocyanic groups in free monomers to reduce certain harmfull effects, united with fixing agents to enhance the ol- factive properties of said paints; and proposes e.g. in US-A 2 103 830 to mask the odour of paints by adding certain volatile fragrants and fixing agents. We have now found, and is the object of the present invention, that definite groups exist of therapeu- 50 tic substances which, if suitably mixed with the components of the paints before the application thereof, within defined concentration limits, are in no way alterating the characteristics thereof, but are vapourized together with the solvents by which the same paints are applied and reach therefore the respiratory and conjunctival mucosae together with them in an amount sufficient to neutralize the noxious effects both of the solvents and of the volatile components of the paints. 55 Moreover, a limited amount of the therapeutical substance remains incorporated within the paint, so as to neutralize the irritating effects of the dusts originated by the sanding. As initially said, the therapeutic substances allowing the present invention to be realized may belong to the categories (a) and (b). They have however certain characteristics which are critically common to all useful substances, and precisely: they do not have reactive groups capable of reacting with and 60 hence altering the components of the paints; they do not show side reactions; they are not photosensi- tive; they are not altered by the components of the paints; they have a high enough vapour pressure in s the adopted solvent system, to be vapourized together with said solvents under the conditions of paint application; their concentration in the system must be such that, considering the equilibrium which is es- V* tablished between the liquid phase and the gas phase, into this latter passes an amount of product 65 enough to produce the desired prophylactic or therapeutical effect. « EP 0 190 449 B1

In practice, it was very difficult to find out substances in harmony with these requisites and in many cases it was necessary to modify the solvent system of the paint, and the application modalities, in order to achieve the desired effect. We have found that substances belonging to the (a) group as hereinabove defined, i.e. substances 5 capable of neutralizing the irritative effect of the solvents and of the volatile monomers on the mucosae, which can be used according to the present invention, are: salbutamol, clenbuterol, terbutaline, fenoterol, isoprotenerol, bitolterol, orciprenaline, ephedrine, and in general the derivatives of phenylethanolamines with therapeutical activity; theophylline and its derivatives, tretoquinol, ketotifen, guaiacol, ethylorthoformate, sobrerol, bromhexine and derivatives thereof, thioproline, acetylcysteine and deriv- 1 o atives thereof, and procaterol. Substances belonging to the group (b) as hereinabove defined, i.e. substances capable of increasing the immunologic defences of the organism, when they are brought into contact with the mucosae, which can be used according to the present invention, are e.g.: cromoglycic acid and its derivatives, oxatomide, astemizole, fenspiride, beclomethasone, and lodoxamide. 15 Substances which are on the contrary belonging to the group (c) as hereinabove defined, i.e., substances suitable to modify the olfactory characteristics of the paints, which are used according to the present invention, are the terpenic substances of alcoholic or phenolic character, such as e.g. terpine- oi, iinalol, eugenoi, iso-eugenol, benzyl-iso-eugenol, geraniol, rhodinol, borneol, tetrahydrolinalol, citronellol, neroi, carvol, farnesol, safrole, thymol and anethole. 20 In association with the aromatic and aromatizing substances, it is generally necessary to use fixative agents, i.e., products capable of modifying the vapour pressure of the terpenes and hence dilute the elimination thereof over a longer time interval. As fixative agents, we may mention as examples vanillin, coumarin, and heliotropin. The terpenic substances, or the system of terpenic substances capable of modifying the olfactory 25 characteristics of the paints, must be defined everytime with reference to well-defined products, according to the additive-containing paint and hence to the particular olfactory problems presented by it. As a general, rule, it is however preferable to use a "system" of terpenes, within which the concentration of each component may range within broad limits, generally comprised between 0 and 50% of total mixture. 30 Also the fixative agents are preferably used as combinations, rather that as single products, the total amount thereof representing generally from 1 to 10% of used terpenes. The compounds of groups (a), (b) and (c) as hereinabove defined, may be used with any types of paints belonging to classes A, B and C. The compounds (a) and (b) are generally used alternatively, whilst the compounds (c) are always used in combination with at least a compound selected from classes (a) and (b). 35 In particular, we have found that the use of terpenes is compatible with the use of prophylactic and therapeutic substances as defined hereinabove, considering that in case of simultaneous use of the two types of products, to the many requisites required for the therapeutic agents, also the chemical inert- ness thereof towards the terpenes is to be added. Moreover, as already mentioned, in many cases it is necessary to modify the solvent system normally 40 employed. In fact, it resulted particularly difficult to identify a combination of solvents capable of acting both as vehicle for the components of the paint, and as vehicle for the therapeutic substance, maintain- ing unchanged the technological-applicative characteristics of the same paints. The novel additive-containing paints according to the present invention may contain, besides the already mentioned substances, also other additives conferring a pleasant smell to the paints, or different 45 additives. The amount of compounds with prophylactic or therapeutic action to be used in the paints according to the present invention, may range within broad limits, depending on the activity of the compound used, on the characteristics of the polymers constituting the film-forming agent of the paints and on the solvents used for the application of the same paints, solvents which after all are the "vehicle" of the therapeutic substances which are brought into contact with the mucosae. 50 As for the terpenic compounds and fixative agents, the amount thereof is adjusted on the basis of the composition of the paint, and in particular on the basis of the composition of the volatile portion. The therapeutic additives and the terpenic compounds can be uniformly incorporated into the paints both by pre- paring partial pre-blends which are then mixed into end products, before the application, and by uniformly incorporating them into the paints immediately before the application. 55 To the purpose of illustrating the invention, we report hereinunder some examples of specific embodi- ments thereof.

