MXPA98007103A - Non-aqueous gel composition of controlled release, for the care of the atmosphere and as a plaguage - Google Patents

Abstract

The present invention relates to non-aqueous controlled release gels for the care of the atmosphere, comprising about 1 to about 50 percent based on weight, of diblock, triblock, multiple block and / or radial blocks based on synthetic thermoplastic rubbers, the proportion of diblock copolymers to multi-block triblock copolymers and / or radial block copolymers can be varied from about 0 percent to about 100 percent in either direction, the material to be gelled is one or more hydrocarbon hydrocarbon-soluble substances or mixtures thereof, which on the basis of their physical properties play an important role in fixing the rate of controlled release, the hydrocarbon composition can vary in carbon length from about C-5 to about C -30, and can vary in vapor pressure to approximately 6OO mm Hg at 20 ° C; idrocarbons on a weight basis is about 20 to about 95 weight percent total of the gelled composition, the controlled release agent or active agent is one or more environmental care active substances such as fragrances, deodorants, masking agents , pest repellents or pesticides, and may comprise from about 0.1 to about 30 weight percent of the g

Description

COMPOSITION IN NON-AQUEOUS QEL OF CONTROLLED RELEASE. FOR THE CARE OF THE ATMOSPHERE AND AS A PLAQUICIDE CROSS REFERENCE TO RELATED REQUESTS This application is a continuation of part of the solitude of the United States Series No. 08/609 »079» filed on February 29, 1999 FIELD OF THE INVENTION The invention relates to products in controlled release polymer gel, for the care of the atmosphere. such as environment refreshers and the like. More particularly, the invention relates to atmospheric care products employing non-aqueous controlled release polymer gels "and more particularly, heterophase hydrocarbon gels. thermally reversible »which are suitable for use in the controlled release of one or more active substances for the care of the atmosphere, or of pesticidal substances. The product for the care of the atmosphere of the invention employs a hydrocarbon gel containing mixtures of block copolymer. the copolymers being preferably derived from styrene and rubber block units.

BACKGROUND OF THE INVENTION Controlled release agents have been used in the art in a variety of applications including the release of pheromones. insect repellents, animal repellents and pharmaceutical agents. For example, U.S. Patent No. 4,469,613 discloses a detergent bar for releasing insect repellents. containing homopolymers of poly (epsilon-caprolactone) "and other polymers (for example polyethylene or polypropylene). U.S. Patent No. 5,150,722 discloses a low density polyethylene / high density polyethylene flake for use in controlled release. The controlled irradiation in the system described therein is affected by the use of a stratified structure, with a nucleus containing the agent to be released and a "burst layer" which restricts the premature release of the active substance. U.S. Patent No. 5,316 * 744 discloses porous particles for the controlled release of an active substance. The particles are blocked by the use of an interlaced hydrogel polymer, the blocking agent being sensitive to its physical environment. Japanese Patent Publication No. 05 345 011 discloses hydrogenated block copolymers of aromatic vinyl compounds, as vehicles for fragrances such as ambient deodorants. U.S. Patent No. 5,221,534 describes gels comprising a mineral oil and copolymer mixtures and include auxiliary components for health and beauty. PCT Patent Application No. W088 / 006O3 of Francis et al. Discloses block copolymer compositions which are described as gels or gelloid extended polymer compositions comprising an intimate mixture of a block copolymer containing blocks. relatively hard and relatively elastomeric blocks. A suitable block copolymer is Kraton 1S51. a tribloque copolymer. The copolymer additionally contains at least 500 parts by weight of extender liquid per 100 parts of the block copolymer. the liquid being present to extend and soften the elastomeric blocks of the block copolymer. European Patent Application No. 224389 to Qamarra et al. Discloses ester-block copolymer compositions, and in particular a mixture of triblock copolymers and a hydrocarbon oil. These compositions are useful as sealing materials. U.S. Patent No. 4,369,284 describes a clear gel prepared from block copolymers and oils, used for molded products. The triblock copolymers used therein accept specific styrene end blocks for the ethylene and butylene center blocks. The proportion of block from end to block of center that is given, is between 31:69 and 40-60. The present invention provides an improved product for the care of controlled control atmosphere, using unique vehicle systems.

BRIEF DESCRIPTION OF THE INVENTION Therefore, an object of this invention is to provide heterophase thermally reversible hydrocarbon gel compositions which have advantageous properties when used as a vehicle to solubilize or suspend an active substance for the care of the atmosphere and to perform the controlled release of said active substance. A further object of the invention is to provide hydrocarbon gel compositions formed with certain diblock, tr block, radial block and / or multiple block copolymers, which have advantageous properties when used as a non-aqueous polymer gel. controlled release for active substances for the care of the atmosphere. A further object of the invention is to provide methods for producing fragrance dispensers, deodorants, pest repellents, pesticides and the like, in controlled release hydrocarbon polymer gel, and articles of manufacture employing them.

