Patent (11) 3,608,06 72 Inventors Franz Alfes Krefeld; 56 References Cited Wolfgang Behrenz, -Stammheim; UNITED STATES PATENTS Karl Raichle, Krefeld-; Kurt 2,956,366 10/1960 Wiesmann...... 43/131 Weirauch, Krefeld, all of 3,169,705 2/1965 Geiger...... 239/43 3,173,223 3/1965 Dunn et al...... 43/13 21) Appl. No. 784,488 3,279,118 10/1966 Allen...... 43/129 (22) Filed Dec. 17, 1968 45) Patented Sept. 21, 1971 3,310,235 3/1967 Zbinden...... 23916 73 Assignee Farbenfabriken Bayer Aktiengesellschaft 3,318,769 5/1967 Folckemeret al...... 424/78 , Germany 3,364,105 l/1968 Geiger et al...... 424/358 X 32 Priority Jan. 16, 1968 3,470,293 9/1969 Geiger...... 424/84 (33) Germany OTHER REFERENCES (31) P 1694,240.8 Miles et al. J. AGR. Food. Chem. 10: 240-244 (1962) 'Stable Formulations For Sustained Release of DDVP" Primary Examiner-Shep K. Rose - Attorney-Burgess, Dinklage & Sprung

(54 SHAPED ARTICLES WITH LONG-TERMWAPOUR ABSTRACT: Shaped articles having long term vapor emis EMSSION sion comprising a thermosetting resin produced from an un 9 Claims, No Drawings saturated polyester and a vinyl monomer copolymerizable 52 U.S.C...... 424/22, therewith, containing an effective amount of 0,0-dimethyl-0- 424/78, 424/219, 43/131,239/6,239/60 (2,2-dichlorovinyl)-phosphoric acid ester as pesticidally, e.g. 51 Int. Cle...... A61k 24/12 insecticidally and/or acaricidally, active compound, in a ratio 50 Field of Search...... 424/78, by weight of active compound to resin of e.g. about 0.25-2: 1, 219, 22; 431131,239/60, 6 and also containing a solid filler, and optionally a liquid filler. 3,608,062 1 2 SHAPED ARTICLES WITH LONG-TERMWAPOUR are obvious; natural products are never homogeneous in their EMISSION structure. This is particularly true of a material with such a The present invention relates to and has for its objects the varying structure as wood. The differences between sapwood provision for particular new shaped articles containing 0,0- and heartwood and the structure of spring-wood laminae and dimethyl-O-(2,2-dichlorovinyl)-phosphoric acid ester, in the summer-wood laminae are only two examples of this. From form of thermosetting resins produced from unsaturated type to type, and even within one type of wood, these struc polyesters and vinyl compounds copolymerizable therewith, tural elements vary considerably, according to the environ and having a long term vapor emission, and methods for mental conditions under which a tree has grown. The expert producing such shaped articles in a simple manner and for knows how differently different pieces of wood behave when using such shaped articles to combat pests, especially insects O impregnated, one piece practically never resembling the and acarids, with other and further objects becoming apparent other. To achieve a uniform evaporation of the active com from a study of the within specification and accompanying ex pound an individual dosage would therefore have to be amples. These shaped articles in accordance with the present worked out for each piece of wood. invention possess the property of giving off the active com The same considerations apply also in regard to a product pound, hereinafter briefly called DDVP, to the surrounding 15 on the market in which cuttlefish shell is used as carrier atmosphere for a long time, for example, several months, in an material for DDVP. This skeletal element of the cuttlefish, of insecticidally and acaricidally effective amount. which likewise no one piece is the same as another, suffers DDVP of the structural formula from the further disadvantage that it is not everywhere readily 20 available in any desired amount. Natural products are there fore most unsuitable for the solution of the problem. CH-0, Furthermore, in German Auslegeschrift No. 1,230,250, 3-0--0 Cla shaped articles with persistent insecticidal effect are described Histo H---- which are characterized by the combination of a volatile, in has long been known as a pesticidally active compound with 25 secticidally effective organic phosphorus compound of insecticidal and acaricidal effect (G. Schrader: "Die Ent specific composition and a thermoplastic, water-insoluble wicklung neuer insektizider Phosphorsaureester," 3rd edition, macromolecular substance, in particular polyvinyl chloride or Verlag Chemie, Weinheim, Bergstrasse). Like most insecti copolymers which contain vinyl chloride. cides, DDVP acts as a contact as well as a stomach and As described in the above German Auslegeschrift No. respiratory poison. Since the compound possesses