65 EP 0190 449 B1

Examples 1-4

Preparation of polyurethane paints

Part A Opaque 1 Opaque 2 Primer Sealer Alkyd resin (60% in xylene) 50 60 60 Saturated polyester resin (100%) - 25 10 Toluene 10 11 15 25 Ethyl acetate 22 13 10 30 Butyl acetate 16 11 13 15 Ethyleneglycol monoether acetate - 3-5 15 Silica 2 2 Zincstearate - _ 2 - PartB Polyisocyanate (75% in ethyl acetate) 15 15 - 35 20 Polyisocyanate (50% in butyl acetate) 10 15 25 Butyl acetate 20 15 20 10 Ethyleneglycol monoether acetate 5 5 5 5 25 Additive DH1 0.2 0.2 0.2 0.2 Ethyl cromoglycate 0.01% 0.01% 0.01% 0.01%

The additive Dhi is a mixture of terpenes in the following proportions: 30 alpha-terpineol 15% linalol 15% eugenol 32% 35 isoeugenol 24% geraniol 5% borneol 3% helkrtropin 3% 40 coumarin 3%

Percentages are by weight. To the same paints instead of ethyl cromoglycate a corresponding percentage (0,01%) of salbutamol, 45 ephedrine, terbutaline, ethylorthoformate has been added, in any case obtaining equivalent results, in the tests indicated hereinunder. Example 5 50 . Unsaturated polyester paint (67% in 83 styrene) Monomer styrene 16.9 55 Paraffin (m. p. 48-58°C) 0.1 Additive DH2 0.2 Ketotifen 0.01%

60 The additive DH2 is a mixture of terpenes in the following proportions:

65 EP 0 190 449 B1

farnesol 15% Tetrahydrolinalol 30% safrole 20% citronellol 20% thymol 2% anethole 5% 10 carvol 5% heliotropin 2% coumarin 1%

15 Paints of equivalent composition have been prepared by replacing ketotifen with the same amount of astemizole, fenspiride, oxatomide, in each case obtaining equivalent results from the viewpoint of the protection from the inflammatory action of the paints, and from the olfactory viewpoint. All the paints prepared as hereinabove shown, have been supplied to skilled users, who have attend- 20 ed to the application thereof for periods ranging from 7 to 30 days. In all cases it has been objectively found that the operating conditions were extremely more comfortable than normally, thanks to the absence of irritation of the eyes and of the respiratory ways and due to the absence of unpleasant smell which often, besides indicating the presence of pollutants, creates in the user a notable discomfort of psychologic character. 25 The series of tests which have been carried out allows it to be stated that by means of the novel paints it is possible to create working conditions more comfortable and less dangerous to the user, thus drasti- cally reducing the incidence of professional diseases and improving the yield. It is moreover clear that the absence of the well-known unpleasant paint smell, persisting within home or working rooms for a long time, is already perse a great advantage and a noticeable technical improve- 30 ment in the field. Claims for the Contracting States BE, CH, DE, FR, GB, IT, LI, LU, NL, SE

