WO2006024360A1

WO2006024360A1 - Coating compounds containing polymer particles containing active compounds with a particular capacity for adhering to substrates

Info

Publication number: WO2006024360A1
Application number: PCT/EP2005/008491
Authority: WO
Inventors: Patrick Amrhein; Uwe Dittrich; Bernhard Schuler; Harm Wiese; Reinhold J Leyrer
Original assignee: Basf Aktiengesellschaft
Priority date: 2004-09-01
Filing date: 2005-08-05
Publication date: 2006-03-09
Also published as: DE102004042694A1

Abstract

The invention relates to coating compounds containing polymer particles consisting of a polymer matrix, and an active ingredient with a particular capacity for adhering to the surfaces of substrates and a good formulation capacity. The invention also relates to the use of said coating compounds as repellents for dogs, cats, and Dictyna civia spiders. The active ingredient is released from the composition in a controlled manner.

Description

Paints containing polymer particles containing active compounds with spe¬ cieller substrate adhesion

description

The present invention relates to paints containing polymer particles of a polymeric matrix and an active ingredient with a special Substratanhaf¬ tion of surfaces and a good formability and the use of these An¬ coating agent as an antibody (repellent) against dogs, cats and masonry. The active ingredient is released from the composition in a controlled manner.

It is known from the prior art to use controlled-release polymer compositions comprising an active substance which is releasably contained in polymeric particles in sprayable agricultural compositions.

EP 305 139 discloses such compositions and their use as insecticides.

No. 6,395,290 discloses sprayable compositions for repelling animals, such as cats and dogs, containing an active ingredient dispersed in a polymer. The polymer is preferably an ethylene-vinyl acetate copolymer and the active ingredient is methyl nonyl ketone. These compositions have the disadvantage that, although they initially contain the active ingredient and can deliver controlled, but the application form is not designed to bind permanently to a substrate. This, in turn, entails the risk of the polymer being e.g. can be easily washed off or rubbed off under mechanical stress and thus the delayed release does not come into play. Furthermore, the polymers are generally selected so that they are used as so-called "stand-alone products", ie, that the corresponding latex particles can not be arbitrarily used as additives in existing formulations due to lack of compatibility ,

The active ingredients (for example semiochemicals) disclosed in EP 617 051, which are likewise introduced into a polymer matrix, have the disadvantage that they have no special adhesion to substrate surfaces and that compatibility with existing formulations is not ensured.

For reasons of hygiene, it is often desirable, especially in larger cities, to keep animals, for example dogs or cats, away from certain objects in order, for example, to prevent the animals from urinating on buildings or walls. In addition to harassing the resident residents, the buildings take on permanent damage. This can begin with the wearing away of the wall paint and up to cause damage to the building fabric. Even concrete is badly attacked by dog urine.

Wall spiders, an introduced spider species from the Mediterranean, which belongs to the genus of the curling spiders, cause black unaesthetic discoloration on the facades through their nets.

With a strongly curled thread, they weave mostly irregular, hand-sized nets directly to the house walls. These nets are almost always found near the roof overhang or under eaves, i. in places where mosquitoes are sheltering from rain and wind at night. In addition to the food residues, a lot of dust collects in the nets so that the facades of the houses soon look dirty. The small spiders live behind or over the nets in cracks in the walls, which they can also extend slightly. Some times, are transported by the wind, whole districts infested.

In addition to many known from the literature as repellents acting drugs and the active ingredient methylnonyl ketone is used. Methylnonyl ketone is a colorless, highly scented oil used to repel dogs or cats. It is used commercially in liquid spray formulations. The disadvantage here, however, on the one hand, the only short-lasting effect due to the high volatility of the active ingredient and, secondly, the occurrence of discoloration on the sprayed materials.

A common problem with the incorporation of drugs into a matrix is the ratio between the uptake of the drug and the delivery / release profile. If the absorption of the active ingredient is easy, the release is often too fast. If the absorption is inhibited, then there may be no release or, if the absorption has taken place only on the surface of the particles, that it is of short duration.