even at 1,230,259, the absorbency of polyvinyl chloride for DDVP is room temperature a high vapor pressure (20 C-1.2X10 limited, despite certain plasticizing properties of the mm. hg.) in comparison with other insecticides, its effect as a phosphoric acid ester on the synthetic material. Thus, for ex respiratory poison is particularly noteworthy. The compound ample, mixtures of powdered polyvinyl chloride which contain 25 percent DDVP, are wet (see column 5, line 65, of German is therefore used in automatic spraying devices as an aerosol 35 Auslegeschrift No. 1,230,259). for the control of noxious insects and spiders. On the other hand, experiments showed that formulations Advantageous for this purpose though its high volatility is, of polyvinyl chloride and DDVP alone are not suitable as such high volatility hinders the attainment of an adequate last vaporizing agents, since, even after only a short time, they ing effect. The DDVP volatilizes and disperses from a room so cease to give off sufficient active compound. To such mix rapidly that the room can, only 1 to 2 hours after application 40 of the active compound, be again infested with vermin without tures, therefore, just as to the montan wax formulations the latter being killed. A further disadvantage of DDVP lies in described in German Auslegeschrift No. 1,207,144, con that it hydrolyzes comparatively rapidly and this impairs its siderable amounts of plasticizers have to be added. The de lasting effect as a respiratory poison. pendence of the effect of DDVP-containing polyvinyl chloride Numerous attempts therefore have already been made to 45 formulations of the plasticizer content can be seen from the control the evaporation of DDVP in a room so that it takes following Table 1 which relates to the duration of activity in place quite gradually to maintain a concentration which is respect of house flies (Musca domestica) of shaped articles of pesticidally effective, but nontoxic to humans, and simultane polyvinyl chloride containing 20 percent DDVP (size: ously to protect the active compound against hydrolytic 12X12.5Xcm.) in relation to their plasticizer content, mea decomposition. 50 sured in a room of 50 cubic meters' size. In regard to such attempts, German Auslegeschrift No. l,207,144, column l, lines 20 to 24, reads in essence: TABLE "The production of long-lasting preparations is difficult, not only because of the high sensitivity to moisture of DDVP but Plasticizer Duration in weeks of activity also because of its incompatability with many carrier sub 55 (dioctylphthalate) such that 50 of the fies were stances.' content in killed within 24 hours in the aforesaid German Auslegeschrift, it is further dis closed that the problem of long-lasting, uniform insecticidal s 2 effect cannot be solved with the aid of mixtures of DDVP and 10 4. montan wax alone since no appreciable vaporization or 60 20 O evaporation of the active compound occurs. Even after 4 weeks' storage at room temperature, the content of active compound of such mixtures is practically the same, so that As the above table shows, considerable amount of they cannot be used for the purpose sought. Hence, German plasticizer are necessary for the shaped articles tested to have Ausiegeschrift No. 1,207,144 claims volatile agents having a 65 a sufficiently long-lasting insecticidal activity as solid vaporiz long-lasting insecticidal effect which consist of a combination ing agents. If the plasticizer is lacking, or if nough of it i of DDVP as active compound, a montan wax and present, the surface of the shaped article very rapidly becomes hydrogenated cottonseed oil or dibutylphthalate. These for impoverished in active compound. Not enough DDVP mulations, however, have the disadvantage that they exude a migrates from the interior of the shaped article, so that it mixture of DDVP and plasticizer which understandably gives 70 quickly becomes ineffective. rise to toxicological problems. lf, therefore, on the other hand the addition of considerable An attempt has been made to soak natural products with amounts of plasticizer is necessary, there results on the other DDVP, British Patent No. 2,072,218 claims a carrier for hand the difficulty that this additibn must take place at the ex DDVP consisting of wood with a moisture content of less than pense of the content of active compound. Also, a formulation 8 percent. The disadvantages of such a mode of application 75 containing relatively large quantities of plasticizer and DDVP 3,608,062 3 4 may have undesirable