DE3103499A1 - Active ingredient-containing gel compositions having a depot action based on a polyurethane matrix and relatively high-molecular-weight polyols, and a process for the preparation thereof - Google Patents

Abstract

The invention relates to active ingredient-containing, anhydrous gel compositions having a depot action, comprising a polyurethane matrix and relatively high-molecular-weight polyols as dispersion medium, and active ingredients, and to a process for the preparation of the gel compositions in the presence of the active ingredients. Active ingredients which can be used are biocides, pharmaceuticals, ethereal oils, fragrances, paints, detergents, anti-ageing agents, lubricants and antistatics, inter alia. The process is characterised in that a) one or more di- and/or polyisocyanates are reacted with b) one or more polyhydroxyl compounds having a molecular weight of from 1000 and 12000 and an OH number of between 20 and 112, c) from 0.1 to 50 % by weight of active ingredients, based on a) -e), optionally d) catalysts for the reaction between isocyanate and hydroxyl groups, and optionally e) fillers and additives known per se from polyurethane chemistry, where the isocyanate characteristic number is between 15 and 60, the product of the functionalities of the polyurethane-forming components is at least 5.2, and the polyhydroxyl compounds are essentially free from hydroxyl compounds having a molecular weight of below 800.

Description

Geimasses containing active ingredients with a depot effect based on

a polyurethane matrix and higher molecular weight polyols, as well as a process for their production The invention relates to active ingredient-containing, anhydrous gel compositions with depot effect, consisting of a polyurethane matrix and higher molecular weight polyols as dispersants and active ingredients, as well as a process for the production of the gel masses in the presence of the active ingredients. Biocides, pharmaceuticals, and essential substances can be used as active ingredients Oils, fragrances, paints, cleaning agents, anti-aging agents, lubricants and antistatic agents and others are used.

Gel masses containing active ingredients with depot effect, in which the active ingredients are released into the surrounding medium over a period of weeks to months, are known, for example, from U.S. Patents 3,822,238 and 3,975,350. It is also known from DE-OS 25 21 265, containing water and / or alcohol Manufacture polyurethane-polyurea gels in the presence of fragrances. Here are carrier materials based on water-containing gels described, which can contain a wide variety of agents, e.g. pharmaceuticals, biocides or Fragrances.

However, such water gels have the disadvantage that many agents e.g. biocides, are decomposed relatively quickly due to the presence of water can and thus the time of the effectiveness of these gels, i.e. the depot effect, strong is shortened. It is also known that active ingredients are massive and / or foamed high molecular weight To incorporate polyurethanes (CH-PS 289 915).

However, such high molecular weight polyurethanes have the disadvantage that a high proportion of the incorporated liquid agents as a result of the pervasive A high molecular structure and / or too high a proportion of hard segments remains in the polyurethane and is therefore lost to the depot effect. Fixed active agents can only do a lot can be used to a limited extent; non-volatile solids do not migrate out and volatile solid agents can only be used for a very short time and in very little time Diffuse out the amount.

It has now surprisingly been found that gel masses with improved Depot effect, constant release of active ingredients, high concentration of active ingredients, good Stability of the active ingredient additives and good migration ability of the active ingredients is maintained, when active ingredients are dissolved or dispersed in higher molecular weight polyols and di- and / or Polyisocyanates, as well as catalysts and, if necessary, conventional additives are mixed in, whereby the requirements to be mentioned must be met.

The advantages of the new gel masses are that in the only partially cross-linked polyurethane matrix a high proportion of higher molecular weight polyols is present, which enables the migration and release of the active ingredients to the outside and controls.

The active ingredient-containing gels are obtained by one or more higher functional, higher molecular weight polyols in the presence of the active ingredients and optionally in the presence of catalysts and customary fillers and additives for polyurethanes, with such an amount of organic di- and / or polyisocyanates that an isocyanate number of about 15 to 60 results. Under "Isocyanate number" In the following, the equivalence ratio (NCO / OH) x 100 is to be understood.

As has been found, elastic ones according to the invention are only produced then and sufficiently dimensionally stable gels made from a covalently crosslinked polyurethane matrix and one or more stuck in it (i.e. without the risk of annoying exudation) bound polyols are built up if the isocyanate reacting with one another or polyol components have a certain minimum functionality and if the Polyols essentially free of fractions with a molecular weight below 800, preferably below 1000.

The present invention thus relates to active ingredient-containing substances Gels consisting of (1) 15-62% by weight, preferably 20-57% by weight, particularly preferred 25-47% by weight, based on the sum of (1) and (2) of a high molecular weight matrix and (2) 85 to 38% by weight, preferably 80-43% by weight, particularly preferably 75-53 % By weight, based on the sum of (1) and (2), of one in the matrix due to secondary valence forces bound liquid dispersant, (3) active ingredients, and optionally (4) 0 to 100% by weight, based on the sum of (1) and (2), of fillers and / or additives, which are characterized in that a) the high molecular weight matrix is covalent is crosslinked polyurethane, b) the liquid dispersant of one or more Polyhydroxyl compounds with a molecular weight between 1000 and 12,000, preferably between 1700 and 6000, and an OH number between 20 and 112, preferably between 28 and 84, particularly preferably between 30 and 56, where- at the dispersant does not have essentially any molecular weight hydroxyl compounds below 800, preferably below 1000, and c) 0.1-50% by weight, preferably 0.5-35% by weight, particularly preferably 0.75-25% by weight, of active ingredient in the active ingredient-containing Gel mass are included.

As already mentioned, the gels according to the invention can surprisingly simply by direct reaction of polyisocyanates with the higher molecular weight mentioned Polyhydroxyl compounds in the presence of the active ingredients in an isocyanate number range from about 15 to 60, preferably 20 to 45, particularly preferably 25 to 40, produced if the polyurethane-forming components (polyisocyanates and polyhydroxyl compounds) together are polyfunctional, i.e.

provided the product of isocyanate functionality and (as below on Described on page 6) polyol functionality to be calculated is greater than 4, i.e. that e.g.

one or more, more than bifunctional components in the polyurethane formation reaction can be used.

