AU618553B2 - Polymeric compositions - Google Patents

Description

i II foe AUSTPIA (1)

PATENT

PCT

(43) AA-A-M294/88 0 WORLD INTELLECTUAL PROPERTY ORGANIZATION International Bureau INTERNATIONAL APPLICATION PUBLISHED UNDER THE PATENT COOPERATION TREATY (PCT) (51) International Patent Classification 4 fInte iati l P bcati iliumb r WO 89/ 01948 CO8F 2/44, A01N 25/18 Al 3 Internat l P ibl'icati at_) 9 March 1989 (09.03.89) (21) International Application Number: PCT/GB88/00692 (74) Agent: LAWRENCE, Peter, Robin, Broughton; Gill Jennings Every, 53 to 64 Chancery Lane, London (22) International Filing Date: 23 August 1988 (23.08.88) WC2A 1HN (GB).

(31) Priority Application Numbers: 8719967 (81) Designated States: AT (European patent), AU, BE (Eu- 8818664 ropean patent), CH (European patent), DE (European patent), DK, FI, FR (European patent), GB, GB (32) Priority Dates: 24 August 1987 (24.08.87) (European patent), IT (European patent), JP, LU August 1988 (05.08.88) (European patent), NL (European patent), NO, SE (European patent), US.

(33) Priority Country: GB Published (71) Applicant (for all designated States except US): ALLIED With international search report.

COLLOIDS LIMITED [GB/GB]; P.O. Box 38, Low Moor, Bradford, West Yorkshire BDI2 OJZ (GB).

(72) Inventors; and Inventors/Applicants (for US only) CHAMBERLAIN, Peter [GB/GB]; 87 Grosvenor Road, Shipley, West A P 1 1 MAY 1989 Yorkshire HAWE, Malcolm [GB/GB]; 3 Broom PA 198 Bank, Birkby, Huddersfield, West Yorkshire (GB).

AUSTRALIAN

3 1 MAR 1989 PATENT

OFFICE

(54) Title: POLYMERIC COMPOSITIONS (57) Abstract Controlled release of a volatile active ingredient, especially an agricultural semiochemical, can be provided by incorporating it during emulsion polymerisation of water insoluble monomeric material in which it is dissolved and which is based primarily on alkyl (meth)acrylates alone or with styrenes, and by appropriate choice of the monomer blend and the Tg of the resultant polymer the rate of release of the active ingredient can be selected.

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2 WO 89/01948 PCT/GB88/00692 Polymeric Compositions This invention relates to controlled-release compositions comprising an active ingredient releasably contained within polymeric particles.

It is well known to try to control the release of an active ingredient from a composition by trapping the active ingredient within polymer particles, so that the active ingredient has to escape from the particles before it can exert its desired activity. There have been numerous proposals in the literature.

Many of the proposals involve forming the polymeric particles and then absorbing the active ingredient into the particles. For instance in JP 58-121212A particles of cross linked sodium polyacrylate are formed and an aqueous emulsion of an active ingredient is then absorbed into the particles. In U.S. 4,269,959 cross linked polymethyl methacrylate beads are formed and active ingredient is absorbed into the beads. In JP 61-5001 an emulsion is formed of very soft polymer particles formed from 2-ethyl hexyl acrylate and other monomers and volatile active ingredient is then absorbed into the particles. In U.S. 4,303,642 an insecticide is absorbed into polymers formed from, for instance, styrene or certain acrylates.

A problem with these absorption methods is that it is difficult to obtain a satisfactory combination of absorption and controlled release. If absorption is easy then release tends to be too fast. If absorption is difficult then release may be non-existent or, if absorption is only at the surface, may be of short duration.

It is also known to incorporate the active ingredient during the formation of the particles. For instance in EP 67533A a film-forming polyacrylate, WO 89/01948 PCT/GB88/00692 2 volatile solvent and particles of the active ingredient are sprayed to form encapsulated polymer particles containing the active ingredient. In U.S. 3,400,093 a solid active ingredient (an insecticide) is stirred into an emulsion of monomer (for instance methyl methacrylate, styrene or certain blends such as methyl methacrylate-ethyl acrylate) and the mixture is then subjected to oil-in-water emulsion polymerisation to form polymer particles containing the solid insecticide.

This product is for use as a floor polish. In Journal Pharmaceutical Sciences volume 59 no.5, May 1970 pages 614 to 618, Khanna et al describe that sustained release pharmaceutical compositions can be formed by bead polymerisation or by emulsion polymerisation in the presence of the pharmaceutically active ingredient, and the examples show the use of, inter alia, methyl methacrylate and/or methacrylic acid.

The active ingredients that have been proposed for incorporation by these and other methods can vary widely.

In many instances the active ingredients are to work by a contact mechanism. For instance they may exert insecticidal activity by contact between the insect and the solid or liquid insecticide. In some instances however they can be volatile and can exert their activity by vapour phase transmission across an atmosphere. For instance many of the disclosures of controlled release compositions mention perfumes as possible active ingredients.