structural properties. Thus, for example shaped articles. The surface of such articles very rapidly shaped articles of polyvinyl chloride which contain 20 percent becomes impoverished in active compound and, because of plasticizer and 18 percent DDVP exude during storage in the cage effect of the three-dimensionally crosslinked ther gastight packs, and also in practical use, considerable amounts mosetting plastics, no, or too little, DDVP diffuses to the sur of a mixture of plasticizer and active compound. Because of 5 face from the deeper layers. The result of this is that the the corrosiveness of this mixture and the toxicological con shaped articles so produced possess no satisfactorily effect. siderations connected therewith, this behavior is very disad Shaped articles as used herein comprise shaped bodies such as vantageous. Since polyvinyl chloride, on the other hand, is plates, spheres, strips, tablets or bars or any geometric solid capable of absorbing only listed amounts of DDVP and (including hollow bodies). plasticizer this disadvantage would be overcome only by 10 It has now been found, in accordance with the present in reducing in the formulations either the protection of active vention, that shaped articles, such as plates, spheres, strips, compound or the proportion of plasticizer, or both at the same tablets or bars based on 0,0-dimethyl-O-(2,2-dichlorovinyl)- time. A lessening of the DDVP content would, however, im phosphoric acid ester (DDUP), incorporated in thermosetting pair the activity and a reduction of the proportion of resins produced from unsaturated polyesters and vinyl plasticizer would affect adversely the diffusion of the active 5 monomer compounds copolymerizable therewith, may now be compound and thus also the effectiveness. For this reason, for provided which have a long term pesticidal vapor emission ef. shaped articles which consist of polyvinyl chloride, DDVP and fect when the shaped articles contain solid fillers, optionally in plasticizer, it is recommended that in use they be accom combination with liquid fillers, and the weight ratio of active modated in a cardboard frame which is to receive the un 20 compound to the unsaturated polyester thermosetting resin is desirable dripping mixture of active compound and between about 1:4 to 2:1. plasticizer. Furthermore, the instant shaped articles have considerable A further disadvantage of the DDVP-polyvinyl chloride for advantage over the formulations described in the literature mulations must be seen in that, even when they contain the based on thermoplastic compositions. maximum of 20 percent plasticizer, a considerable part of the 25 The present invention also provides a process for the active compound does not reach the surface and is therefore production of shaped articles having a long term pesticidal wasted. Such shaped articles which have been used for 16 vapor emission effect, in which a mixture of 0,0-dimethyl- 0 weeks under practical conditions and no longer possess a (2,2-dichlorovinyl)-phosphoric acid ester, as active com satisfactory biological activity still contain, by chemical analy pound, and an unsaturated polyester is copolymerized with a sis (infrared measurement after extraction), about 50 to 60 30 vinyl compound, the copolymer containing one or more solid percent of their original DDVP content. This method of appli fillers, the weight ratio of active compound to the resulting cation therefore appears very uneconomical. copolymer being from between about 1:4 to 2:1. Finally, it must also be taken into account that, for the Suitable solid, e.g. inert, fillers usable according to the production of shaped articles of polyvinyl chloride plasticizer present invention are, for example: fibers of glass, sisal, hemp, and DDVP a considerable amount in terms of equipment is 35 nettles, coconut, flax and other vegetable products or necessary because the mixture has to be extruded, which synthetic fibers of the conventional type. Further examples of presupposes the presence of suitable machinery. Moreover, solid fillers are those of mineral nature, for example barium since production takes place at high temperatures (170 to sulfate, titanium dioxide, iron oxides, kaolin, quartz, and other 180° C.), losses of the very volatile active compound occur inert materials of the conventional type. which necessitate extensive protective measures for the work 40 Suitable liquid, e.g. inert, fillers are those with carrier effect, men engaged in the manufacture. for example