Otherwise there will be no gels made from a covalently cross-linked polyurethane matrix and not converted polyols, but those known per se from polyurethane chemistry, liquid OH prepolymers.

In general, the polyurethane-forming components must all the more be more functional, the lower the isocyanate number, the used Polyol can have primary and / or secondary OH groups.

In the case of using mixtures of polyols with primary and secondary OH groups, it should be noted that the primary hydroxyl compounds are preferred react with the isocyanate component, so that under "functionality of the polyol component" then - essentially the OH functionality of the primary polyol is to be understood. For the purposes of the present invention, however, should be used to calculate the isocyanate index the total amount of the polyol component is used in each case.

In the manufacture of the polyurethane matrix, the product is said to have isocyanate functionality and, as described above, the polyol functionality to be calculated at least 5.2, preferably at least 6.2, in particular at least 8, particularly preferably even be at least 10.

A functionality product of 5.2 is, for example, a key figure range of about 60 is achieved when using a polyol component with a functionality of 2.6 and a diisocyanate is used.

In the case of an isocyanate number of 50 and purely primary and secondary Polyol component should be the product of the functionalities at least 6.2, preferably 8 loading wear; in the case of an isocyanate number of 30 and pure primary or secondary polyol component, at least 9, preferably at least 10 .. More details in this regard can be found in the exemplary embodiments.

The invention therefore also relates to a method for production of active ingredient-containing, anhydrous gel masses with depot effect based on Polyurethane gels, which is characterized in that a) one or more Di- and / or polyisocyanates with b) one or more polyhydroxyl compounds with a molecular weight between 1000 and 12,000, preferably between 1700 and 6000, and an OH number between 20 and 112, preferably between 28 and 84, particularly preferably between 30 and 56, c) 0.1 to 50% by weight, preferably 0.5 to 35% by weight and particularly preferably 0.75 to 25% by weight of active ingredients, based on the sum a-e, optionally d) catalysts for the reaction between isocyanate and Hydroxyl groups and, if appropriate, e) known per se from polyurethane chemistry Fillers and additives, mixes, with the isocyanate number between 15 and 60, the product of the functionalities of the polyurethane-forming components is at least 5.2, preferably 6.2, in particular 8, particularly preferably 10 and the polyhydroxyl compounds are essentially free of hydroxyl compounds with a molecular weight below 800, preferably below 1000.

The consistency of the gels according to the invention can vary between a jelly or gelatinous and a more or less highly elastic state. This As is explained in the exemplary embodiments, the range becomes wide with variation the isocyanate number and the functionality of the starting components swept over.

It is particularly surprising that the gels according to the invention are extraordinary are stable. Even after prolonged storage there is no significant phase separation a. The dispersant polyol is therefore very firmly held in the gel. By suitable selection of the mixing partners, gels can be obtained in which one The dispersant is not released even at temperatures of 50 to 1000C. As a result of the insolubility in dimethylformamide, one can assume that the polymer chains are at least partially covalently crosslinked in the gels according to the invention, while the remaining part of the polymer chains or the free polyols above Secondary valence forces or mechanical entanglements are bound. It seems a lot Surprisingly, a large part of the polyols apparently also after the reaction with polyisocyanates is still present in the polyurethane matrix without polyurethane formation, since it is as such e.g. can be extracted.

As explained, the polyol or polyols fulfill their function in addition to their function as a structural component for the polyurethane matrix also the role of the dispersant, this also for the solubility, migration and release of the active ingredients from the gel plays an essential role.

In the case of the higher molecular weight polyols to be used according to the invention it is preferably those known per se in polyurethane chemistry, at room temperature or a little above liquid polyhydroxy polyester or polyether, -polythioethers, -polyacetals, -polycarbonates or -polyesteramides of the above Molecular weight range, OH number range and OH functionality.

The possible hydroxyl group-containing polyesters are e.g. reaction products of polyvalent, preferably divalent and optionally additionally tri and tetravalent alcohols with polyhydric, preferably dihydric Carboxylic acids. Instead of the free polycarboxylic acids, the corresponding related Polycarboxylic acid anhydrides or corresponding polycarboxylic acid esters of lower alcohols or mixtures of these can be used to produce the polyesters. The polycarboxylic acids can be aliphatic, cycloaliphatic, aromatic and / or heterocyclic Be natural and optionally substituted and / or unsaturated, for example by halogen atoms be.

Examples of such polycarboxylic acids and their derivatives are called: adipic acid, sebacic acid, phthalic acid, phthalic anhydride, tetrahydro- or hexahydrophthalic anhydride, isophthalic acid, trimellitic acid, maleic anhydride, di- and trimerized unsaturated fatty acids, dimethyl terephthalate and Terephthalic acid bis-glycol ester.

Polyhydric alcohols include, for example, ethylene glycol, propylene glycol, 1,4-butanediol and / or 2,3, 1,6-hexanediol, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane, 2-methyl-1,3-propanediol, glycerine, trimethylolpropane, hexanetriol-1,2,6, pentaerythritol, Quinitol, mannitol, and sorbitol, formitol, methyl glycosite, as well as di-, tri-, tetra- and higher polyethylene, polypropylene and poly-butylene glycols are possible.

The polyesters can have a proportion of terminal carboxyl groups. Also polyesters from lactones, e.g. g-caprolactone or hydroxycarboxylic acids, e.g. # -Hydr oxyc i-hydroxycaproic acid can be used.

Also the at least 2 in question according to the invention in the Usually 2 to 8, preferably 2 to 3, polyethers containing hydroxyl groups those of the type known per se and are made, for example, by polymerizing epoxides such as ethylene oxide, propylene oxide, butylene oxide, tetrahydrofuran, styrene oxide or epichlorohydrin with itself, e.g. in the presence of Lewis catalysts, or by attachment these epoxides, preferably ethylene oxide and propylene oxide, optionally in a mixture or one after the other, on starting components with reactive hydrogen atoms such as Water, alcohols, ammonia or amines, e.g. ethylene glycol, propylene glycol, diethylene glycol, Dimethylolpropane, glycerine, sorbitol, succrose, formitol or formose, as well as 4,4'-dihydroxydiphenylpropane, Aniline, ethylenediamine or ethanolamine.