Other objects and advantages of the present invention will become apparent as the description of the invention proceeds. To meet the above objectives and advantages. The present invention provides in a "non-aqueous gel composition controlled release for the care of the atmosphere" comprising: (a) from about 20 to about 95 percent by weight of a hydrocarbon, and optionally one or more soluble substances in the hydrocarbon »< e) of about 50 weight percent of a diblock, triblock, radial block and / or multiple block copolymers or mixtures thereof, comprising from about O to about 100 Y * by weight of one or more coding diblock quenches and from about 100 to about O 54 by weight of one or more triblock copolymers. of radial block and / or of multiple blocks "and (c) from about 0.1 to about 305. by weight of one or more active substances for the care of the atmosphere. The hydrocarbon used in the composition preferably has a vapor pressure of up to about 600 m Hg at 20 ° C. The invention further provides methods of producing manufacturing articles that are dispensers of controlled release active substances, and methods of using the hydrocarbon gels of polymer in these articles.

BRIEF DESCRIPTION OF THE DRAWINGS Reference is now made to the drawings appended to the application, wherein: Figure 1 represents a comparison of the release of fragrance »with the passage of time, of gels for the care of the atmosphere comprising different hydrocarbons; and Figure 2 represents the weight loss of a gel of the invention with the passage of time.

DETAILED DESCRIPTION OF THE INVENTION The present invention is directed to novel non-aqueous controlled release vehicles for the regulated release in time of active substances for the care of the atmosphere. By the term "atmospheric care" is meant substances that are active to affect the atmosphere in any way, this term includes fragrances, deodorants, masking agents, pest repellents, pesticides, and the like. Controlled release vehicles are block copolymer gels containing hydrocarbon. The products of the invention are useful for the controlled release of refreshers from the fragrance environment, air deodorants, pesticides, pest repellents and the like, such as those employed in the home (eg in rooms, cabinets, garages, workshops, of the pavement and cabinets), in offices, vehicles (for example, car, truck, van, train, airplane, boats, etc.) and industrial and institutional facilities * including public toilets, warehouses, factories, restaurants and stores. The non-aqueous controlled-release gel compositions for the care of the atmosphere of the invention comprise a hydrocarbon, optionally comprising one or more hydrocarbon-soluble substances »one or more copolymers of dib» one or more triblock copolymers. of radial block and / or of multiple blocks, or a mixture thereof "and one or more active substances for the care of the atmosphere. Therefore, the invention can be described as a controlled release gel for the care of the atmosphere comprising: (a) from about 20 to about 95 weight percent of a hydrocarbon, which optionally contains one or more soluble substances in hydrocarbon, or mixtures thereof. ib) Approximately 1 to about 50 weight percent a diblock, triblock copolymer. of radial block and / or of multiple blocks or a mixture thereof »which comprises approximately O to about 100 weight percent of one or more copolymers of diblock and B Approximately 100 to approximately 0 percent by weight of one or more triblock compolymers. of radial block and / or of multiple blocks; and (c) from about 0.1 to about 30 weight percent of one or more active substances for the care of the atmosphere such as fragrances or fragrance mixtures »one or more essential oils, and / or a deodorant or deodorant mixture; wherein deodorants may or may not be fragrances by themselves and / or masking agents, pest repellents, pesticides, etc. "as the active ingredient (s). In a preferred composition of the invention, the copolymers or mixtures thereof comprise from about Ol to about Z5 percent by weight, preferably from Ol to about 10 percent by weight, of one or more diblock copolymers and from ? approximately 70 to about 99.9 percent "weight of one or more triblock, radial block and / or multiple block copolymers. When formed in gels, the copolymers or mixtures thereof comprise approximately 1 to about 50 percent by weight of the total weight of the composition. Preferably, the total weight of the content of the hydrocarbon ranges from approximately 30 weight percent, preferably from 5 to 20 weight percent, preferably from 7 to 1.3 weight percent, although this preference it can change depending on the particularities of the desired application, as will be evident to the expert in the field. Each of the diblock »triblock copolymers. radial block and / or multiple blocks, used in the invention, contains at least 2 thermally incompatible therm segments. With the term "thermodynamically incompatible" with respect to polymers, it is understood that the polymer contains at least 2"compact" segments, for example, at least one hard segment and one soft segment. In general, in a triblock polymer, the proportion of segments is a hard one, a soft one, a hard one, or copolymer A-B-A. On the other hand, the diblock copolymers are of type A-B and sequential with respect to hard and soft segments. The multiple block and radial block copolymers can contain any combination of hard and soft segments, provided they have both hard and soft characteristics. These copolymers are fully described in U.S. Patent No. 5,221,534, the disclosure of which is incorporated herein by reference. Commercially available thermoplastic rubber type polymers, which are especially useful in the formation of the compositions of the present invention, are sold under the trademark Kraton® of the Shell Chemical Company. These Kraton® rubber polyesters are described as elastomers that have an unusual combination of high strength and low viscosity and an IO unique molecular structure of linear diblock copolymers »triblock and radial blocks. It is said that each Kraton rubber molecule "consists of block segments of monomeric units of styrene and monomer units of rubber and / or comonomer, each block segment can consist of 100 or more monomers or comonomer units. the triblock copolymer is the ABA linear block type mentioned above, styrene-butadiene-styrene (SBS) and styrene-isoprene-styrene (SIS) »which is the series of rubber -.raton" D. A second polymer of this The general type is the Kraton1 * G series. This copolymer comprises a styrene-ethylene-butylene-styrene structure (S-EB-S). The Kraton * T series is preferred in the practice of the invention »since the copolymers of this series are hydrogenated and therefore are thermally more stable» that is »less likely to occur decomposition during the mixing of the polymers of the series G with the hydrocarbon or mixture of hydrocarbons (the polymers of the D series have unsaturation inside the rubber block). Kraton * G rubbers are indicated as compatible with only and naphthenic oils "and triblock copolymers are reported to take more than 20 times their weight in oil to make a product that can vary in consistency, from a "Jello?" up to a strong elastic rubber material, depending on the grade and concentration of the rubber. The ABA structure of the Kraton * rubber molecule has polystyrene end blocks and elastomeric middle part blocks. A preferred triblock polymer is a triblock polymer of the type Kraton * G. in particular Kraton * 6-1650. This Kraton * G-1650 is a SEBS triblock copolymer having a specific gravity of approximately 0.91 »and is said to have a tensile strength of approximately 35 Kg / cm2, as measured by the ASTM method of tension clamp tester D -412 »with separation speed of 25 cm / min. The manufacturer states that the rubber-styrene content of Kraton * G 1650 is about 29:71, and the Brool.fleld viscosity is about 8000 (solution in toluene, cps at 25 ° C »25 weight percent). The Shore A hardness is about 75. The diblock polymers include the AB type, such as styrene-ethylene-propylene (S-EP) and styrene-ethylene-butylene (S-EB), styrene-butadiene (SB) and est-isoprene (SI). ). A preferred diblock copolymer is Kraton * G-1702. When gels are formed, the hydrocarbon, optionally one or more hydrocarbon solute substances, or mixtures thereof, comprise from about 20 to about 95 weight percent of the total weight of the composition. Preferably, the total weight of the hydrocarbon, one or more hydrocarbon-soluble substances or "mixtures thereof" contained in the composition "ranges from about 65 to about 95 weight percent" and preferably ranges from about 80 to about 93. percent in weight. Most preferably »the total weight of the hydrocarbon» one or more hydrocarbon-soluble substances »or mixtures thereof, in the composition of the invention, is about 85 weight percent» although this preference may change depending on the particular application desired »As will be apparent to the person skilled in the art. Although not limited by theory, it is believed that generally at the shorter carbon chain length of the hydrocarbon, one or more hydrocarbon-soluble substances or mixtures thereof will be more volatile the hydrocarbon. According to the invention, it is believed that the hydrocarbon »one or more hydrocarbon-soluble substances» or mixtures thereof »act as a vehicle for the active substance in the composition. Thus »when a hydrocarbon is chosen» optionally including one or more hydrocarbon soluble substances, to be used in the invention »care must be taken to ensure that the hydrocarbon, or optionally one or more hydrocarbon soluble substances, is of sufficient chain length to get to bond conveniently with the polymer mixture »in such a way that the desired gel consistency can be obtained for the particular application intended. Under these considerations, it is generally preferred that the volatile hydrocarbon components useful in the practice of the invention, comprise at least about 5 carbon atoms, preferably at least 8 carbon atoms, and less than about 30 carbon atoms. , and which may also contain one or more functional groups selected from the group consisting of hydroxyl, carboxylic acid and carboxylic acid esters, and having a vapor pressure of up to about 600 mm Hg at 20 ° C. The active ingredients will be released from the gel by evaporation (volatilization). Alternately, the fragrance or fragrances and / or the deodorant or deodorants and / or the pest repellent or pesticide active agent, may be released by forced air evaporation, or by heating. The hydrocarbons useful in the gels of the invention as defined above include, but are not limited to, mineral oils, mineral solvents, mineral spirits, synthetic hydrocarbons (oils and volatile solvents)., animal oils, vegetable oils »and mixtures of these hydrocarbons. A preferred group of hydrocarbon oils are the synthetic isoparaffin hydrocarbons sold under the Isopar * brand, such as those listed in Table 1 and mixtures thereof.