dioctylphthalate, chloroparaffin or alkylsulfonic In German Auslegeschrift No. 1,230,259, exclusively ther acid aryl ester, a.e. a mixture of Cous alkylsulfonic acid phen moplastic water-insoluble macromolecular substances are yiesters. claimed as carrier materials, particular examples being: It has proved particularly advantageous to use the aforesaid polymeric vinyl compounds, polyolefins, polyacrylates, 45 solid and liquid fillers in combination with one another. polyvinylacetals, polyvinylidene compounds, and synthetic The amount of the fillers must, as already mentioned, be and natural elastomers, for example rubber and cellulosic such that the weight ratio of DDVP to the thermosetting synthetic materials. Examples of preferred vinyl compounds plastic is between about 1:4 to 2:1, and preferably about 1:30 are polyvinyl halides, such as polyvinyl chloride and fluoride, to 1:1, i.e. 0.25-2:1, and preferably 0.33-1: 1. polyacrylate esters and polymethacrylate esters, for example 50 It has been shown that thermosetting plastics in the polymethylacrylate and polymethylmethacrylate; and aforesaid form, in particular unsaturated polyester resins, pos polymeric benzene compounds, such as polystyrene and sess in accordance with the present invention the following ad polymerized vinyltoluene. The polymers or copolymers of vantages overthermoplastic compositions: vinyl chloride are said to be particularly suitable and they al 55 1. They have a better absorbency for DDVP (up to 50 per legedly exhibit, besides good physical properties, a very good cent); compatibility with the insecticidal organic phosphorus com 2. Since they retain less active compound, there results a pounds to be used. better quantitative utilization of the latter; In addition it is expressly emphasized in the said 3. They possess a better activity; Auslegeschrift No. 1,230,259 that only with the use of a non 60 4. The shaped article according to the invention do not drip; crosslinked material, that is, a thermoplastic material, is the 5. The production of the shaped articles can take place at desired effect achieved, namely the active compound is given room temperature; off into the atmosphere in controlled amounts continuously 6. The production is possible to carry out merely by pouring and uniformly for months. the mass into simple molds consisting of any desired From Swiss Patent No. 289,915, too, it is learned that 65 material, for example wood, without the use of machines; hardened shaped articles with active compounds worked into 7. The method of production according to the present in them, for example hardened products of phenolformaldehyde vention renders possible the providing of a structure for resins, soon stop exhibiting any useful insecticidally active the shaped articles in the form of layers with different vaporization. For one skilled in the art, the impression is DDVP and filler contents. clearly given that such thermosetting plastics are wholly un 70 For the production of the formulations according to the in suitable for such formulations. vention, mixtures of unsaturated polyester thermosetting These results published in the technical literature were con resins and DDVP are hardened according to methods custo firmed by our own experiments, since it was not possible to at mary for the processing of unsaturated polyesters resins with tain, by the incorporation of DDVP into unsaturated polyester the aid of polymerization-initiating radicals (see example "I. resins, a long-lasting insecticidally active vapor phase in 75 Bjorksten et al.: Polyesters and their Application," Reinhold 3,608,062 5 6 Publishing Corp., New York, 1959). Since losses of the readily polyethers or polyesters, epoxides, phenolformaldehyde and volatile active compound may occur at higher temperatures, it urea- or melamine-formaldehyde is advantageous to use conventional initiator-accelerator The shaped articles according to the present invention can systems effective even at room temperature, or high-energy be reason of their pesticidal activity be used for the control of rays such as ultraviolet or electron beams, for the conven the most diverse types of pests, such as insects and spiders. tional production of the polymerization-initiating radicals. The present invention also provides a method of combating Of the initiator-accelerator systems effective at room tem insect or arachnid (including acarids and spiders) pests in a perature, the combinations consisting of a diacylperoxide, confined space (such as a room or cupboard) which