Polythioethers, polybutadienes, polyacetals, Polycarbonates or polyester amides can be used as starting materials. Even already Polyhydroxyl compounds containing urethane and / or urea groups, and optionally modified natural polyols such as castor oil are suitable.

According to the invention, polyhydroxyl compounds can optionally also be used are used in which high molecular weight polyadducts or polycondensates or Polymers are contained in finely divided or dissolved form.

Such polyhydroxyl compounds are obtained, for example, if Polyaddition reactions (e.g. conversions between different polyisocyanates and amino-functional compounds) or polycondensation reactions (e.g. between Formaldehyde and phenols and / or amines) in situ in the above-mentioned hydroxyl groups having compounds can drain.

The vinyl polymers are also modified polyhydroxyl compounds, such as, for example, the polymerization of styrene and / or acrylonitrile in the presence of Polyethers or polycarbonate polyols are obtained for the invention Procedure suitable.

Representatives of the higher molecular weights mentioned to be used according to the invention Polyhydroxyl compounds are described, for example, in High Polymers, Vol. XVI, "Polyurethanes, Chemistry and Technology ", written by Saunders-Frisch, Interscience Publishers, New York, London, Volume I, 1962, pages 32-42 and pages 44-54 and Volume II, 1964, pages 5 - 6 and 198 - 199, also in the Plastics Handbook Volume VII, Vieweg-Höchtlen, Carl-Hanser-Verlag, Munich, 1966, e.g. on pages 45 to 71, and in DE-OS 29 20 501, page 17 to page 24. Mixtures of the above can of course be used Compounds, e.g. mixtures of polyethers and polyesters, can be used.

According to the invention, those in polyurethane chemistry per se are preferred known polyhydroxy polyethers of the type mentioned with 2 to 6, particularly preferred with about 2 to 3 hydroxyl groups from the molecule and one random or segmented incorporated ethylene oxide content of at least 10% by weight, preferably more than 15, particularly preferably at least 20% by weight, as higher molecular weight polyols used. Polypropylene ether polyols with at least 20% by weight of ethylene oxide, in which at least 15% by weight of the OH end groups are primary Are hydroxyl groups.

The content of polyols in the gel-forming compound to be used according to the invention Mixture is about 80-99% by weight, preferably about 85 to 98% by weight, based on based on the total weight of the gel-forming mixture of polyurethane starting components.

In the case of the organic to be used in the gels according to the invention Di- and / or polyisocyanates are used in polyurethane chemistry known aliphatic, cycloaliphatic, araliphatic, aromatic and heterocyclic di- or polyisocyanates' such as those by W. Siefken in Justus Liebigs Annalen der Chemie, 562, pages 75 to 136 are described, the Diisocyanates as monomers or in a modified form, e.g. biuretized, allophanated, carbodiimidized, trimerized or polyol-modified, can be used.

Examples include: 1,6-hexamethylene diisocyanate, 1,12-dodecane diisocyanate, also cyclobutane-1t3- diisocyanate, cyclohexane-1,3- and 1,4-diisocyanate, and any mixtures of these positional and / or stereoisomers, 1-isocyanato-3,3,5-tri-methyl-5-isocyanatomethyl-cyclohexane, 2,4- and / or 2,6-hexahydrotoluylene diisocyanate, hexahydro-1,3- and / or 1,4-phenylene diisocyanate, Perhydro-2,4'- and / or -4,4'-diphenylmethane diisocyanate, as well as any mixtures these positional and / or stereoisomers, also 1,3- and 1,4-phenylene diisocyanate, 2,4- and 2,6-tolylene diisocyanate, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, and any mixtures of their isomers, and naphthylene-1,5-diisocyanate.

Furthermore, for example: Triphenylmethane-4,4 ', 4 "-triisocyanate, Polyphenyl-polymethylene polyisocyanates, as produced by aniline-formaldehyde condensation and subsequent phosgenation are obtained, m- and p-Isocyanatophenylsulfonyl-isocyanate, perchlorinated aryl polyisocyanates, polysocyanates containing carbodiimide groups, Norbornane diisocyanates, polyisocyanates containing allophanate groups, isocyanurate groups containing polyisocyanates, polyisocyanates containing urethane groups, acylated Polyisocyanates containing urea groups, polyisocyanates containing biuret groups, Polyisocyanates prepared by telomerization reactions containing ester groups Polyisocyanates, reaction products of the above-mentioned isocyanates with acetals and polymers Polyisocyanates containing fatty acid esters are suitable. This for implementation suitable Polyisocyanates are described in detail in DE-OS 29 20 501, page 13, lines 13 to Page 16, line 2. Preferred aromatic di- and triisocyanates are 2,4- and / or 2,6-tolylene diisocyanates and 4,4'- and / or 2,4'-diphenylmethane diisocyanate and their modified types, as well as those with tri- and tetrafunctional polyols prepared multifunctional derivatives or trimerization products. Preferred Polyisocyanates are e.g. 1,6-hexamethylene diisocyanate, isophorone diisocyanate, methylcyclohexane-2,4- and / or -2,6-diisocyanate, dicyclohexylmethane-2,4'- and / or -4,4'-diisocyanate and their biuretized or trimerized polyfunctional derivatives.

All of the above di- and / or polyisocyanates can also be used in any Mixtures are used.

The content of di- and / or polyisocyanates in the gel-forming mixtures from polyols and polyisocyanates is about 1 to 20 wt .-%, preferably 2 to 15% by weight, based on the total weight of the mixture.