Ct, APRQ A Non-aqueous controlled release gels for the care of the atmosphere of the invention "all incorporate one or more active substances in the gel" that are released into the atmosphere or the environment. These active substances are generally employed in concentrations ranging from about 0.01 to about 30 weight percent of the total gel composition. However, it will be recognized by the person skilled in the art that active substances can be used up to their characteristic level of solubility, when so required. Active substances for the care of the atmosphere useful in accordance with the invention include but are not limited to. synthetic deodorants »natural deodorants, natural fragrances» synthetic fragrances »synthetic essential oils and natural essential oils. Fragrances may include but are not limited to perfumes, essential oils, aromatic chemical agents, absolutes, balms, concentrated oils, extracts, infusions and mixtures of pampering. Examples of synthetic and natural fragrances include, but are not limited to, terpene hydrocarbons. esters »ethers» alcohols, phenols, ketones. acetals, oximes and derivatives thereof and mixtures thereof. Examples of terpene hydrocarbons include lime terpene, lemon terpene and limonene dimer. Examples of the esters include ga ma-undecalactone. ethylmethyl phenylglycate »allyl caproate. allyl salicylate »amyl benzoate» amyl acetate. benzyl acetate. benzyl benzoate »benzyl salicylate or» benzyl propionate »butyl acetate, benzyl butylate, benzyl phenylacetate, cedril acetate, citronellyl acetate, citronellyl format» p-cres acetate, 3-t acetate -penty I cyclohexyl »cyclohexyl acetate, cis-3-he enyl acetate, cis-3-hexenic acid salicylate, dimethylbenzyl acetate, diethyl phthalate, a-decalactone dibutyl phthalate, ethyl butyrate, ethyl acetate» ethyl benzoate »fenchyl acetate» geranyl acetate »ga ma-dodecalac ona, dihydrojas methyl onate» isobornyl acetate. beta-isoprope salicylate? ieti »lina acetate! ino »methyl benzoate» 2-t-butylcyclohexa acetate? it »methyl salicylate» ethylene brassylate »ethyl dodecanoate, methyl phenylacetate» phenylethyl isobutyrate »feni leti ifeni lo acetate, phenylethyl acetate, methylphenyl carb nyl-acetate, 3,5,5-trimethyl acetate This is terpinyl acetate, triethyl citrate, 4-t-butylcyclohexyl acetate. and vetiveril acetate. Examples of ethers include p-cresylmethyl ether, diphenyl ether, methyleugenol and phenyl isoamyl ether. Examples of alcohols include n-octyl alcohol, n-nonyl alcohol, beta-pheni leti Idimeti 1-carbinol »dimethyl benzylcarbinol, carbitol, dihydromircenol, dimethyl octanol, henoligol, linalool, leaf alcohol, nerol, enoxiethanol, 3-phenyl-1-propanol »beta-phenylethyl alcohol» methylphenylcarbinol, terpineol »tetrahydroalocimenol» tetrahydrol nalool and 9-decen-l-ol. Examples of aldehydes include n-nonyl aldehyde. undecylenic aldehyde. methylnonylacetaldehyde »anisaldehyde. benzaldehyde »cyclane! dehyde, 2-hexanal exanal, aldehyde hey 1-cinnamic» in 1-acetaldehyde, 4- (4-hydroxy-4-methyl-1-pentene) -3-cyclohexane-1-carboaldehyde, aldehyde pt -bu la-met Ihidroci ico »hydrox c troné! al» al a-am? Ici ama! Dehyde, and 3,5-dimeti 1 ~ 3-cyclohexan-1-carboaldehyde. Examples of phenols include eugenol. Examples of ketones include 1-carvone, α-da ascona, ioneone, 4-t-pentylcyclohexanone, 3-ami, 1-4-acetoxy-tetrahydropyran, tonne, methyl ionone, p-t-amylcyclohexanone, and acetyl-lyerene.