1 . Paints containing additives having such a therapeutic or prophylactic action, as to neutralize or pre- 35 vent the irritating effect of the volatile components of the paints on the respiratory and conjunctival mucosae, said additives comprising at least one substance selected from the following groups a) and/or b) and at least one substance of the following group c): a) therapeutic substances capable of neutralizing the irritating effect of the volatile components of the paints and selected from the group constituted by the derivatives of phenylethanolamines, teo- 40 phylline and its derivatives, tetroquinol, ketotifen, guaiacol, sobrerol, ethylorthoformate, bromhexine and derivatives thereof, thioproline, acetylcysteine and derivatives thereof, procaterol; b) propylactic substances capable of increasing the immunologic defenses of the organism when they are brought into contact with the mucosae, and selected from the group constituted by cromoglycic acid and its derivatives, oxatomide, astemizole, fenspiride, beclomethasone and lodoxamide; 45 c) terpenic substances of alcoholic or phenolic character, capable of modifying the olfactory characteristics of the paint and selected from the group constituted by terpineol, linalol, eugenol, isoeugenol, benzylisoeugenol, geraniol, rhodinol, berneol, tetrahydrolinalol, citronellol, nerol, carvol, farnesol, safrole, thymol and anethole. 2. Paints according to claim 1 wherein the substances of group a) the class of phenylethanolamines de- 50 rivatives are selected from salbutamol, clenbuterol, terbutaline, fenoterol, isoprotenerol, bitolterol, orciprenalina, ephedrine. 3. Paints according to claim 1 wherein the terpenic substances of group c) are used in combination with a fixative agent selected from vanillin, coumarin and heliotropin.

55 Claims for the Contracting State AT

1 . Paints containing additives having such a therapeutic or prophylactic action, as to neutralize or prevent the irritating effect of the volatile components of the paints on the respiratory and conjunctival mucosae, said additives comprising at least one substance selected from the following groups a) and/or b) 60 and at least one substance of the following group c): a) therapeutic substances capable of neutralizing the irritating effect of the volatile components of the paints and selected from the group constituted by the derivatives of phenylethanolamines, teo- phylline and its derivatives, tretoquinol, ketotifen, guaiacol, sobrerol, ethylorthoformate, bromhexine and derivatives thereof, thioproline, acetylcysteine and derivatives thereof, procaterol; 65 b) propylactic substances capable of increasing the immunologic defenses of the organism when they EP 0 190 449 B1

are brought into contact with the mucosae, and selected from the group constituted by cromoglycic acid and its derivatives, oxatomide, astemizole, fenspiride, beclomethasone and lodoxamide; c) terpenic substances of alcoholic or phenolic character, capable of modifying the olfactory characteristics of the paint and selected from the group constituted by terpineol, linalol, eugenol, isoeugenol, 5 benzylisoeugenol, geraniol, rhodinol, berneol, tetrahydrolinalol, citronellol, nerol, carvol, farnesol, safrole, thymol and anethole. 2. Paints according to claim 1 wherein the substances of group a) of the class of phenylethanolamines derivatives are selected from salbutamol, clenbuterol, terbutaline, fenoterol, isoprotenerol, bitolterol, orciprenalina, ephedrine. 10 3. Paints according to claim 1, wherein the terpenic substances of group c) are used in combination with a fixative agent selected from vanillin, coumarin and heliotropin. 4. Process for obtaining paints wherein the irritating effect of the volatile components of the paints on the respiratory and conjunctival mucosae is substantially reduced, characterized in that in the paints are incorporated by mixing at least one substance selected from the following groups a) and/or b) and at 15 least one substance of the following group c): a) therapeutic substances capable of neutralizing the irritating effect of the volatile components of the paints and selected from the group constituted by the derivatives of phenylethanolamines, teophyl- line and its derivatives, tretoquinol, ketotifen, guaiacol, sobrerol, ethylorthoformate, bromhexine and derivatives thereof, thioproline, acetylcysteine and derivatives thereof, procaterol; 20 b) propylactic substances capable of increasing the immunologic defenses of the organism when they are brought into contact with the mucosae, and selected from the group constituted by cromoglycic acid and its derivatives, oxatomide, astemizole, fenspiride, beclomethasone and lodoxamide; c) terpenic substances of alcoholic or phenolic character, capable of modifying the olfactory characteristics of the paint and selected from the group constituted by terpineol, linalol, eugenol, isoeugenol, 25 benzylisoeugenol, geraniol, rhodinol, berneol, tetrahydrolinalol, citronellol, nerol, carvol, farnesol, safrole, thymol and anethole.