In the case of the catalysts to be used for the gel formation for the reaction between hydroxyl and isocyanate groups are preferably those of a type known per se in polyurethane chemistry, e.g.

tertiary amines, such as triethylamine, n-tetramethylethylenediamine, 1,4-diaza-bicyclo- (2,2,2) -octane, N, N-dimethylbenzylamine, N-methyl-N'-dimethylaminoethylpiperazine, Pentamethyldiethylenetriamine, or Mannich bases, known as catalysts, from secondary amines, such as dimethylamine and aldehydes (formaldehyde) or ketones (acetone) and phenols are also possible Silaamines with carbon-silicon bonds, e.g. 2,2,4-trimethyl-2-silamorpholine and 1,3-diethylamino-methyl-tetramethyl-disiloxane. According to the invention, organic ones also come Metal compounds, in particular organic tin compounds, as catalysts can be used, e.g. tin (II) acetate, tin (11 -) - ethylhexoate and the tin (IV) compounds, e.g.

Dibutyltin dichloride, dibutyltin dilaurate, dibutyltin maleate into consideration. Further suitable catalysts are in DE-OS 29 20 501 on pages 29, line 5 to page 31, line 25.

The catalysts are preferably used in an amount between 0.05 and 10% by weight, based on the total weight of the gel, are used. Of course all catalysts can be used as mixtures.

According to the invention, for example, the following groups of substances can be used as active ingredients or substances are used: 1. Biocides, such as bactericides, fungicides, Algicides, herbicides, virus cides, larvicides, nematicides, ectoparasiticides such as tickicides or insecticides.

2. Pharmaceuticals and / or skin care and protective agents, such as e.g. antimycotics, antiallergics, anti-inflammatory drugs, antiseptics, local anesthetics, circulation-promoting Agents, venous agents, wound treatment agents, antipruritic agents, and dermatological agents; agents containing moisture, UV-absorbing substances, Bacteriostatics, cosmetics and deodorizing substances such as halophenols or salicylic acid derivatives or disinfecting substances.

3. Natural active ingredients, such as essential oils, e.g. eucalyptus oil, menthol oils, Attractants (pheromones), vitamins or enzymes.

4. Fragrances of a natural or synthetic nature, including ethereal ones Oils, perfumes or fragrances made from known fragrant individual components or compositions are to be understood, e.g. anise oil, bergamot oil, camphor oil, clove oil, lemongrass oil, Lavender oil, peppermint oil, rose oil, or cinnamon oil; other suitable components are listed in DE-OS 25 21 265.

5. Stamp and block colors, or erasure of ink and crayons Substances.

6. Cleaning and care products for leather and plastics, e.g. if necessary colored waxes, stain removers.

7. Anti-aging agents, e.g. antioxidants such as dodecyl gallate or tert-butyl-substituted phenols, UV absorbers, light stabilizers, antistatic agents such as ethoxylated alkylphenols and preservatives.

8. Plant nutrients such as inorganic salt mixtures, as well as freshness-keeping agents for flowers and growth regulators.

9. Antifouling agents and wood preservatives: e.g. powder of copper, Mercury or tin compounds, as well as pentachlorophenols and dinitrophenols.

10. Detergents and washing aids, such as alkylarylsulfonates, fatty alcohol sulfates, Fatty alcohol-ethylene oxide adducts, fabric softeners, molding detergents, foam suppressors and brighteners.

11. Photohardenable Mixtures.

The content of active ingredients in the gel compositions according to the invention is 0.1 to 50% by weight, preferably 0.5 to 35% by weight and particularly 0.75 to 25% by weight, based on the total weight of the gel mass (components 1-4). However, it can with very active additives, e.g. pheromones, also lower (e.g. <), 01 t).

A possible limitation of the type of active ingredients to be used results with such active ingredients that contain chemical groups so reactive that she largely or completely under the conditions of the gel-forming polyurethane reaction are and remain fixed and the active ingredients are no longer able to escape are.

As optionally additionally contained in the gels according to the invention Fillers and additives are the substances known per se in polyurethane chemistry to understand, such as fillers, pigments and short fibers on inorganic and organic base, metal powder, coloring agents such as dyes and color pigments, water-binding agents, surface-active substances such as silicones, and also flame retardants or liquid extenders with a boiling point above 1500C. As organic fillers be for example heavy crevice, chalk, gypsum, soda, titanium dioxide, zeolites, quartz sand, Called kaolin, soot and glass microspheres.

Of the organic fillers, e.g. powders based on polystyrene, Polyvinyl chloride, urea formaldehyde and polyhydrazodicarbonamide can be used. Short fibers include, for example, glass fibers from 0.01 to 1 mm in length or fibers that are more organic Origin, e.g. polyester, polyamide, aramid or carbon fibers in question. Metal powder, e.g.

Iron or copper powder can also be used. To the Coloring of the gels can contain non-migrating dyes and color pigments on organic or inorganic base can be used.

Surface-active substances are e.g. cellulose powder, activated carbon and called silicic acid preparations. Sodium polymethaphosphates, for example, can be used as flame retardants can be added. As a liquid Extenders or plasticizers can the usual compounds can also be used, e.g. alkyl-, alkoxy- or halogen-substituted ones aromatic compounds such as dodecylbenzene, ortho-dichlorobenzene, chlorinated paraffin or dodecyl sulfonic acid ester. Higher molecular weight extenders can also be used as liquid extenders Polyols are used whose hydroxyl groups are etherified, esterified or urethanized are. The content of these extenders and fillers is up to 50%, preferably less than 25%, based on the sum of 1 + 2.

For the formulations the one adapted to the respective application Gel compositions according to the invention can also use a wide variety of auxiliaries can be used with. Should, for example, pharmaceuticals be incorporated into the gels according to the invention absorption aids such as phospholipids and solubilizers can be used such as polyethylene glycols or polypropylene glycols, emulsifiers such as glycerol fatty acid esters, Spreading agents such as silicone oils, fatty acid esters or triglycerides, as well as skin care products Substances such as 2-octyl-dodecanol are added during gel formation.

For formulations containing biocides that contain solid active ingredients it is advantageous to use spreading agents and, in particular, plasticizers, such as dibutyl phthalate, to be added during gel formation.