The object of the present invention was therefore to provide a paint containing polymer particles of a polymeric matrix and an active ingredient and its use as a repellent against animals, in particular against dogs, cats or masonian spiders, in a satisfactory combination of absorption and controlled release of the active ingredient Substrate adhesion or resistance to weathering and good formability.

According to the invention, the object has been achieved by a paint containing A) 1-30% by weight of polymer particles of a) 10-60% by weight of polymeric matrix and b) 0.1-50% by weight, based on the weight of the polymeric matrix active ingredient, B) 15-65 wt .-% of an inorganic filler

C) 0.1-5% by weight of surface-active substances

D) 0-15 wt .-% customary auxiliaries and

E) 25-60% by weight of water.

Another object of the invention is the use of the paint as Ab¬ wehrstoff against dogs, cats or masonry spiders.

In the case of the coating material according to the invention, the active ingredient is released from the polymeric matrix in a controlled manner. It is particularly advantageous that the permeability of the polymer to the volatile active ingredient can be chosen in advance to achieve release at a desired and controlled rate.

As the polymeric matrix (a) are polymers containing aa) 40-95 wt .-% of at least one acrylic or methacrylic acid ester of

C _r C ₈ -alkanol or mixtures thereof, bb) 0-50% by weight of vinylaromatic monomers cc) 0-15% by weight of ethylenically unsaturated monomers and d) 0.1-20% by weight of further monomers containing functional groups einge¬ sets.

The functional groups of the monomers dd) are correspondingly chosen so that an optimal compatibility between the polymer to be administered containing Po¬ lymer optionally used in a corresponding formulation and the ausge¬ selected substrate surface is guaranteed.

The glass transition temperature of the polymeric matrix is 90-150 ⁰ C, preferably 95-130 ⁰ C and most preferably 98-125 ⁰ C. The einzuformulierenden active compound, the original glass transition point of the pure polymer but is first lowered, the polymer is plasticized and reaches its original glass point only approximately after complete release of the active compound.

The acrylic or methacrylic acid esters aa) are preferably selected from the group n-, iso-, t-butyl, n-hexyl or 2-ethylhexyl acrylate, methyl methacrylate or butyl methacrylate. Particular preference is given to using methyl methacrylate. The acrylic or methacrylic esters are used in amounts of 40-99% by weight, preferably 50-98% by weight and more preferably 55-97% by weight.

The vinylaromatic monomers bb) used are preferably styrene or styrene derivatives, such as alkylstyrenes, for example .beta.- or .gamma.-methylstyrene or vinyltoluene. They are in Quantities of 0-50 wt .-%, preferably 0-40 wt% used. Particular preference is given to using 5-30% by weight of styrene.

The monomers cc) are selected from the group of ethylenically unsaturated mono- or dicarboxylic acids containing 3-5 C atoms, acrylic acid or methacrylic acid are preferably used. They are used in amounts of 0-15 wt .-%, preferably 0-10 wt.%. Particular preference is given to using 5-10% by weight of methacrylic acid.

The monomers dd) may be C1-C8 (meth) acrylates having functional groups such as OH, NH _2, CN, C (O) -NH _2, COOR or epoxy groups, for example Urei- domethacrylat, N-methylol (meth) acrylamide, butanediol diacrylate, Methacryloxypropyltrimethylsiloxane or allyl methacrylate. It is also possible to use monomers from the series of dimethylaminopropyltrimethacrylamide, trimethylammoniumethyl (meth) acrylate, dimethylaminoethyl (meth) acrylate, trimethylammoniumpropylmethacrylamide and further acrylic acid esters containing protonatable or already quaternized amino groups. They are used in amounts of 0.1-20 wt .-%, preferably 0.1-15 wt.%.

For example, 3-5 wt .-% Dimethylaminopropylmethacrylamid used.

Through the use of monomers with functional groups, which have an optimal interaction with the active ingredient, the release rate can be selectively controlled. In addition, the substrate binding properties can be adjusted in a targeted manner by means of the corresponding monomers.