It is particularly important to be able to preselect the permeability of the polymer to the volatile active ingredient, in order to provide for release to occur at a desired and controlled rate. Many of the polymers that are used in the compositions are of a character such that it is difficult or impossible to preselect their permeability to the active ingredient. For example r WO 89/01948 PCT/GB88/00692 3 typical polymers are cellulosic, polyurethane or ethylene vinyl acetate polymers. With all such polymers the only practicable ways of changing the permeability is by including an absorbent diluent, such as silica, in the composition (such as in JP 59-139301) or by changing to an entirely different type of polymer. Accordingly each different active ingredient requires the use of an entirely different type of polymer or method, and this is inconvenient.

Another type of controlled release composition comprises capsule particles in which the active ingredient is in the centre of the capsule and is retained by a capsule wall of a polymer, but again the selection of the polymer is subject to the same disadvantages as those discussed above.

A wide variety of controlled release compositions, and polymer systems for use in them, are therefore known but they are all subject to various disadvantages and, in particular, no system is available that can conveniently be adapted, by very minor and easy modifications in the polymer, to be suitable for providing predetermined rates of release for a wide range of very different volatile active ingredients.

The existence of these difficulties is demonstrated by the particular problems that arise when attempts are made to provide controlled release of an agricultural semiochemical. A semiochemical is a communications chemical that will influence the behaviour of a particular species, for instance by attraction or repulsion. The pheromones are semiochemicals.

Typically a semiochemical is a sex attractant for a particular species. By volatilising an extremely small amount of it into the atmosphere, that species is attracted to the area where it has been volatilised and can, for instance, be destroyed in that area by treating i

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4 it with an insecticide. This "lure and kill" technique is of particular value for treating flying insects, especially where the climate is warm with an average day temperature between 25 or 30 0 C and 40 0

C).

There are some proposals in the literature indicating that it should be possible to provide controlled release pheromone compositions in which the pheromone is within the matrix of polymeric particles. For instance reference is made to EP 67533A, JP 58-121212A, JP 59-136301A and U.S.

4,269,959 as discussed above.

In EP 256549A, pheromone is absorbed into previously formed polymer and so the system suffers from the disadvantages of absorption methods, as discussed above.

In GB 2,141,932 a polymer is formed of monomers such as methyl methacrylate and lauryl methacrylate and/or vinyl pyrollidone. The polymer can be made as an emulsion and then dissolved to form a solution in an organic solvent or can be made initially by polymerisation in organic solvent.

Pheromone is added to the solution and this is sprayed.

20 The process is unsatisfactory as it releases organic solvent into the atmosphere and pheromone is inevitably lost during the spraying.

FR 1598644 relates to controlled delivery of certain volatile substances from compositions formed by polymerisation of monomers in the presence of active ingredient or by pre-polymerisation and later addition of active ingredient. The monomers used to dissolve the active ingredient are not one or more alkyl (meth) acrylates for blends of one or more alkyl (meth) acrylate with one or more styrenes.

Commercial practice has confirmed that it is not conveniently possible to make satisfactory controlled release techniques by any of these methods, since the commercially available, agricultural, semiochemical, controlled-release compositions are all entirely different from these. They all tend to comprise bulk semiochemical trapped within a protective envelope. For instance the a a A a i -lla~ 4a semiochemical may be in the central part of a hollow fibre, in which event it may volatilise out of the open end, or it may be trapped within a spherical wall as a small capsule, or between two sheets as a laminate. Examples are in EP 61192A and EP 243007A.

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WO 89/01948 PCT/GB88/00692 A dispersion of the small capsules can be applied by spraying but the dispersion tends to be unstable.

Manufacture and positioning of the hollow fibres and i laminates is inconvenient. Thus there is an urgent need to provide an agricultural semiochemical sustained release composition that is much easier to make an? to apply in the chosen place of use and that can give a preselected rate of release of the semiochemical.

A controlled release composition according to the invention comprises an active ingredient releasably contained with polymeric particles and is characterised in that the active ingredient is a volatile active ingredient that exerts its activity by vapour phase transmission across an atmosphere, the particles are emulsion-polymerised particles having a particle size at least 90% below 1m and consist of a polymeric matrix with the active ingredient distributed throughout the matrix, the composition is an oil-in-water emulsion of the particles and has been formed by oil-in-water emulsion polymerisation of water insoluble monomeric material in which the active ingredient is dissolved and at least by weight of which is selected from one or more alkyl (meth) acrylates and blends of one or more alkyl (meth) acry.ates with one or more styrenes, and the water insoluble (as explained below) monomeric material is selected such that the polymer has Tg which is between 0 and 120 0 C and which is such that the active ingredient is, at a preselected temperature, released into the atmosphere at a preselected rate. Tg is generally below 110 0 C and usually below 105°C or 100IC.

Tg is the glass transition temperature of the polymer.

It may be determined by standard methods.