Examples of acetals include phenylacetaldehyde dimethylacetal. Examples of oximes include 5-methyl 1-3-heptanone oxime. The active ingredient may also be one or more repellents of pests or pesticides. The term "pests" is considered to include any dangerous or destructive organism, including insects, nematodes, fungi or the like. Therefore, the invention includes all these plague and plague repellents. for example »insecticides» nematocides and fungicides »as well as materials that repel these pests. Pesticides useful as active substance in the invention include N-cp (4-chlorophenyl) -aminocarbonyl 13-2,6-difluorobenzamide; 1 »1» - (2 »2» 2-trichloroeti1 ide) is (4-chloro-benzene); 2'-2-dimethyl-1'-3-benzodioxol-4-yl) ethylcarbamate »0,0-diethyl-0-6-methyl-2- (l-methylethyl) -4-pyridinyl} -phosphothioate and O-ethylphosphonothioothioate ethyl-S-phenyl. The pesticides can be of several types; lethal and stomach preparations, including Hydrometi lnon (CAS-67485-29-4), Fenoxicarb (CAS-79127-80-3) and Avermectin; lethal residual contact preparations such as synthetic pyrethroids "including permethrin (CAS-52S45-53-1) and cypermethrin (CAS-66841-24-5). carbamates including Propoxur (CAS-114-26-1) and Carbar 1 (CAS-63-25-2). osphorothioates such as Diazinon (CAS-333-41-5); fumigant lethal preparations including organophosphates such as DDVP (CAS-62-73-7) and Clor eni fas (CAS-470-90-6). chrysanthemums including D-trans-Aletrina »and juvenile hormones such as methoprene (CAS.40596-69-8) and idroprene (CAS-41096-46-2). Examples of insect repellents that serve as active substance in the gels of the invention are phyto-diethyl-m-toluamide "commonly referred to as" DEET ". for mosquitoes and D-empenthrin for moths, and citronella oil. These insect repellents and insecticides are illustrative of the active substances useful in the practice of the invention. Other insecticides and insect repellents can be conveniently used as active substance as is known to the person skilled in the art. In summary, virtually any hydrocarbon-soluble active substance for the care of the atmosphere known to the person skilled in the art can be used in the composition of the present invention. However, typically the active substance is one or more fragrance agents, deodorant and / or more volatile high-load masking agent used in environmental refreshers and when possible, the non-polar should be preferred as much as possible. , to maximize compatibility with the gel material. In Figure 1. three different oils are used with the same formulation for illustrative evaporation rates. Each sample consisted of 91.5 weight percent hydrocarbon solvent, 8.4 weight percent Kraton * G 1650 triblock copolymer, and 0.1 weight percent Kraton * G 1702 diblock copolymer. Each sample had a surface area e about 20 cm * »and allowed to evaporate at room temperature (about 22 ° C.> during the indicated period.The three oils were operable but at different speeds.The gels may also contain other additives to change the velocity of volatility and / or to assist in the solubilization of the active substance for the care of the atmosphere with the gel »for example» surfactants together with ingredients added to change the physical state of the gel.These ingredients are oil-soluble materials that can soften the gel » such as petrolatum »resins, waxes and materials that can soften the gel or change the release rate of volatile materials» such as surfactants and oil-soluble liquids, such as esters and silicones. A preferred silicone is cyclomethicone »available from Dow Corning. Additionally, antioagulants and other stabilizers may also be present or added to the gels. Up to 50 weight percent of the hydrocarbon can be replaced with these solubilizing substances. The consistency of the gel of the invention is controlled by varying the amount, proportion and types of certain polymers, preferably diblock, triblock, radial block and / or multiple block copolymers. The amount of each polymer and the amount of the mixture contained in the hydrocarbon determines the final shape of the gel. In general »the higher the copolymer content. the gel will be more rigid. In addition »the greater the amount of triblock copolymer» radial block and / or multiple blocks in the polymer mixture »the gel mixture will be more rigid. The gels of the present invention vary from thin to rigid »as needed, and they are generally transparent gels. The polymers of the invention provide gels that have convenient rheological properties, and thus provide novel applications, particularly with respect to non-aqueous active substance additives for the care of the atmosphere which are, at best, sparingly soluble in aqueous gels. Product formation is achieved from block copolymers that form three-dimensional networks or gels by physical entanglements. The entanglements in these block copolymers occur due to the formation of sub-microscopic particles of a particular block, referred to as a domain. Interlacing of the insoluble domains can be obtained by factors affecting the interlacing density of the networks, including the length of insoluble block domains, the length of soluble block domains, and the number of interlacing sites. For example, branched or star polymers and other multi-block copolymers will have more entanglements than triblock or diblock polymers. The type of solvent or plasticizer to which the blocks are subjected also affects these characteristics. Certain gels exhibit syneresis when separation of liquid from the gel occurs by shrinkage, by virtue of the concentration of insoluble blocks present in the triblock copolymer. The higher the insoluble block concentration, as exemplified by styrene, the greater the phase separation and the interlacing that occurs. However, according to this invention, the amount of syneresis that occurs can be controlled by mixing these systems with diblock copolymers, triblock, radial block and / or multiple blocks, which do not exhibit syneresis. The composition of the invention has the advantage that the gel consistency can be varied from an i-rigid gel to a rigid gel, depending on the composition of the polymer mixture and, as such, is suitable for uses that are not possible using particulates and gels without autosoporte. For example, the hydrocarbon gels of the present invention can be used for self-sustaining atmosphere care products such as air fresheners, which have a suitable consistency for self-supporting applications. An additional advantage of hydrocarbon gels for the care of the atmosphere of the invention is that the base of the gel is not aqueous. Therefore, these gels are more easily usable with non-aqueous actives including, for example, organic compounds not readily soluble in aqueous controlled release