Active substance b) used may be an odorous substance, for example selected from the group of mercaptans, lactones, ketones, terpenes, quinines, dialkyladipate heptylnony-ladipates, methyl salicylates, cinnamaldehydes or pine oils.

Examples of mercaptans are isoamylmercaptan, butylmercaptan or crotylmercaptan.

By the lactones is meant, for example, γ-alkyl-γ-butyrolactone or δ-alkyl-δ-valerolactone.

The ketones are understood as meaning, for example, methyl nonyl ketone, ethyl butyl ketone, methyl isoamyl ketone, isobutyl heptyl ketone, ethyl amyl ketone, methyl octyl ketone, geranylacetone or heptylideneacetone, preferably methyl nonyl ketone.

Examples of terpenes are substances such as α-terpinyl methyl ether, citronellyl nitrile or D-limonene. The active ingredient can be added to the polymeric matrix both during and after the polymerization. In the subsequent formulation, the wt .-% - proportion of the active ingredient is 0.1-15 wt .-% based on the polymeric matrix, preferably 1-10 wt .-% and in the formulation of the active ingredient during the polymerization of the polymeric Matrix is the wt .-% - 0.1-50 wt .-%, preferably 1-40 wt .-% - share (in each case based on the polymeric matrix).

The polymeric matrix a) can be carried out by conventional polymerization processes as substance polymerization, solution polymerization, emulsion, dispersion or suspension polymerization. It is also possible to carry out the polymerization as a precipitation polymerization if the solubility of the polymer in the reaction mixture is sufficiently poor.

In the polymerization methods mentioned, preference is given to operating under exclusion of oxygen, preferably in a stream of nitrogen. For all polymerization methods, the customary apparatuses are used, for. B. Rührkessel, Rührkessel¬ cascades, autoclaves, tubular reactors and kneaders. Preference is given to the methods of solution and emulsion polymerization. If the preparation of the polymers according to the invention is carried out by free-radical, aqueous emulsion polymerization, it is advisable to add interface-active substances C), for example emulsifiers or protective colloids, to the reaction medium. A compilation of suitable. Emulsifiers and protective colloids can be found, for example, in Houben Weyl, Methods of Organic Chemistry, Volume XIV / 1 Macromolecular Substances, Georg Thieme Verlag, Stuttgart 1961, p. 411 ff.

The polymerization may be carried out in solvents or diluents, e.g. Toluene, o-xylene, p-xylene, cumene, chlorobenzene, ethylbenzene, technical mixtures of alkylaromatics, cyclohexane, technical Aliphatenmischungen, acetone, cyclohexanone, tetrahydrofuran, dioxane, glycols and glycol derivatives, polyalkylene glycols and their derivatives, diethyl ether, tert. Butyl methyl ether, tetrahydrofuran, methyl acetate, isopropanol, ethanol, water or mixtures such as Isopropanol / water mixtures are carried out. The solvent or diluent used is preferably water, if appropriate with proportions of up to 60% by weight of alcohols, glycols or polyalkylene glycols. Particular preference is given to using water.

The polymerization can be carried out at temperatures from 0 to 300, preferably from 0 to 15O ⁰ C and particularly preferably 20 - 12O ⁰ C. For the polymerization Emulsions¬ be used specifically temperature ranges of 0-100 ⁰ C, preferably 5- 95 ° C. Depending on the choice of the polymerization conditions, it is possible to obtain weight-average molecular weights (M _w ) z. B. from 1000 to 2 00 000, preferably 5000 - set 150000. M _w is determined by gel permeation chromatography. The polymerization is preferably carried out in the presence of free-radical-forming compounds. Of these compounds, it is necessary to use up to 30, preferably 0.05 to 15, particularly preferably 0.2 to 8,% by weight, based on the monomers used in the polymerization. For multicomponent initiator systems (eg redox initiator systems), the above weights are based on the sum of the components.