comprises such as benzoyl peroxide, and a dialkylamine, for example a situating or locating in the confined space a shaped article dimethylaniline; or a ketone peroxide, such as methylethyl 10 according to the present invention which emits a pesticidal ketone peroxide or cyclohexanone peroxide, and a cobalt ac vapor. celerator, such as cobalt naphthenate, resinate, octoate or The following examples illustrate, without limitation, the acetylacetonate; can be used, but in the presence of DDVP a production and long term vapor emission life of the shaped ar distinctly reduced speed of hardening is observed. On the ticles provided by the present invention, "parts" meaning other hand, initiator-accelerator systems consisting of a solu 15 parts by weight unless otherwise expressly stated. ble vanadium compound, for example the vanadium salt of The unsaturated polyester resins used as starting substances phosphoric acid dibutylester or a solution of vanadyl-p-tolune may be prepared in the conventional manner as follows: sulfonate, in butyl acetate containing .1 percent by weight of Resin A: A polyester of an acid number of 44 prepared from vanadium with peroxides attractive thereto, for example per 7,253 parts maleic anhydride, 43,883 parts phthalican esters, per-ketals, or alkyl-hydroperoxides, preferably cumene 20 hydride, 29,267 parts 1,2-propanediol and 4.2 parts hydroperoxide, retain practically all of their effectiveness in hydroquinone is dissolved in 28,000 styrene. the presence of DDVP and are therefore preferably used. Resin B: The unsaturated polyester is prepared from 647 An advantageous form of application is also the working in parts maleic anhydride, 2,284 parts phthalic anhydride, of the DDVP into polyester foams which, for example, may be 25 1,276 parts 1,2-propanediol, 724 parts dipropyleneglycol produced according to the methods described in French Pat. (HO-CH-0-CH-OH) and 0.125 parts hydroquinone. specification Nos. 1.535.795 and 1.535.796. After an acid number of 35 is reached, the product is dis The instant articles may be regarded as crosslinked or solved in 1510 parts styrene. hardened thermosetting, i.e. thermoset, resins produces from Resin C: A polyester of an acid number of 31 prepared from a copolymerized mixture of an unsaturated polyester, a vinyl 30 1294 parts maleic anhydride, 1598 parts phthalic an monomer copolymerizable therewith, DDVP and a solid filter. hydride, 986 parts 1,2-propanediol, 374 parts glycol, 636 The hardening products on which the shaped articles of parts diglycol (HOCHCH-O-CH-CHOH) and 0.72 synthetic materials are based are the usual mixtures of unsatu parts hydroquinone is dissolved in 1910 parts styrene. rated polyesters and monomeric vinyl compounds capable of being added thereto by polymerization, in the ration of 20:80 35 Example 1 to 90:10 percent by weight. The unsaturated polyesters are prepared in known manner Into a mixture of 1935 parts of polyester resin A (see by polycondensation of polyhydric, in particular dihydric, al above) and 774 parts DDVP are stirred successively 90 parts cohols, e.g. lower dihydric alkanols, such as 1,2-propanediol, of a 40 percent solution of methylethylketone peroxide in 1,3-butanediol or 2,2-dimethyl-1,3-propanediol, or polycon 40 dimethylphthalate and 30 parts of a cobalt octoate solution in densation of lower dihydric alkanolmono- and di-lower alkyl dictylphthalate which contains 1 percent by weight of cobalt. ethers, such as di- or tri-ethyleneglycol, with a 13-unsaturated From this mixture there is prepared in a closed mold a 5-mm. dicarboxylic acids or anhydrides thereof, especially, a, 6-un thick molded plate with a glass content of about 30 percent by saturated lower alkandioic acids and anhydrides, for example, weight, using a glass fibermat of 450 g. weight per square me fumaric acid or maleic anhydride, optionally with addition of 45 ter. The plate is released from the mold after 2 hours and then saturated dicarboxylic acids and anhydrides, especially lower, cut into shaped articles of the size 12x12 cm. The test articles e.g. up to C, alkandioic acids and anhydrides, benzene dicar possess a dry and nontacky surface. boxylic acids and anhydrides, etc., such as phthalic acid or its Example 2 anhydrides, isophthalic, succinic, adipic, or sebacic acid. The main physical characteristics of the unsaturated polyester 50 1533 parts of unsaturated polyester resin B (see above) are resins are the following: intimately mixed with 851 parts DDVP, 596 parts dioc tylphthalate, 90 parts of a 