systems. This increased solubility additionally allows for a higher concentration of many active substances than can be achieved by using aqueous gel controlled release systems, thereby providing products that have fragrance and / or stronger deodorizing potentials when desired. Examples of suitable hydrocarbons include: peanut oil, oils and paraffinic solvents. unique isopara oils »naphthenic oils and solvents. natural mineral oils. synthetic oils »synthetic sun and similar. In a particularly preferred embodiment of the invention, the gel comprises a mixture of a Kraton * triblock copolymer and a Kraton diblock copolymer as described herein in combination with hydrocarbon, particularly natural or synthetic hydrocarbon which is It knows has a homogeneous smooth consistency, and an active substance for the care of the atmosphere, repellent of plague or plagicida. For bars. gels »creams» lotions »etc.» insect repellents »the particularly preferred repellent is N, N-diethyl-m-toluamide (DEET). Also, citronella oil is a preferred repellent. It is preferred in the present invention that the end-to-block block ratio of ethylene and butylene center in the block copolymer be less than 31:69. The non-aqueous controlled release gels for the care of the atmosphere of the invention are prepared by mixing one or more triblock copolymers in the hydrocarbon. of radial block and / or multiple blocks, or mixtures thereof, and optionally one or more diblock copolymers, each in the desired amount. In a preparation method, the hydrocarbon is first heated to a temperature of about 65 ° C to about 85 ° C. Then, one or more triblock, radial block and / or multiple block copolymers or mixtures thereof are added slowly, and optionally one or more diblock copolymers, each in the desired amount, to the heated hydrocarbon with stirring. The temperature of the mixture is maintained for a sufficient time to dissolve the copolymer or mixtures of the mißmoß in the hydrocarbon. The mixing can be carried out in any conventional manner, and again it is preferred in this step. In general, the polymer mixture dissolves sufficiently in approximately 30 to 60 minutes when the hydrocarbon / polymer mixture becomes clear and homogeneous. For certain highly volatile hydrocarbons, this mixing can occur in pressure vessels. Generally, the active substance adds to the gel in the desired amount in the cooling step, although in the case of certain active substances, notably solid active substances, the addition of the active substance may be conveniently before the composition is heated to increase the solubility of the active substance. The composition is then poured into a mold or container and subsequently allowed to cool to form a gel. Alternatively, if the active substance is a particular volatile substance, it will generally be added to the composition at a point in the cooling process in which the premature loss of the active substance is minimized. In another embodiment of the invention, the hydrocarbon is first heated to a temperature of about 65 ° C to about 85 ° C.; at this point »the copolymer mixture is added to the desired weight percentage» as indicated herein. After sufficient time for the copolymer to melt in the hydrocarbon, the composition is poured into a mold or into a container and then allowed to cool to form a gel. The active substance is usually added during cooling. Similar variations of the method of the invention and known to the skilled person, in the light of the present description, are within the scope of the present invention. In the manufacture of the controlled release gels of the invention, it is particularly preferred to cool the polymer composition in a container or mold, depending on the desired final application. The container can be of any type suitable for the indicated use, as is generally known in the art. As an example of container urx, conventional, clear, colored, or otherwise decorated containers are conveniently employed to contain the non-aqueous controlled release gels of the invention. A mold is used to impart external characteristics to the final products for those applications in which said characteristics are desired in the final product. Additionally, a mold can be used to impart a particularly desired shape to the product. It is also within the scope of the present invention to cool the product in a container directly suitable for final use, or compatible with a suitable container for final use. The non-aqueous controlled release gels for the care of the atmosphere of this invention may also contain approximately 0.01 to approximately 5.0 percent by weight of one or more additives conventionally employed, such as stabilizers, antioxidants, dyes, etc. phosphorescent agents and the like, in an amount that does not affect or reduce the desired properties of the gel, particularly the ability of the gel for controlled release to perform its desired function. With respect to antioxidants, specific reference is made to BHT, which is generally employed at approximately 0.02 weight percent. The composition can also be packaged in a conventional aerosol container. Any conventional propellant can be used. However, for most applications that include pesticide sprays, it is preferred to use hydrocarbon, dimethyl ester, or R-134a »gases as examples of propellants that do not adversely affect the environment. When necessary, the dyes are useful in the invention, since the gel composition is generally transparent. In this way, the gels of the invention can vary from completely colorless to those having an intense color, as desired, by controlling the amount of dye employed. Rigid gels can be made in multiple colors or have layers of color. Other design variations will be readily apparent to the person skilled in the art, in light of the present description, and are within the spirit and scope of the invention. The following examples are presented to illustrate the invention, and this should not be considered as limited thereto. In the examples, the parts are by weight per 100 parts by weight of the composition (ie% by weight). unless otherwise indicated. In these examplesß. The diblock and triblock polymers used are the preferred Kraton polymers 1702 and 1650 described above, and obtained from the Shell Chemical Company. Pennreco 2257 is a hydrocarbon oil with an average carbon chain length of approximately 14 carbons, available from Pennsoil Products Company. Geahlene * 1600 comprises mrt mineral oil and a mixture of polymers, best described by its definition of CFTA: "Copolymer of mineral oil (and) hydrogenated butylene / ethylene / styrene, (and) hydrogenated ethylene / propylene / styrene copolymer". Geahlene * 1600 is also available from Penzzoil Products Company.