The following substances can be used as spreading agents: Silicone oils different viscosities, fatty acid esters such as lauric acid hexyl ester, dipropylene glycol pelargonate, Esters of branched fatty acids of medium chain length with saturated C16-C18 fatty alcohols' such as isopropyl myristate, isopropyl palmitate, caprylic / capric acid esters of saturated Fatty alcohols of chain length C12 to C18 'isopropyl stearate, oleic acid decyl ester, waxy fatty acid esters such as adipic acid diisopropyl ester triglycerides, such as caprylic / capric acid triglyceride, Triglyceride mixtures with vegetable fatty acids of chain length C8 to C2 or others specially selected natural fatty acids, partial glyceride mixtures or monoglycerides, also fatty alcohols, such as isotridecyl alcohol, 2-octyl dodecanol or oleyl alcohol, or fatty acids such as oleic acid or stearic acid. Oils that spread particularly well are Isopropyl myristate, isopropyl stearate, isopropyl palmitate, lauric acid hexyl ester, oleic acid decyl ester, Dibutyl stearate, dibutyl sebacate, paraffin oil, ethylhexyl palmitate / stearate or iso-tridecyl stearate.

The production of the active ingredient-containing gel compositions according to the invention can be carried out continuously or discontinuously. The way of working depends, inter alia, on the form that the gels according to the invention are given with regard to want to give their application.

You can work according to the one-shot or the prepolymer process. In the one-shot process, all components, i.e. polyols, di- and / or polyisocyanates, Active ingredients, catalysts and given if fillers and additives put together at once and mixed together intensively, with the active ingredients are preferably dissolved or dispersed in the polyol components.

There are two ways of working with the prepolymer process. Either one first produces an isocyanate prepolymer by adding a corresponding Proportion of the amount of polyol (+ active ingredient) of the total amount intended for gel formation Reacts amount of isocyanate, and then adds the remaining amount to the prepolymer obtained of polyol (optionally other active ingredients), and optionally other fillers and additives and mix intensively, or you put the whole, for gel formation intended amount of polyol (+ active ingredient) with part of the amount of polyisocyanate to an OH prepolymer and then mixes the remaining amount of polyisocyanate to.

A particularly advantageous mode of operation according to the invention is one Variant of the one-shot process and the OH prepolymer process. Here will be the polyol or polyol mixture, the active ingredients, optionally the fillers and additives, the catalyst and two different diisocyanates combined in one shot and intensively mixed, with a di- or polyisocyanate aromatic and a di- and / or polyisocyanate is aliphatic in nature. One can assume that through the very different reactivity of the two polyisocyanates initially a hydroxyl prepolymer arises, which then occurs within Minutes with the other polyisocyanate reacts with gel formation. This results in gels with particularly high toughness obtain.

These procedures can involve conveying, dosing and mixing of the individual components or component mixtures with those for the person skilled in the art of polyurethane chemistry known devices take place.

It is particularly surprising for the person skilled in the art that even with relative low isocyanate index (e.g.

30) and a polyol component with uniformly reactive OH groups (so that no selective reaction of part of the polyol component with the polyisocyanate expected) gels with a high molecular weight, crosslinked, in dimethylformamide insoluble matrix and not just liquid polyols modified by urethane groups (OH prepolymers) can be obtained.

In order to achieve a good matrix structure, it is advantageous to the conversion between the polyols and the polyisocyanates at relatively low Temperatures, e.g. below 50 ° C, preferably at room temperature.

If you want to manufacture e.g. molded parts for the application, the discontinuous one Recommended working method.

However, if the polyurethane gel according to the invention is to be more suitable in pieces Dimensions are made then a continuous process is often cheaper. In this case you first produce an endless film or plate, which you then can cut into individual pieces.

In continuous production, the active ingredient can contain gelable mixture before it solidifies due to gel formation, sprayed, poured or be doctored. Here, the gelable, active ingredient-containing mixture on the A wide variety of materials based on natural or synthetic raw materials can be applied, e.g. on mats, fleeces, knitted fabrics, knitted fabrics, foam foils, plastic foils or plates, or poured into desired shapes.

The conditions during gel formation can also be in the manner vary to obtain either compact or foamed gels. For example, becomes air When hammered into the gelable mixture, foam gels are obtained.

The active ingredient-containing gel compositions according to the invention can be used in a wide variety of forms, such as granules, foils, plates, blocks, sticks or molded part. The choice depends on the particular application and the desired one Release concentration of the active ingredients. The active ingredients can be used for weeks and months diffuse out of the gels according to the invention and as a function on their volatility in the gas phase and / or on contact with the invention Gel masses with solid or liquid materials or substances (e.g. the animal skin or water) are released to the contacted materials.

The active ingredient-containing gels according to the invention are suitable for longer-term Release of the incorporated active ingredients for a wide variety of purposes, such as plasters containing dermatological substances for attachment the skin, as insecticide-containing tapes and plates to control flies and Vermin, e.g. to remove ticks and fleas from animals, as fragrance-containing Panels and molded parts for scenting rooms, as deodorising masses for transfer on the skin, as printing or stamp plates with little tendency to dry, as shoe polish for applying paint and wax, as an insecticide-containing tree ring against the effects of insects, as a lubricant with an antistatic effect and more.

A major advantage of the active ingredient-containing gels according to the invention Compared to the water-containing active ingredient gels, there is a higher stability of those susceptible to hydrolysis active reagents, such as insecticides, pesticides, fragrances or Pharmaceuticals during storage and the period of action of the gels.

Another major benefit of the new gel masses is that too incorporated solid or non-volatile active ingredients migrate out and thus over can be effective for a longer period of time, though she a certain Have solubility in the polyols as dispersants. Ask in this regard the gels according to the invention are a valuable improvement over such massive ones and foamed polyurethanes, in their manufacture the reactive components are used in amounts corresponding to an isocyanate index of 70 to 200, and in which there are no significant amounts of free polyols according to the invention Effect, but on the contrary, the high network density encourages expatriation hampered by solid active ingredients.

Experimental part The following examples illustrate the present invention. Quantities are given as percentages by weight or

To understand parts by weight, unless otherwise indicated.

The following polyisocyanates and polyols were used in the examples used: polyisocyanate 1: 1,6-hexamethylene diisocyanate polyisocyanate 2: commercially available biuretized 1,6-hexamethylene diisocyanate with a medium NCO functionality of 3.6, an NCO content of 21% and an average molecular weight (number average) of approx. 700 (Desmodur N from Bayer AG).