Revendications pour les Etats contractants BE, CH, DE, FR, GB, IT, LI, LU, NL, SE 30 1. Peintures contenant des additifs ayant une action therapeutique ou prophylactique telle qu'ils neu- tralisent ou previennent I'effet irritant des constituants volatils des peintures sur les muqueuses respiratoires et conjonctives, caracterisees en ce que ces additifs comprennent au moins une substance choisie parmi les groupes (a) et/ou (b) suivants, et au moins une substance du groupe (c) suivant: a) des substances therapeutiques capables de neutraliser I'effet irritant des constituants volatils des 35 peintures, et choisies parmi les derives des phenylethanolamines, la theophylline et ses derives, le tretoquinol, le ketorifene, la guaiacol, le sobrerol, I'orthoformiate d'ethyle, la brohexine et ses derives, la thioproline, I'acetylcysteine et ses derives, le procaterol; b) des substances prophylactiques capables d'augmenter les defenses immunologiques de Porganisme lorsqu'elles sont amenees au contact des muqueuses, et choisies parmi I'acide cromoglycique et ses 40 derives, I'oxatomide, I'astemizole, le fenspiride, la beclomethasone et le lodoxamide; c) des substances terpeniques de caractere alcooiique ou phenolique, capables de modifier les carac- tiristiques olfactives de la peinture, et choisies parmi le terpineol, le linalol, I'eugenol, I'isoeugenol, le benzylisoeugenol, le geraniol, le rhodinol, le borneol, le tetrahydrolinalol, le citronellol, le nerol, le carvol, le farnesol, le safrol, le thymol et I'anethol. 45 2. Peintures selon la revendication 1 , caracterisies en ce que les substances du groupe (a) de la clas- se des derives de phenylethanolamines sont choisies parmi le salbutamol, le clenbuterol, la terbutaline, le fenoterol, I'isoproterenol, le bitolterol, I'orciprenaline, I'ephedrine. 3. Peintures selon la revendication 1 , caracterisees en ce que ies substances terpeniques du groupe (c) sont utilisees en association avec un agent fixateur choisi parmi la vanilline, la coumarine et I'heliotro- 50 pine.

Revendications pour I'Etat contractant AT 1. Peintures contenant des additifs ayant une action therapeutique ou prophylactique tels qu'ils neu- 55 tralisent ou previennent I'effet irritant des constituants volatils des peintures sur les muqueuses respiratoires et conjonctives, caracterisees en ce que ces additifs comprenant au moins une substance choisie parmi les groupes (a) et/ou (b) suivants, et au moins une substance du groupe (c) suivant: a) des substances therapeutiques capables de neutraliser I'effet irritant des constituants volatils des peintures, et choisies parmi les derives des phenylethanolamines, la theophylline et ses derives, le 60 tretoquinol, le ketotifene, le guaiacol, le sobrerol, I'orthoformiate d'ethyle, la brohexine et ses derives, la thioproline, I'acetylcysteine et ses derives, le procaterol; b) des substances prophylactiques capables d'augmenter les defenses immunologiques de I'organisme lorsqu'elles sont amensees au contact des muqueuses, et choisies parmi I'acide cromoglycique et ses derives, I'oxatomide, I'astemizole, le fenspiride, la beclomethasone et le lodoxamide; 65 c) des substances terpeniques de caractere alcooiique ou ph<§nolique, capables de modifier les carac- EP 0 190 449 B1