40 percent solution of methylethyl viscosity at 20°C. (DIN 53015) 600-2,000 Centipoise ketone peroxide in dimethylphthalate and 30 parts of a cobalt density at 20° C. 1,05-1,34 g/cm. 55 octoate solution in dioctylphthalate which contains 1 percent amount of thermal conductivity 0,10-0, 15 kcal/mh. C. cobalt. Using a glass fiber plate of density 450 g/m., there is specific heat 0.30-0,50 calfg. C. acid number ninor than 70 prepared from this mixture in a closed mold a 5-mm. thick OH-number minor than 100 molded plate with a glass content of about 30 percent by molar weight of the unsaturated weight. After 24 hours, the plate with nontacky, dry surface is polyester 800-5,000 60 taken out of the mold and cut into test pieces of the dimen sions 12X12 cm. Vinyl monomers which can be added in the usual way by Example 2a polymerization are ethylenically unsaturated monomers, for (comparative test) example styrene, mono- and dichlorostyrene, divinylbenzene, 65 vinyltoluene; vinyl esters such as vinyl acetate and vinyl 800 parts of the unsaturated polyester resin A (for penetra benzoate; acrylic esters and acrylonitrile; methacrylic acid tion, see above) and 200 parts DDVP are well mixed. The esters; and allyl esters such as allyl acrylate, phthalic acid dial mixture is then catalyzed with 30 parts of a 40 percent solu lyl ester and triallyl phosphate. tion of methylethylketone peroxide in dimethylphthalate and Inhibitors which may be optionally concurrently used in the 70 10 parts of a cobalt octoate solution in dioctylphthalate which conventional way are, for example: quinone, hydroquinone, contains 1 percent cobalt, and from this mixture a 5-5-mm. toluene hydroquinone, 2,5-di-tert-butyl-quinone or 2,6-di thick molded plate is produced in a closed mold. After 24 tert.-butyl-p-cresol. hours the plate is released from the mold and cut into test Further suitable thermosetting plastics are, for example, pieces of the dimensions 12x12 cm. which feel dry to the conventional resins based on diisocyanate-modified 75 touch. 3,608,062 7 8 EXAMPLE 3 TABLE 3 A a plate produced according to example 2a (comparative Occurrence of LT50 in the case of Musca domestica (in hours) after the hanging up of the shaped test) as well as, in each case, one of the plates obtained ac articles for cording to Examples 1 and 2 are suspended individually in the Preparation accord- --- ing to Example 0 wik. wk. 4 wks. 6 wks. 10 wiks.

middle of rooms of equal size of 50 cubic meters volume and, in each case, 2,000 house flies (Musca domestica) were ex 1. 2 2 2.5 3 posed to it. Observation is undertaken to see whether all the 1.5 2 3 3.5 5 flies have been killed in the course of 24 hours or not. The tests are repeated at an interval of 1 week in each case until a 100 percent destruction of the flies within 24 hours is no O EXAMPLE 7 longer observed. The lasting effect of the plate resulting 45 parts of unsaturated polyester resin A (for preparation, therefrom can be seen from the following table 2: see above) and 25 parts DDVP are very well mixed with 30 parts barium sulfate, 2.1 parts of a 40 percent solution of 15 methylethylketone peroxide in dimethylphalate and 0.7 of a TABLE 2 cobalt octoate solution in diocthylphthalate which contains 1 percent cobalt. The mixture is poured into a mold which con sists of 2 glass plates of the dimensions 20X20x0.3 cm, which Shaped articles according Duration of activity to Example in weeks internally are kept at a distance of 5 mm. by a plastic tube. 20 After 24 hours, the molded plate is released. The surface of the shaped article is free from tackiness and is dry. 9 to 10 2 3 to 4 2a (comparative Test) to 2 EXAMPLE 8 45 parts unsaturated polyester resin A (for preparation, see 25 above) and 25 parts DDVP are ground with 30 parts of most finely ground, readily dispersible rutile (i.e. crude TiO), 0.7 parts cumene hydroperoxide and 0.7 parts of an accelerator EXAMPLE 4 solution which contains 1 percent by weight of vanadium. The mixture is hardened at room temperature in the mold Into a mixture of 225 parts of polyester resin A (for described in example 7. When released after about 2 hours, a preparation, see above) and 75 parts DDVP are stirred suc plate with a surface which is free from tackiness and which is cessively 9 parts of a 40 percent solution of methylethylketone dry is obtained. peroxide in dimethylphthalate, and 3 parts of a cobalt octoate solution in dioctylphthalate which contains 1 percent cobalt. EXAMPLE 9 From this mixture there is produced in a closed