EJEP Q j.

A cooling gel of the controlled release air is prepared in the following manner: Drakeol mineral oil * 45.50 Penreco 2257 37.00 Polymer 1650 16.00 Polymer 1702 0.50 Fragrance 1 imon 1.00 The hydrocarbon mixture is heated to about 75 ° C, after which the polymers, which have been mixed, are sieved over the mixture slowly with constant stirring. The temperature is maintained for about 60 minutes to allow the polymer to dissolve in the hydrocarbon, thereby forming a clear homogenous mixture which is then allowed to cool. As the mixture begins to gel, the active ingredient is added with continuous agitation. Then the gel is allowed to cool further to room temperature to give a rigid transparent gel, suitable for use as the care product of the atmosphere, such as an environment refresher.

EXAMPLE 2 A refreshing air is formed by mixing the following: Geahlene * 1GOO. 99.OO lemon fragrance l.OO Geahlene * is heated to 70 ° C and mixed for about 45 minutes to obtain a molten mixture. The mixture is allowed to cool, with the active ingredient added as the gel begins to form. A soft clear gel forms after subsequent cooling, and is useful as a refresher of air with lime effluence » EXAMPLE 3 A re-air bar is prepared in the following manner: Isopar L (isoparaffinic oil) 37.00 Penreco 2257 40.50 Polymer 1650 16.00 Polymer 1702 0.50 Lemon fragrance 3.00 Lime fragrance 3.00 First, the hydrocarbons are heated and the polymer mixture is mixed slowly while maintaining the temperature as in example 1. As the hydrocarbon / polymer mixture cools and the gelation begins, the active ingredients are added with continuous agitation. Deßpuéß, the mixture is transferred to a mold that gives it the shape of a bar. Deßpuéß de ßu cooling »ße forms a rigid hydrocarbon gel in the form of a stick» which is then put into a suitable thermoplastic housing to use environmental deodorizers and air fresheners. The resulting product is useful as an ambient or auto deodorant and as an air freshener.

EXAMPLE 4 An ambient deodorant is prepared as follows: Active substance (l monomer dimer) 5.00 Cetearyl octanetoate 10.OO Cyclomethicone 5.00 Drakeol mineral oil * 73.20 Polymer 1650 6.45 Polymer 1702 O.35 The hydrocarbon and polymer are heated as in Example 1, cooled to the beginning of gelation, and the active substance is added. The resulting product is useful as an air freshener.

EXAMPLE 5 Oil Penreco 2257 76.50 Kraton 1650 15.OO Kraton 1702 O.50 Fragrance 8.00 EXAMPLE 6 Isopar L 76.50 Kraton 1650 15.OO Kraton 1702 0.50 Fragrance S.OO Examples 5 and 6 are treated as described in Example 1, yielding or resulting products useful as air fresheners.