teristiques olfactives de la peinture, et choisies parmi le terpinSol, le linalol, I'eugSnol, I'isoeug6nol, le benzylisoeugSnol, le geYaniol, le rhodinol, le borneol, le telrahydrolinalol, le citronellol, le nerol, le carvol, le farn§sol, le safrol, le thymol et I'aneihol. 2. Peintures selon la revendication 1 , caracterisees en ce que les substances du groupe (a) de la clas- 5 se des de>iv6s des ph§nyl6thanolamines sont choisies parmi le salbutamol, le clenbuteYol, la terbutaline, le fenoteYol, I'isoprote're'nol, le bitolterol, I'orcipr6naline, I'ephedrine. 3. Peintures selon la revendication 1 , caracterisees en ce que les substances terpeniques du groupe (c) sont utilisees en association avec un agent fixateur choisi parmi la vanilline, la coumarine et I'heliotro- pine. 10 4. Precede de preparation de peintures dans lesquelles I'effet irritant des constituants volatils des peintures sur les muqueuses respiratoires et conjonctives est notablement r§duit, caracterise en ce qu'on a incorpor6 aux peintures, par melange, au moins une substance choisie dans les groupes (a) et/ou (b) suivants et au moins une substance du groupe (c) suivant: a) des substances therapeutiques capables de neutraliser I'effet irritant des constituants volatils des 15 peintures, et choisies parmi les derives des phenytethanolamines, la theophylline et ses deYiv6s, le tretoquinol, le ketotifene, le guaiacol, le sobrerol, Porthoformiate d'ethyie, la brohexine et ses derives, la thioproline, I'acetylcysteine et ses derives, le procaterol; b) des substances prophylactiques capables d'augmenter les defenses immunologiques de I'organisme lorsqu'elles sont amenees au contact des muqueuses, et choisies parmi I'acide cromoglycique et ses 20 derives, I'oxatomide, I'astemizole, le fenspiride, la beclomethasone et le lodoxamide; c) des substances terpeniques de caractere alcoolique ou phenolique, capables de modifier les carac- teristiques olfactives de la peinture, et choisies parmi le terpineol, le linalol, Peugenol, I'isoeugenol; le benzylisoeugenol, le geraniol, le rhodinol, le borneol, le tetrahydrolinalol, le citronellol, le neYol, le carvol, le farnSsol, le safrol, le thymol et I'an&hol. 25

Patentanspriiche fur die Vertragsstaaten BE, CH, DE, FR, GB, IT, LI, LU, NL, SE 1. Anstriche, die Additive mit derartiger therapeutischer oder prophylaktischer Wirkung enthalten, 30 dal3 sie die Reizwirkung der fluchtigen Bestandteile der Anstriche auf die Atmungs- und Binde- hautschleimhaute neutralisieren oder verhindern, welche Additive mindestens eine Substanz ausgewahlt aus den folgenden Gruppen a) und/oder b) und mindestens eine Substanz der folgenden Gruppe c) umfassen: a) therapeutische Substanzen, die die Reizwirkung der fluchtigen Bestandteile der Anstriche neutrali- 35 sieren kQnnen und ausgewahlt sind aus der Gruppe bestehend aus den Derivaten von Phenylathanol- aminen, Theophyllin und dessen Derivaten, Tretochinol, Ketotifen, Guajacol, Sobrerol, Athylorthofor- miat, Bromhexin und dessen Derivaten, Thioprolin, Acetylcystein und dessen Derivaten und Procate- rol; b) prophylaktische Substanzen, die die immunologischen Abwehrkrafte des Organismus erhohen kon- 40 nen, wenn sie mit den Schleimhauten in Beruhrung gebracht werden, ausgewahlt aus der Gruppe bestehend aus Cromoglycinsaure und deren Derivaten, Oxatomid, Astemizol, Fenspirid, Beclomethason und Lodoxamid. c) Terpensubstanzen mit alkoholischem oder phenolischem Charakter, die die Geruchsmerkmale des Anstriches modifizieren konnen und ausgewahlt sind aus der Gruppe bestehend aus Terpineol, Lina- 45 lol, Eugenol, Isoeugenol, Benzylisoeugenol, Geraniol, Rhodinol, Borneol, Tetrahydrolinalol, Citronel- lol, Nerol, Carvol, Farnesol, Safrol, Thymol und Anethol. 2. Anstriche nach Anspruch 1, worin die Substanzen der Grupe a) der Klasse von Phenylathanolamin- derivaten ausgewahlt sind aus Salbutamol, Clenbuterol, Terbutalin, Fenoterol, Isoprotenerol, Bitolterol, Orciprenalin und Ephedrin. 50 3. Anstriche nach Anspruch 1, worin die Terpensubstanzen der Gruppe c) in Kombination mit einem Fi- xiermittel ausgewahlt aus Vanillin, Cumarin und Heliotropin verwendet werden.