mold, with the 35 use of a glass fiber mat of 450 percent weight per square me 225 parts of polyester resin C (for preparation see above), ter, a 5-mm. thick molded plate with a glass content of about 125 parts DDVP, 1.7 parts cumene hydroperoxide and 2.0 30 percent by weight. The plate, the surface of which is free parts of an accelerator solution which contains 1 percent from tackiness, is released from the mold after 2 hours, then vanadium are intimately mixed. From this mixture there is tempered at 40°C. for 4 hours in a gastight container and cut 40 produced in a closed wooden mold, with the use of glass staple into shaped articles of the size 12x12 cm. fibers of 6 mm. length, a 5-mm. thick molded plate with a glass content of about 30 percent by weight. The plate is released EXAMPLE 5 after 2 hours with a nontacky and dry surface. 66.5 parts polyester resin B (for preparation, see above) EXAMPLE 10 and 3.5 parts DDVP are intimately mixed with 1.75 parts of a 45 40 percent solution of methylethylketone peroxide in 80 parts of polyester resin C (for preparation, see above) dimethylphthalate and 0.7 parts of a cobalt octoate solution in are intimately mixed with 20 parts chloroparaffin (70 percent dioctylphthalate which contains 1 percent by weight cobalt. by weight chlorine), 40 parts DDVP, 1.4 parts cumene From the mixture obtained there is produced, using a glass hydroperoxide and 1.4 parts accelerator solution which con fiber mat of 450 g. weight per square meter, a 1-mm. thick 50 tains 1 percent vanadium. Using a glass fiber mat of surface molded plate with a glass content of about 30 percent by density 450 g. per square meter there is produced in a closed weight. After slight gelling, there is laminated onto both sides wooden mold a 5-mm. thick molded plate with a glass content of this molded plate, a further 1-mm. thick plate which of about 30 percent by weight and the plate is removed form likewise contains about 30 percent by weight of glass fiber the mold after 24 hours with a surface free from tackiness and mat, but also 10 percent by weight DDVP. Finally, after slight 55 which is dry. During suspension for 3 months in a closed room, gelling of these layers, there is again applied to the upper and no drip formation is observed. lower surface in each case a further 1-mm. thick layer with a DDVP content of 50 percent by weight and a glass fiber mat EXAMPLE 11 content of about 30 percent by weight and the external sur 60 A plate produced according to example 2 as well as one in faces of the test piece are covered with cellophane film. After accordance with the prior art and consisting of polyvinyl hardening and removal of the film, the surface of the shaped chloride which contains 20 percent plasticizer and 18 percent article is free from tackiness and is dry. DDVP are freely suspended for 16 weeks in a room and the EXAMPLE 6 DDVP content is then determined analytically (infrared 65 method after extraction). The plate according to example 2 Various preparations produced according to Examples 4 had given off to the atmosphere 71 percent of its original and 5 are individually suspended in the middle of rooms of DDVP content, whereas the comparative plate of polyvinyl equal size of 50 cubic meters volume and exposed in the later chloride had given off only 35.5 percent of its original DDVP to, in each case, 1,000 house flies (Musca domestica). The Content. time is then observed as to when 50 percent of the flies have 70 It will be appreciated that the instant specification and ex been filled (LTs). At specific intervals of time, which can be amples are set forth by way of illustration and not limitation, seen from the following table 3, flies are again released in the and that various modifications and changes may be made test rooms and the tests are evaluated in the same manner as without departing from the spirit and scope of the present in previously. Between the individual experiments, the rooms are vention. aired adequately. 