Suitable polymerization initiators are, for example, peroxides, hydroperoxides, peroxodisulfates, percarbonates, peroxide esters, hydrogen peroxide and azo compounds. Examples of initiators which may be water-soluble or water-insoluble are hydrogen peroxide, dibenzoyl peroxide, dicyclohexyl peroxydicarbonate, dilauroyl peroxide, methyl ethyl ketone peroxide, di-tert. Butyl hydroperoxide, acetylacetone peroxide, tert-butyl hydroperoxide, cumene hydroperoxide, tert-butylpemeodecanoate, tert-amyl perpivalate, tert-butyl perpivalate, tert-butyl perbenzoate, lithium, sodium, potassium and ammonium peroxodisulfate and azobisisobutyronitrile, 2,2'-azobis (2-amidinopropane) - dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutyramidine) dihydrochloride, 2,2'-azobis (N, N'-dimethyleneisobutyramidine), 4,4'-azobis (4-cyanopentanoic acid) , 2,2 'Azobis (2,4-dimethylvaleronitrile).

The initiators can be used alone or mixed with each other, for. B. mixtures of hydrogen peroxide and sodium peroxodisulfate. Water-soluble initiators are preferably used for the polymerization in aqueous medium.

The known redox initiator systems can also be used as polymerization initiators. Such redox initiator systems contain at least one peroxide-containing compound in combination with a redox coinitiator, e.g. reducing sulfur compounds, for example bisulfites, sulfites, thiosulfates, dithionites and tetra- ationates of alkali metals and ammonium compounds. Thus it is possible to use combinations of peroxodisulfates with alkali metal or ammonium hydrogen sulfites, e.g. Ammonium peroxodisulfate and ammonium bisulfite. The amount of the peroxide-containing compound to the redox coinitiator is 30: 1 to 0.05: 1.

In combination with the initiators or the Redoxinitiatorsystemen transition metal catalysts may additionally be used, for. Salts of iron, cobalt, nickel, copper, vanadium and manganese. Suitable salts are, for. As iron (II) sulfate, cobalt (II) chloride, nickel (II) sulfate, or copper (L) chloride. Based on the monomers, the reducing transition metal salt is used in a concentration of 0.1 ppm to 1000 ppm. So you can use combinations of hydrogen peroxide with iron (II) salts, such as 0.5 to 30% hydrogen peroxide and 0.1 to 500 ppm Mohr's salt. Also in the polymerization in organic solvents, redox coinitiators and / or Übergangsmetallkataly¬ catalysts can be used in combination with the initiators mentioned above, z. B. benzoin, dimethylaniline, ascorbic acid and or¬ ganisch soluble complexes of heavy metals such as copper, cobalt, iron, manganese, nickel and chromium. The amounts of redox coinitiators or transition metal catalysts usually used are about 0.1 to 1000 ppm, based on the amounts of monomers used.

In order to control the average molecular weight of the polymers, it is often expedient to carry out the copolymerization in the presence of regulators. Conventional regulators may be used for this purpose, for example compounds containing organic SH groups, such as 2-mercaptoethanol, 2-mercaptopropanol, 3-mercaptopropionic acid, cysteine, N-acetylcysteine, but also sodium hypophosphite or sodium hydrosulfite. The polymerization regulators are generally used in amounts of from 0.1 to 10% by weight, based on the monomers. Also by the choice of the appropriate solvent can be influenced on the average molecular weight. Thus, the polymerization in the presence of diluents with benzylic H atoms leads to a reduction in the average molecular weight by Kettenübertra¬ supply.

In order to increase the molecular weight of the polymers, it may be expedient to carry out the copolymerization in the presence of small amounts of crosslinkers. Conventional crosslinkers such as bis (acrylic acid esters) of diols, such as ethylene glycol, diethylene glycol bisacrylate, trietylene glycol or polyethylene glycol in an amount of 0.01-5%, based on the monomers, can be used for this purpose.

If the polymer is obtained by the process of a solution polymerization in water, usually no separation of the solvent is necessary. Be¬ still the desire to isolate the polymer, z. B. a spray drying or precipitation (pH, salt, temperature) are performed.