Patentanspriiche fur den Vertragsstaat AT 55 1. Anstriche, die Additive mit derartiger therapeutischer oder prophylaktischer Wirkung enthalten, daB sie die Reizwirkung der fluchtigen Bestandteile der Anstriche auf die Atmungs- und Binde- hautschleimhaute neutralisieren oder verhindern, welche Additive mindestens eine Substanz ausgewahlt aus den folgenden Gruppen a) und/oder b) und mindestens eine Substanz der folgenden Gruppe c) 60 umfassen: a) therapeutische Substanzen, die die Reizwirkung der fluchtigen Bestandteile der Anstriche neutralisieren konnen und ausgewahlt sind aus der Gruppe bestehend aus den Derivaten von Phenylathanol- aminen, Theophyllin und dessen Derivaten, Tretochinol, Ketotifen, Guajacol, Sobrerol, Athylorthofor- miat, Bromhexin und dessen Derivaten, Thioprolin, Acetylcystein und dessen Derivaten und Procate- 65 rol; EP 0 190 449 B1

b) prophylaktische Substanzen, die die immunologischen Abwehrkrafte des Organismus erhohen konnen, wenn sie mit den Schleimhauten in Beruhrung gebracht werden, ausgewahlt aus der Gruppe bestehend aus Cromoglycinsaure und deren Derivaten, Oxatomid, Astemizol, Fenspirid, Beclomethason und Lodoxamid; 5 c) Terpensubstanzen mit alkoholischem oder phenolischem Charakter, die die Geruchsmerkmale des Anstriches modifizieren konnen und ausgewahlt sind aus der Gruppe bestehend aus Terpineol, Lina- lol, Eugenol, Isoeugenol, Benzylisoeugenol, Geraniol, Rhodinol, Borneol, Tetrahydrolinalol, Citronel- lol, Nerol, Carvol, Farnesol, Safrol, Thymol und Anethol. 2. Anstriche nach Anspruch 1, worin die Substanzen der Gruppe a) der Klasse von Phenylathanol- 10 aminderivaten ausgewahlt sind aus Salbutamol, Clenbuterol, Terbutalin, Fenoterol, Isoprotenerol, Bitol- terol, Orciprenalin und Ephedrin. 3. Anstriche nach Anspruch 1, worin die Terpensubstanzen der Gruppe c) in Kombination mit einem Fi- xiermittel ausgewahlt aus Vanillin, Cumarin und Heliotropin verwendet werden. 4. Verfahren zum Herstellen von Anstrichen, worin die Reizwirkung der fluchtigen Bestandteile der 15 Anstriche auf die Atmungs- und Bindehautschleimhaute wesentlich vermindert ist, dadurch gekenn- zeichnet, daB den Anstrichen durch Einmischen mindestens eine Substanz ausgewahlt aus den folgenden Gruppen a) und/oder b) und mindestens eine Substanz derfolgenden Gruppe c) einverleibt werden: a) therapeutische Substanzen, die die Reizwirkung der fluchtigen Bestandteile der Anstriche neutralisieren konnen und ausgewahlt sind aus der Gruppe bestehend aus den Derivaten von Phenylatha- 20 nolaminen, Theophyllin und dessen Derivaten, Tretochinol, Ketotifen, Guajacol, Sobrerol, Athylortho- formiat, Bromhexin und dessen Derivaten, Thioprolin, Acetylcystein und dessen Derivaten und Pro- caterol; b) prophylaktische Substanzen, die die immunologischen Abwehrkrafte des Organismus erhohen konnen, wenn sie mit den Schleimhauten in Beruhrung gebracht werden, ausgewahlt aus der Gruppe be- 25 stehend aus Cromoglycinsaure und deren Derivaten, Oxatomid, Astemizol, Fenspirid, Beclomethason und Lodoxamid; c) Terpensubstanzen mit alkoholischem oder phenolischem Charakter, die die Geruchsmerkmale des Anstriches modifizieren konnen und ausgewahlt sind aus der Gruppe bestehend aus Terpineol, Lina- lol, Eugenol, Isoeugenol, Benzylisoeugenol, Geraniol, Rhodinol, Borneol, Tetrahydrolinalol, Citronel- 30 lol, Nerol, Carvol, Farnesol, Safrol, Thymol und Anethol.