Polyisocyanate 3: isomer mixture of 80% 2,4- and 20% 2,6-tolylene diisocyanate.

Polyisocyanate 4: liquefied by prepolymerization with tripropylene glycol 4,4'-diisocyanatodiphenylmethane; middle NCO functionality 2.05, NCO content 23%.

Polyisocyanate 5: prepolymer made from 159 parts of polyisocyanate 3 and 1200 Parts of a polyether with an OH number of 28, produced by the addition of 60 parts Ethylene oxide and 40 parts of propylene oxide on glycerine.

The polyether polyols used in the examples are shown below Table compiled. TMP stands for trimethylolpropane in the table; PG for 1,2-propylene glycol; Gly for glycerine and PE for pentaerythritol.

Polyol No. Propylene Oxide Ethylene Oxide Starter OH OH Molecule Number Functionality 1 80 20 TMP 36 3 2 100 - PG 56 2 3 45 55 TMP 56 3 4 100 - TMP 56 3 5 90 10 TMP 56 3 6 85 15 TMP 56 3 7 83 17 TMP 34 3 8 100 - Sorbitol 46 6 9 40 60 Gly 28 3 10 100 - TMP / PG 46 2.75 (84:16) 11 100 - PE 45 4 12 50 50 PG 56 2 13 80 20 PG 28 2 14 82 18 TMP 35 3 15 63 37 Sorbitol 30 6 Polyol 16 is a partially branched polyester made from Adipic acid, diethylene glycol and TMP. Average molecular weight: approx. 2000; middle OH functionality: 2.3.

Example 1 80 parts of the polyether (1), 15 parts of methyl butyrate as Fragrance, 1.2 parts of dibutyltin dilaurate and 4 parts of polyisocyanate (2) are within Mix intensively for 1 minute. An elastic gel forms after 15 minutes. In Shape of a shaped body such as a cone, a plate or a rose replica, this gel can be used for long-term scenting of cupboards, rooms, automobiles or rubbish bins.

Example 2 10 parts of polyether 1, 40 parts of polyether 2 and 8 parts of a perfume oil (from 60% by weight isobornyl acetate and 40% by weight of the adduct of 10 moles of ethylene oxide to 1 mole of nonylphenol, 50 parts of polyether (3) and 0.15 part K-sorbinate, 1.5 parts of dibutyltin dilaurate and 6 parts of polyisocyanate (2) are within Mix intensively for 1 minute. After 15 minutes a clear, elastic one forms Gel with a non-sticky surface that acts as a fragrance dispenser to freshen the air can be used in rooms. The fragrance gel retains its structure and effectiveness for months at.

Example 3 Analogously to Example 2, a gel is produced from 10 parts Polyether 4, 50 parts Polyether 5, of 4 parts of the perfume oil from Example 2 contains 40 parts of polyether (6) containing 0.18 parts of sodium benzoate as a bactericide contains 1.5 parts of dibutyltin dilaurate and 6 parts of polyisocyanate (2).

Example 4 100 parts of polyether (3), 5 parts of triethylene glycol dimethyl ether, 8 parts of fragrance oil 83/117 (scented lemon; product from Colgate Palmolive Peet Inc., USA), 2.5 parts of dibutyltin dilaurate and 8 parts of polyisocyanate (2) become intense mixed and poured into an open mold to a height of 3 mm. You get a 3 mm thick gel sheet, which is cut into 1.5x10 cm strips. A such a strip can be attached to the inner part of the lid of a package, which contains 4 to 5 kg of detergent powder. In this way you can achieve a fragrance of the detergent without the risk of the fragrance being destroyed by the Components of the detergent (oxidizing agent).

Example 5 3500 parts of polyether (3) containing 350 parts of pentachlorophenol contains, 700 parts of polyether 7, which contains 14 parts of K-sorbinate, 2800 parts of polyether 2 mixed with 50 parts of a high molecular weight polyethylene oxide and 35 parts Dibutyl tin dilaurate are mixed homogeneously in a stirred kettle at 22 ° C.

The mixture is fed to a static mixer using a gear pump fed. This mixer is made from a separate storage container by means of a another gear pump at the same time4 73 parts of polyisocyanate (2) fed in such a way that at all times the mixing ratio of the components is the same and the ratio corresponds to the total quantities. The whitish-cloudy flowing out of the static mixer Solution is poured into a square envelope. After the gelation reaction is completed, becomes a soft, dimensionally stable, deformable under pressure Gel obtained as a deodorizing gel stick to prevent perspiration odor can be used by bacterial decomposition.

Example 6 75 parts of polyether (1), 20 parts of o, o-dimethyl-o- (2,2-dichlorovinyl) phosphoric acid ester (DDVP, insecticide), 1.2 parts of dibutyl tin dilaurate and 3.8 parts of polyisocyanate 2 are mixed intensively within 1 minute. After about 10 minutes it forms an elastic gel that comes in the form of a strip that is placed in a perforated plastic container is inserted as an insecticidal gel for long-term fumigation of the atmosphere, e.g. to control vermin or cockroaches in kitchens can.

Example 7 1000 parts of polyether 8 containing 100 parts of the insecticide DDVP (see Example 6) contains 45 parts of polyisocyanate (3) and 30 parts Dibutyltin dilaurate are added using a laboratory stirrer with a stirring disk Intensive mixing at room temperature within 1 minute. You get a soft, elastic, dimensionally stable gel, which under the influence of an acting on it Can easily deform force.

Example 8 100 parts of polyether 9, 4.0 parts of hexachlorophene and 0.48 Parts containing ethyl p-hydroxybenzoate are mixed with 5.0 parts of polyisocyanate 4 and 2.8 parts of dibutyl tin dilaurate to form a soft, elastic, dimensionally stable Gel implemented. The gel is suitable for brushing skin to prevent bacterial decomposition of perspiration.