If the polymer is prepared by the method of solution, precipitation or suspension polymerization in a steam-volatile solvent or mixture of solvents, the solvent can be separated by passing in steam so as to obtain an aqueous solution or dispersion. The polymer can also be separated from the organic diluent by a drying process.

Preferably, the polymers are in the form of an aqueous solution with Feststoffgehal¬ th of preferably 10 to 60 wt .-%, in particular 20 to 55 wt .-% before. As component B) it is advantageous to add carbonaceous, sulphatic or siliceous fillers, such as crystalline calcium carbonate, mica, talc, barite, quartz powder or aluminum silicates.

Furthermore, the term inorganic fillers includes pigments such as titanium dioxide, chromium oxide or iron oxides of different colors. In general, the fillers are added in fine grain size.

In addition, the paints according to the invention may contain in total up to 15% by weight of customary auxiliaries D), such as low molecular weight organic substances suitable as external plasticizers, e.g. Adipinsäureester or phthalic acid ester, organic solvents such as Trimethylpentandiolmonoisobutyrat, preservatives, biocides, foam-suppressing agents, thickening substances or matting agents.

Advantageously, the water used for the emulsion polymer for the preparation of A) forms component E). However, water can also be added in pure form to the preparations to be used according to the invention. The preparation of the preparations to be used according to the invention is expediently carried out by stirring the fillers into a template composed of water, the fillers dispersing agents and optionally thickening and foam-damping agents, then optionally external plasticizers and / or organic solvent and finally a component A) as a disperse phase containing 40 to 70 wt .-% aqueous starting dispersion admits.

The term paint is understood to mean both paints and lacquers or coatings. These may be unpigmented or transparently pigmented coatings, but may also be opaque systems. Exemplary are glazes and gloss coatings, wall paints, elastic coatings, wood paints, corrosion protection paints, oil pan coatings, swimming pool paints, anti-bite paints, floor paints, barrier paints and barrier primers (against wood ingredients, Niko¬ tin etc) and barrier coatings (such as against carbon dioxide and water) and Muiticolor paints called.

The amount of active polymer particles used in a coating depends on the desired effect. In order to defend against animals, the agent concentrations appropriate to the odor must be set individually to the type of animal to be defended. For this purpose, the release rate of the active substance must be adjusted to the desired Abwehreffekten by the choice of the polymer composition, the formulation of the coating and the Ausgangs¬ amount of the active substance used. An optimal interaction of the dispersion with the substrate (eg a wall) can be adjusted and thus z. As a washing or photochemical degradation of the drug can be prevented. Depending on the substrate to be coated, this can be optimized by copolymerizing suitable adhesion promoters or by formulating the coating. Examples are given, inter alia, in "Water-based Acrylates for Decorative Coatings" (Vincentz-Verlag, ISBN 3-87870-726-6, authors: Manfred Schwärt and Roland Baumstark) and the references cited therein.

Examples

a) subsequent formulation of the active ingredient in the prepared dispersion by stirring:

In one example, 2000 g of dispersion (solids content: 50%) were mixed with 25.2 g of 2-undecanone (methyl nonyl ketone) (2.5% solids to solid (f / f)). The mixing was carried out by stirring the substance until no more organic phase was visible on the Oberflä¬ surface.

Template: 69 g of water

5% of feed 1

10% of feed 2 Feed 1: 383 g of water

40 g emulsifier 1

30 g of methacrylic acid (MAS)

570 g of methymethacrylate (MMA) Feed 2: 96 g of Na ₂ S ₂ O ₈ (2.5% strength)

Emulsifier 1: C ₁₂ -C ₁₄ alkyl sulfonate sodium salt, ethoxylated with 30 EO (Disponil ^® FES77)

The original is heated under N ₂ to 8O ⁰ C, added portion of feed 1 and feed 2 and 10 minutes anpolymerisert. Add feed 1 in 2 hours and feed 2 in 2.5 hours. Postpolymerize for 30 minutes. FG: 50%, TG: 200-250 nm, Tg: 118-122 ⁰ C.