EXAMPLE 7 BASE FOR AIR REFRESHING Isopar L 80.00 Kraton 1650 19.50 Kraton 1702 0.50 This example is prepared as in Example 1, with the exception that no fragrance or deodorant is added during the preparation. The air-freshener bar then heats and adds the fragrance and / or deodorant, and the product is shipped in suitable containers or molded in an appropriate manner. The product can then be packaged »if desired, and is useful as a care product for the atmosphere. gJEMPLQ 8 Isopar M 63.98 Cyclomethicone (Dow Corning 344) 15.00 Kraton 1650 15.00 Fragrance 6.00 BHT 0.02 The mixture of Example 8 contains a hydrocarbon and hydrocarbon soluble silicone mixture. The mixture is treated as in Example 1, with the fragrance added as the gel flows. The gel in cooling process is poured into an open round aluminum pan and allowed to solidify at room temperature. The surface area of the gel is approximately 3019 mm8 *. The mass of the object is recorded periodically and the weight loss is noted. Figure 2 represents the percentage of weight loss of the gel as a function of time.

EXAMPLE 9 Isododecane (Per ethyl 99A) 67.64 Penreco oil 2251 9.80 Kraton 1650 9.80 Fragrance 9.80 Isopropyl myristate 1.96 Kraton 1702 0.98 BHT 0.02 The hydrocarbon mixture is prepared as in Example 1. The resulting rigid gel is useful as an air freshener or deodorant.

EXAMPLE 0 A controlled-release sebum insecticidal gel is prepared as follows: DraKeol mineral oil * 45.50 Penreco 2257 10.OO Peanut oil 27.OO Polymer 1650 16.00 Polymer 1702 0.50 Hydro-ethylnon (CAS-67485-29-4) 1.00 The hydrocarbon mixture is heated to about 75 ° C, after which the polymers »which have been mixed» are sifted onto the mixture slowly with constant stirring. The temperature is maintained for about 60 minutes to allow the polymer to dissolve in the hydrocarbons, thereby forming a clear mixture that is left to cool. As the mixture begins to gel, the active sub-presence is added with continuous agitation. Then the gel is allowed to cool down further to room temperature to produce a rigid gel useful as a tallow for insects.

EXAMPLE 11 A residual insecticidal gel is formed by mixing the following: Geahlene * 1600 99.00 Permethrin 1.00 The Geahlene * gel is heated to about 70 ° C and mixed for about 45 minutes to obtain a molten mixture. The mixture is allowed to cool. Then »permethrin is added with stirring» as the gel starts to form again »as before. A mild gel is formed which is useful as a residual insecticidal composition.

EXAMPLE 12 An insecticide is prepared having both volatile and residual activities, as follows: Isopar L (acetyl paraffinic acid) 37.00 Penreco 2257 40.50 Po1 number 1650 16.00 Polymer 1702 0.50 Active Sub-active - Hydroprene 5.00 Active Sub-presence - Permethrin 1.00 The hydrocarbons are first heated and the polymer mixture is mixed slowly, keeping the temperature at the same time as in example 10. As the hydrocarbon / polymer mixture cools and gelation begins, the active ingredients are added with stirring. After complete cooling »a rigid gel is formed which is useful as a volatile and surface contact insecticide.

EXAMPLE 13 An insect repellent gel »suitable for application to the skin of a user» is prepared from the following mixture: Active substance - DEET 10.00 Cetearyl octaneate 5.00 Cyclomethicone 5.00 Drakeol mineral oil * 7 73.20 Polymer 1650 6.45 Polymer 1702 0.35 The oil / polymer mixture is heated as in example 10. It is cooled to the beginning of the gelation "and the active substance is added. After subsequent cooling "a resulting hydrocarbon gel is formed" which is an "insect repellent gel" suitable for application to the skin of a user. The invention can also be carried out in other specific ways, without departing from the essential spirit or characteristics thereof. Therefore, the present embodiments are considered in all respects as illustrative and not as restrictive of the scope of the invention indicated by the appended claims, "and not with the foregoing description" and therefore "all changes are intended to be". within the meaning and range of equivalents of the reivifications »are covered in it. As the invention has been broadly described, it is intended that the scope of the appended claims be constructed broadly accordingly.

Claims (13)

QVEPAQ Q A? FtQ RE VIDICTIONS

1. A non-aqueous controlled release composition for the care of the atmosphere comprising a hydrocarbon, optionally comprising one or more hydrocarbon-soluble sub-acids, one or more diblock copolymers, one or more triblock copolymers of radial block and / or of multiple blocks »or a mixture thereof» and one or more active substances.

2. The non-aqueous controlled release composition for the care of the atmosphere in accordance with claim 1, characterized in that it comprises: (a) Approximately 20 to about 95 weight percent of a hydrocarbon comprising: optionally one or more substances soluble in hydrocarbon; (b) from about 1 to about 50 weight percent of one or more diblock copolymers, one or more triblock copolymers of radial block and / or multiple blocks, or a mixture thereof comprising from about 0 to about 100 weight percent of one or more of the diblock copolymers mentioned, and approximately 100 to about 0 weight percent of one or more of the triblock, radial block and / or multiple block copolymers mentioned; and (c) from about 0.1 to about 30 percent by weight of one or more active substrues for the care of the atmosphere.