Example 9 100 parts of polyether (1) with a temperature of 70au, 30 parts of 2-isopropoxyphenyl-N-methyl-carbamate (an insecticide), 60 parts of isopropyl myristate, 5 parts of permethric acid fentafluorobenzyl ester (an insecticide), 2 parts of dibutyl tin dilaurate, 0.3 parts of iron oxide pigment and 5.5 parts of polyisocyanate (2) are mixed intensively. The reaction mixture is poured into an open mold that is lined with synthetic leather is poured up to a layer thickness of 5 mm. Become a gel after hardening 15 mm wide strips cut, consisting of a leather decor layer and an active ingredient Consist of gel layer. These Strips are provided with a buckle and can then be used as collars against fleas and ticks on pets such as cats or use dogs.

Example 10 Analogously to Example 1, with variation of the OH or. NCO functionality of the starting gels produced, with the isocyanate number each was 50. The properties of the gels thus obtained are as follows Table compiled; "Liquid" means that as a result of insufficient functionality no gel structure has yet been formed (not according to the invention). As an isocyanate component are polyisocyanate (1), polyisocyanate (2) or mixtures thereof with the specified middle NCO functionality used; the polyol components consisted of the Polyols 10 or 11 or 1: 1 mixtures of 2 and 10 or

Lv 10 and 11, in the polyol each 5 wt. 8 xatendel oil is used as a fragrance. Functionality; 2 2.3 2.75 3.75 4 NCO OH # # 2 liquid very soft * 2.1 # very soft * soft ** 2.2 liquid soft ** hard ** 2,3 very soft * soft ** 2,4 # very soft * 2.6 liquid soft ** 2.8 very soft * 3.1 # soft ** 3.6 liquid hard ** *) according to the invention **) preferred according to the invention Fragrance carrier gals are obtained.

Example 11 Analogously to Example 10, the dependence of the gel consistency on the functionality for the isocyanate number 30 was investigated. The polyols 10, 11, 8 or a 1: 1 mixture of 11 and 8 were used as hydroxyl components, the polyols each containing 4% by weight of lavender oil. Functionality: 2.75 4 4.8 6 NCO / OH ~ b I. 2, t \, \ t liquid 2.1 | very soft ** 2.15 liquid soft * ** 2.2 very soft soft-hard * ** 2.3 1 very soft hard ** ** 2.4 liquid soft hard * ** * 2.8 liquid very soft soft hard * ** 3.6 very soft soft According to the invention, preferred according to the invention. Fragrance carrier gels are obtained which show a long-lasting release of fragrance.

Example 12 In analogy to Example 10, the dependence of the gel consistency on the isocyanate index and the NCO functionality was investigated. A 1: 1 mixture of polyols 2 and 12, which contain 10% by weight of lavender oil as a fragrance, is used as the polyol component. Mixtures of polyisocyanates 1 and 2 with the specified average NCO functionality are used as isocyanate components. Functionality; NCO / - 2.6 2.8 3.0 3.2 identification number V t Versleich 52.5 liquid ** 50 invention 1 very very soft soft * ** ** invention * * k ** 47.5) according to (liquid) very soft soft hard According to the invention, preferred according to the invention Example 13 Dependence of the gel consistency on the NCO functionality with constant isocyanate index (50) and OH functionality (3).

Experiment 1: Polyol components: Polyol 6 Iso., Yanaikomponente: Various Mixtures of polyisocyanates 1 and 2.

Experiment 2: Polyol component: polyol 4 / polyol 6 (1: 1), (8 wt. Methyl butyrate contained as a fragrance); Isocyanate component: as experiment 1.

NCO functionality Experiment 1 Experiment 2 2 liquid liquid 2.1 liquid very soft-soft * ** 2.2 very soft soft ** ** 2.3 soft soft-hard ** ** 2.4 soft-hard hard ** * 2.6 hard hard ** * 2.8 hard very hard *, **: Meaning sh. example 12 Example 14 Dependence of the gel consistency on the polyether mixing ratio with primary hydroxyl groups / polyethers with secondary hydroxyl groups. The polyols contained 10% by weight methyl butyrate.

Isocyanate index: 35 Isocyanate component: polyisocyanate 2 The gels were produced analogously to Example 1.

Experiment polyol 6 (%) polyol 4 (%) gel consistency 1 0 100 very soft 2 5 95 soft 3 15 85 soft to hard 4 25 75 hard 5 35 65 very hard 6 45 55 hard 7 75 25 hard 8 100 0 soft to hard Example 15 For the experiment of example 14 was investigated how much of the (practically non-reactive) polyol 4 with otherwise the same Recipe (10 wt .-% methyl butyrate in the polyol mixture) added to the reaction mixture can be so that a gel is still obtained. As the following table shows, the limit of gel formation for the selected starting components is one Composition, which (theoretically calculated) 28 wt .-% polyurethane matrix and 72 Corresponds to weight-free polyol. Extraction tests of the polyol show practical Results as calculated theoretically.

Recipe (parts) Polyol 6 35 35 35 35 35 Polyol 4 65 100 105 120 150 Polyisocyanate 2 7 7 7 7 7 dibutyltin dilaurate 3 3 3 4 5% polyurethane matrix 38 29 28 25 21 Consistency very * very * very ** gel liquid hard soft soft partial gel Gel Gel chen in liquid *) and **) meaning as in example 12 speed example 16 Example 15 was repeated for Experiment 7 from Example 14. The limit of gel formation was here at 27% polyurethane matrix.