b) addition of the active ingredient during the polymerization:

Template: 112 g of water

5% of feed 1

10% of feed 2 Feed 1: 383 g of water

40 g emulsifier 1 25.2 g MAS 480 g MMA 102 g 2-undecanone (methylnonyl ketone)

Feed 2: 81 g of Na ₂ S ₂ O ₈ (2.5%)

The original is heated under N ₂ to 8O ⁰ C, added portion of feed 1 and feed 2 and 10 minutes anpolymerisert. Feed 1 (undecanone is stirred for 30 sec. With the monomers MMA / MAS, then the water + emulsifier is drawn in and stirred again for 30 sec.) In 2 h and feed 2 in 2.5 h. Postpolymerize for 30 minutes. FG: 50%, TG: 190 nm, Tg: 70 ^° C., Repellent (20% f / f)

Hunderepolenzfarbe

Parmetol ^® A 26: Schülke & Mayr Lusolvan ^® FBH, Lumiten ^® N-OC 30, Acronal ^® S 790, Luconyl ^®: BASF Westmin ^® 30 E, Omyacarb ^® 5 GU: Omya Agitan ^® 731: Tego Chemie Kronos ^® 2043: Kronos

wall attempt

A heavily frequented by dogs wall is coated with the above-described color with a coating weight of about 300g / m ² with typical painter technology. In this case, portions with appropriate active substance-free color, others with active substance-containing paint are painted. After six months of frequent use by the local dog population, the surfaces coated with active substance-free paint are strongly darkened by Hun¬ deurin, the surfaces provided with the active ingredient have no corresponding discoloration. This clearly points to different dog preferences for the various segments of the wall.

Claims

claims

Containing 1. paints

A) 1-30% by weight of polymer particles of a) 10-60% by weight of polymeric matrix and b) 0.1-50% by weight, based on the weight of the polymeric matrix, of active ingredient,

B) 15-65 wt .-% of an inorganic filler

C) 0.1-5% by weight of surface-active substances

D) 0-15 wt .-% customary auxiliaries

E) 25-60% by weight of water.

2. Paints according to claim 1, characterized in that the polymeric matrix a) aa) 40-95 wt .-% of at least one acrylic or methacrylic acid ester of a d-Cβ-alkanol or mixtures thereof, bb) 0-50 wt .-% vinylaromatic monomers cc) contains 0-15% by weight of ethylenically unsaturated monomers and also dd) contains 0.1-20% by weight of other monomers containing functional groups.

3. Coating according to one of claims 1 or 2, characterized in that the glass transition temperature of the polymeric matrix 90-150 ⁰ C.

4. paints according to any one of claims 1 to 3, characterized in that the acrylic or methacrylic esters aa) are selected from the group n-, iso-, t-butyl, n-hexyl or 2-ethylhexyl acrylate, methyl methacrylate or butyl methacrylate ,

5. paints according to one of claims 1 to 4, characterized in that the vinyl aromatic monomers bb) are selected from the group of styrenes, styrene derivatives or vinyl toluenes.

6. paints according to one of claims 1 to 5, characterized in that the monomers cc) are selected from the group of ethylenically unge¬ saturated 3-5 carbon atoms-containing mono- or dicarboxylic acids.

7. paints according to one of claims 1 to 6, characterized in that the active ingredient b), an odorant.

8. paint according to any one of claims 1 to 7, characterized in that the active ingredient b) is selected from the group of mercaptans, Lactones, ketones, terpenes, quinines, dialkyl adipate heptyl nonyl adipates, methyl salicylates, cinnamaldehydes or pine oils.

9. Coating composition according to one of claims 1 to 8, characterized in that the active ingredient is added during or after the polymerization of the polymeric matrix.

10. paints according to any one of claims 1 to 9, characterized in that the active ingredient is released in a controlled manner.

11. Use of the paint according to any one of claims 1 to 10 as Ab¬ wehrstoff against dogs, cats or mason spiders.