3. The non-aqueous controlled release composition for the care of the atmosphere in accordance with the rei indication 1, characterized in that one or more of the active substances mentioned for the care of the atmosphere is selected from the group consisting of fragrances, deodorants , masking agents, plague repellents and pesticides.

4. The non-aqueous controlled-release composition for the care of the environment according to claim 2, characterized in that one or more of the active β-subsistences for the care of the atmosphere mentioned are fragrances.

5. The non-aqueous controlled release composition for the care of the atmosphere in accordance with the rei indication 1, characterized in that said hydrocarbon comprises about 5 to about 30 carbon atoms.

6. The non-aqueous controlled release composition for the care of the atmosphere in accordance with the rei indication 1, further characterized in that it comprises one or more solubilizers.

7. The non-aqueous controlled release composition for the care of the atmosphere in accordance with the rei indication 6, characterized in that said solubilizer is a surfactant.

8. A non-aqueous controlled release composition for the care of the atmosphere according to claim 1, further characterized in that it comprises a stabilizer.

9. The non-aqueous controlled release composition for the care of the atmosphere according to claim 8. characterized in that said stabilizer is an antioxidant.

10. The non-aqueous controlled release composition for the care of the atmosphere in accordance with re-indication 3. characterized in that said active substance is a repellent of pests or a pesticide.

11. The non-aqueous controlled release composition for the care of the atmosphere in accordance with claim 10. characterized in that said active substance is an insect repellent, insecticide or necotocide or fungicide.

12. An article of manufacture comprising an aqueous controlled release composition for the care of the atmosphere comprising: (a) from about 20 to about 95 weight percent of a hydrocarbon »one or more hydrocarbon soluble substances» or mixtures thereof; (b) from about 1 to about 50 percent by weight of a mixture of diblock copolymers and triblock »radial block and / or multi-block copolymers» said mixture approximately comprises from O to about 100 weight percent of one or more diblock copolymers, and about 100 to 0 weight percent of one or more triblock, radial block and / or multiple block copolymers; and (c) from about 0.1 to about 30 weight percent of one or more active substances for the care of the atmosphere.

13. The article of manufacture according to claim 12, characterized in that said active substance for the care of the atmosphere is selected from the group consisting of fragrances, deodorants and masking agents. 14.- E! article of manufacture according to claim 12, characterized in that said active substance for the care of the atmosphere is selected from the group consisting of repellents of pests and pesticides. 15. The article of manufacture in accordance with the rei indication 12, characterized in that said article is an insect repellent bar or a gel, cream or insect repellent lotion. 16. The article of manufacture according to claim 15, characterized in that said repellent composition of i sects comprises N, W-diethyl-m-toluamide or citronella oil. 17. The non-aqueous controlled-release pesticidal composition according to claim 1, characterized in that it comprises: (a) from about 20 to about 95 weight percent of a hydrocarbon, optionally comprising one or more subsurfaces soluble in hydrocarbon; (b) from about 1 to about 50 weight percent of one or more diblock, triblock, radial block and / or multiple block copolymers, or a mixture of the dies, ranging from about O to about 100 weight percent of one or more of the mentioned diblock copolymers, and about 100 to about 0 weight percent of one or more of the triblock copolymers. of radial block and / or of multiple blocks mentioned; and (c) from about 0.1 to about 30 weight percent of one or more pesticides as the active substance. IB.- The non-aqueous controlled-release pesticidal composition according to claim 17, characterized in that said active substance comprises approximately from 1 to about 20 weight percent. 19. The non-aqueous controlled release pesticidal composition according to claim 17, characterized in that said active substance is selected from the group consisting of tallow, lethal preparations for the stomach, lethal residual contact preparations and fumigant insecticides. 20. A method for repelling or exterminating insects comprising: providing a rigid hydrocarbon controlled release gel comprising about 20 to about 95 weight percent of a hydrocarbon; and, about 1 to about 50 by weight percent of one or more diblock, triblock, radial block and / or multiple block copolymers, or a mixture thereof, comprising from about 0 to about 100 weight percent of one or more of said diblock copolymers, and about 100 to about 0 weight percent of one or more of the mentioned triblock, radial block and / or multiple block copolymers; heating said controlled release hydrocarbon gel to form a substantially molten hydrocarbon / polymer mixture; and adding approximately from 0.1 to about 30 weight percent of an active substance, wherein said active sub-activeness is selected from the group consisting of at least one pest repellent or at least one pesticide. HQJA ANNEX (FIELD 57) SUMMARY OF THE INVENTION Non-aqueous controlled release gels for the care of the atmosphere, comprising approximately 1 to approximately 50 percent by weight, of diblock, triblock, multiple block and / or radial blocks based on synthetic thermoplastic rubbers; the ratio of diblock copolymers to triblock, multi-block and / or radial block copolymers can be varied from about 0 percent to about 100 percent in either direction; the material to be gelled is hydrocarbon, one or more substances soluble in hydrocarbon, or mixtures of the same, which on the basis of their physical properties, play an important role in fixing the rate of controlled release; the hydrocarbon composition may vary in carbon length from about C-5 to about C-30, and may vary in vapor pressure to about 600 mm Hg at 20 ° C; the scale of hydrocarbons on a weight basis is about 20 to about 95 weight percent total of the gel composition; the controlled release agent or active agent is one or more active substances for the care of the environment such as fragrances, deodorants, masking agents, repellents of pests or pesticides and may appropriately comprise from 0.1 to about 30 percent in gel weight.