Formulation (parts) Polyol 6 75 75 75 75 75 Polyol 4 25 65 75 90 100 Polyisocyanate 2 7 7 7 7 7 Dibutyltin dilaurate 3 4.5 4.5 5 5% Polyurethane matrix 38 28 26 24 22 * Consistency hard very * very gel liquid gel soft, soft partial gel gel, in *) according to the invention, liquid liquid Example 17 For polyisocyanates 2, 3 and 4, it was investigated which isocyanate index must at least be complied with in order to react with various polyols (with the addition of 3% by weight methyl butyrate fragrance) to obtain a gel according to the procedure of Example 1: The limit values found for the isocyanate index are compiled in the table below. Polyisocyanate no / »2 4 3 Polyol no. 8 20 30 15 18 35 37 11 30 45 47 3 25 55 60 9 25 55 65 10 32 65 70 12 40 - - 13 50 50 52 16 20 50 52 Example 18 100 parts of polyether 1 with a temperature of 700 ° C., 25 parts of 2-isopropoxyphenyl-N-methyl-carbamate (insecticide), 10 parts of 3-phenoxy-4-fluoro-1, -cyanobenzyl-2,2-dimethyl-3- - (4-chlorophenyl) -2-chlorovinyl7-cyclopropanecarboxylate (insecticide), 2.5 parts of dibutyltin dilaurate and 5.5 parts of polyisocyanate 2 are mixed intensively. The gel obtained can be attached in the form of plates, strips or shaped bodies to farm animals, such as cattle, in a suitable manner to the tail, neck, horns or ears (ear tags). In this way, the animals are protected against numerous harmful animal parasites (ectoparasites) for weeks.

Example 19 100 parts of polyether 1, 15 parts of diphenyl-acetylenylimidazolyl-methane (Algicide), 2 parts of dibutyltin dilaurate and 5 parts of polyisocyanate 2 are intense mixed. An elastic gel is obtained after 15 minutes. One such gel is for coating e.g.

Suitable for ships, sea barrels or quay walls in the underwater area, to prevent the growth of algae, barnacles, mussels and other marine life impede.

Example 20 100 parts of polyether 3, 5 parts of menthol, 2.5 parts of dibutyltin dilaurate and 8 parts of polyisocyanate 2 are mixed intensively. The reaction mixture obtained is poured onto a close-meshed, rigid plastic grid made of polyethylene and solidifies to an elastic gel mass within 30 minutes.

Such a menthol-containing strip can be used for medical purposes (Inhalation of menthol).

Example 21 100 parts of polyether 1, 5 parts of nonylphenol, 5 parts of dodecylbenzyldimethylammonium chloride, 1.5 parts of dibutyltin dilaurate and 5 parts of polyisocyanate 2 are mixed intensively. The reaction mixture is poured into an open mold with the dimensions 1x2x10 cm. The gel stick obtained is placed in a 2x2x10 cm bowl that is in the toilet bowl is attached in a suitable form such that the gel when rinsing with water is heavily watered. In this way a long-term disinfection can be achieved of the toilet bowl.

Example 22 100 parts of polyether 3, 30 parts of potassium dichromate / pentachlorophenl (1: 1), 3 parts of dibutyltin dilaurate and 8 parts of polyisocyanate 2 are mixed intensively.

The reaction mixture obtained is applied to a polyester fabric in 5 mm Starch applied on which the mixture hardens to a gel. Coated in this way Polyester fabrics can be used in the form of bandages for cladding wooden poles in the transition area Earth / air can be used to protect the wood against rot.

Example 23 100 parts of polyether 3, 15 parts of sodium dodecylbenzenesulfonate, 2.5 parts of dibutyltin dilaurate and 8 parts of polyisocyanate 2 are mixed intensively and on a 10 mm thick open-cell film made of polyurethane foam (polyester base) sprayed. Such an impregnated film, glued to a sponge made of flexible polyether foam, can be used for cleaning purposes.

Example 24 100 parts of polyether 3 with a temperature of 40 ° C., 15 Parts 1-methyl-1-alkylamidoethyl-2-alkyl-imidazolinium methosulfate (cationic quaternary imidazoline compound from Ashland Chemical, Co., USA; Laundry softener), 0.2 parts of Heliofast-Yellow C.I. No.

11680, 2 parts of dibutyltin dilaurate and 8 parts of polyisocyanate 2 are used intensely mixed. The reaction mixture obtained is in a 3 mm thick layer poured onto a polypropylene fleece. After about 10 minutes you get an elastic one Gel layer. The gel-coated fleece is used to soften laundry in drum dryers suitable.

Claims (6)

Claims 1) Active ingredient-containing, anhydrous gels, consisting of 15 to 62% by weight, based on the sum of (1) and (2), of a high molecular weight matrix; 85 to 38% by weight, based on the sum of (1) and (2), of one in the matrix liquid dispersant bound by secondary valence forces; Active ingredients, as well optionally 0 to 100% by weight, based on the sum of (1) and (2), of filling and / or additives, characterized in that a) the high molecular weight matrix is a covalently crosslinked polyurethane, b) the liquid dispersant from a or more polyhydroxyl compounds with a molecular weight between 1000 and 12,000 and an OH number between 20 and 112, the dispersant essentially no hydroxyl compounds with a molecular weight below 800 contains, and c) 0.1 to 50% by weight of active ingredients in the active ingredient-containing gel composition are included. 2) Process for the production of active ingredient-containing anhydrous gel masses with depot action based on polyurethane gels, characterized in that a) one or more di- and / or polyisocyanates with b) one or more polyhydroxyl compounds with a molecular weight between 1000 and 12,000 and an OH number between 20 and 112, c) 0.1 to 50% by weight of active ingredients, optionally d) catalysts for the reaction between isocyanate and hydroxyl groups, and optionally e) the polyurethane chemistry implements known fillers and additives, the Isocyanate number is between 15 and 50, the product of the functionalities of the Polyurethane-forming components is at least 5.2 and the polyhydroxyl compounds are essentially free of hydroxyl compounds having a molecular weight below 800 3) Method according to claim 2, characterized in that the polyhydroxyl compounds have a molecular weight between 1700 and 6000 and the product of the functionalities the polyurethane constituent components is at least 6.2. 4) Process according to claims 2 and 3, characterized in that 0.5 to 35% by weight of active ingredients dissolved or dispersed in polyol compounds will. 5) Process according to Claims 2 to 4, characterized in that Active ingredients from the group of biocides, pharmaceuticals, natural substances such as essentials Oils, fragrances, paints, detergents and washing aids, stamp and printing inks, Anti-aging agents, lubricants and antistatic agents, cleaning and care products, Antifouling agents and wood preservatives, as well as plant nutrients, freshness preservatives and are growth regulators. 6) Process according to Claims 2 to 5, characterized in that the active ingredients are free of reactive groups under the conditions of Gel formation react largely or completely with fixation.