75 What is claimed is: 3,608,062 9 10 1. Shaped article molded into the form of plates, spheres, solid fillers is present. strips, tablets, bars or hollow bodies and having a long term 4. Article according to claim 1 wherein at least one inert pesticidal vapor emission effect which consists essentially of liquid filler is also present. (a) a cross-linked or hardened thermosetting resin produced 5. Article according to claim 1 wherein said unsaturated from an unsaturated polyester and a vinyl monomer 5 polyester and vinyl monomer are present in a ratio by weight copolymerizable therewith, and a containing a pesticidally ef of between about 20:80 to 90:10. fective amount of (b) 0,0-dimethyl-O-(2,2-dichlorovinyl)- 6. Article according to claim 1 wherein said unsaturated phosphoric acid ester, as effective compound, and (c) as a polyester is prepared by the polycondensation of a polyhydric solid filler therein an effective amount of member selected alcohol with a member selected from the group consisting of from the group consisting of glass fibers, sisal, hemp, nettles, 10 o, g-unsaturated dicarboxylic acids and anhydrides thereof. coconut, flax, synthetic fibers, barium sulfate, titanium diox 7. Article according to claim 1 wherein said unsaturated ide, iron oxides, kaolin and quartz, said active compound polyester is prepared by the polycondensation of maleic an being present in a ratio by weight to the resin of between hydride, phthalic anhydride, and 1,2-propane-diol in the about 0.25-2:1, said molded shaped article having been presence of hydroquinone, and is copolymerized with styrene produced by curing the uncured form of (a) together with (b), 15 as vinyl monomer. (c) and a conventional polymerization initiating and ac 8. Article according to claim 7 wherein said unsaturated celerating system effective for curing (a) under conditions polyester is prepared by the polycondensation of maleic an which avoid high temperature loss of the readily volatile active hydride, phthalic anhydride, 1,2-propane-diol, and ingredient (b), (c) providing a long term pesticidal vapor dipropylene glycol in the presence of hydroquinone, and is emission effect to the surface of such shaped molded cross- 20 copolymerized with styrene as vinyl monomer. linked thermosetting plastic article, the surfaces of which 9. Article according to claim 7 wherein said unsaturated otherwise become very rapidly impoverished with little or no polyester is prepared by the polycondensation of maleic an (b) diffusion to the surface from the deeper layers. hydride, phthalic anhydride, 1,2-propane-diol, glycol, and 2. Article according to claim 1 wherein said ratio by weight diglycol in the presence of hydroquinone, and is is between about 0.33-1: 1. 5 copolymerized with styrene as vinyl monomer. 3. Article according to claim 1 wherein a mixture of inert

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75 E" Nij}) SAJ S '''I'ENT OF CIE /(, CE r RE (AEf : Y JE (). CO & RJECTr Y ONr a tent c. 3608062 buted September 21, 1971 -

Inventor(s). Franz Alfes et all ---ar------r-ra-a-a-a-all-well-e-ear Jt is cort if 3rd that error app cars in the abov c-identified patent and that said J.C. t t e is a tent are cre by corrected as shown b clow: - Col. 2, line 21 "1,230,250" should be -- 1,230,259 --; line 28 "described' should be -- disclosed --; line 47 "12 x 12.5 xcm' should be -- 12 x 12.5 x 0.5 cm --; line 63 'amount" should be -- amounts --. Col. 4, line 13 "DDUP' should be - - DDVP -- ; line 48 'l : 30' should be - - 1 : 3 - -; line 59 'article' should be -- articles --; line 73 'polyesters' should be -- polyester --. E" UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION at cnt No. 3608062 I)atod September 21, 1971 Inventor(s) Franz Alfes et al. PAGE - 2 mammar It is cortific d that crror appears in thc above-identified patent and that said Le: t t c is 'at cnt arc lec by corr ccted as shown bolo :

Awav Col. 5, line l "1959" should be - - 1956 - -; line 17 \ "tolune" should be -- toluene --; line 18 "... 1" should be -- 1 --; line 28 "produces' should be -- produced -- line 54 (in the Table) 'l,05-1, 34' should be -- l. 05-1.34 - -; line 55 (in the Table) "O, 10-0, 15" should be -- 0.10-0.15 --; line 56 (in the Table) "0, 30-0,50" should be -- 0.30-0.50 --

-A-S-L-A-Col. 6 line 4 'be" should be -- by -- fo-100 NED STATES PATENT O). FICE . (5/9) CER CATYy f J () CC)rv R RECTIONY r 1 l’at cnt No. 3608062. l)atcd September 21, 1971

Inventor(s). Franz Alfes et-age-ruroumr-arramew-a-ra-ra-re-re-r-r-ruhamma------all PAGE - 3. ---a-- It is certified that error a cars in thc abovc-idcntific d patcnt and that said letters i'a tent are eleby corr CC tod as shown b clow:

Col. 6, line 9 Delete 'a' (first occurrence) Col. 7, line 36 "450 percent" should be -- 450 g --; line 68 'later" should be -- latter --;

Col. 8, line 15 'dimethylphalate' should be -- dimethylphthalate -- plumn 9, line 9 after "of" insert -- a -- Signed and sealed this 9th day of May 1972.

(SFAL) At-- - test:-

EP:FETCHER,tie Sting Officer CommissionerROBERT GOTTSCHALK of Patents