WO 89/01948 PCT/GB88/00692 6 The invention is primarily of value when the active ingredient is an agricultural semiochemical. Despite all the difficulties in the prior art of providing convenient controlled release semiochemical compositions, the invention can easily provide a sprayable and stable composition that can give convenient prolonged release of a semiochemical even at relatively high ambient temperatures, up to 40 0 C. Also, by minor and easy modifications in the polymerisation it is possible to adapt the polymer to give a chosen rate of release according to the ambient temperature of a wide range of active ingredients.

The semiochemical is generally a volatile liquid at 0 C. It may be a pheromone which may be naturally occurring or synthetically manufactured, or it may be some other synthetic compound that acts in a similar manner to pheromones or other semiochemicals.

Spiroketal is a suitable semiochemical for use in the invention and is a sex attractant pheromone for the olive fly. Trimedlure is a synthetic semiochemical that can S be used in the invention and is a sex attractant for the Mediterranean fruit fly.

Instead of being an attractant, the semiochemical can be a repellant. For instance a semiochemical can be applied to an area to repel insects from approaching that area. Thus it may be applied to plants to protect the plants or it may be applied to, for instance, timber to protect it from wood-boring insects.

Numerous pheromones and pheromone inhibitors that can be used in the invention are known. Many are described in GB 2,141,932A.

Antioxidant and/or light stabiliser may be dissolved into the monomers with the semiochemical or other active ingredient if that ingredient is unstable in light or oxygen.

h.: -ra r WO 89/01948 PCT/GB88/00692 The composition preferably contains a relatively low amount of the semiochemical, based on the weight of polymeric matrix. Thus the amount' is generally below usually below 10% by weight of the polymeric matrix plus semiochemical (or up to 10% based on total composition). It is usually at least 0.1% and preferably at least about Good results are generally achieved with concentrations of from about to often around These low concentrations are in contrast to the concentrations of contact insecticide in conventional sustained release polymeric, agricultural insecticidal compositions. If attempts are made to formulate a semiochemical, sustained-release, composition containing the typical insecticidal amounts of 30% or above, 50%, it is usually found that there is very rapid release initially of most of the pheromone or other semiochemical and thus most of it is not properly utilised. However when the semiochemical is of low volatility higher amounts, up to 50%, may be suitable. It is surprising that, by keeping the concentration low, it is possible to obtain an agriculturally useful rate of release over many days exposure of the composition to the atmosphere. For instance useful release can easily be achieved over a period of above 10 days, and often 20 days or longer.

The polymer is an oil-in-water emulsion polymer of alkyl (meth) acrylate, optionally with a styrene and optionally with other monomers. It is possible in the invention easily to modify the rate of release by changing the monomer blend so as to change the glass transition temperature, Tg. If the rate of release is too fast then the polymer needs to have a higher Tg, whilst if the rate of release is too slow then the polymer needs to have a lower Tg. If the rate of release is satisfactory at one temperature, a slightly

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i WO 89/01948 PCT/GB88/00692 8 higher Tg may be required to provide the same rate of release at a higher temperature.

The invention therefore includes a method of making a controlled release composition comprising determining the desired rate of release of the active ingredient from the polymer particles at a preselected temperature, selecting water insoluble monomeric material which, when polymerised by oil-in-water emulsion polymerisation, will form particles that provide this rate of release and that have Tg between 0 and 130 0 C and in which the active ingredient is soluble and of which at least 60% by weight is selected from the specified alkyl (meth) acrylates alone or with styrene, and forming the particles by oil-in-water emulsion polymerisation of the water insoluble monomeric material in which the active ingredient is dissolved. Thus, routine experimentation will show the rate of release of any particular active ingredient at any particular temperature and the monomer blend is selected so as to give the desired rate of release of that active ingredient at that temperature.

r ~Similarly, for any particular combination of monomers the rate of release varies with Tg and so adjustment of the proportions in the blend to adjust Tg to a preselected value is another convenient way of providing a composition that will have predetermined controlled release characteristics.

j The water insoluble monomeric material may consist of a single monomer in which event that monomer must be water insoluble and must be capable of dissolving the active ingredient in the amount that is required in the composition, since the active ingredient must be present in the monomer particles during the polymerisatidn.

Often however a blend of monomers is used in which event the entire blend must be water ins6luble and capable of dissolving the active ingredient. The active ingredient i ii WO 89/01948 PCT/GB88/00692 9 should preferably be soluble in the polymer particles, in the sense that it is trapped within them and can diffuse slowly out of them.

By saying that the monomer, or monomer blend, is water insoluble we mean that its solubility in water is so low that it can be polymerised by oil-in-water emulsion polymerisation without serious coagulation of the emulsion particles.

In order that the polymer can be made from readily available monomers that can be easily varied to adjust Tg and the rate of release, it is necessary that the majority, by weight, of the total monomer should be alkyl (meth) acrylate alone or blended with a styrene, and often the entire water insoluble monomeric material is provided by such monomer or monomer blend. However other monomers can be included provided the resultant blend is water insoluble and does dissolve the active ingredient and can be emulsion polymerised to give the desired Tg and release properties.

A particular advantage of the specified monomers is that it is easy to adjust Tg and the rate of release by adjusting the proportions of monomers that give high (above 25 0 C) Tg homopolymers (referred to below as "hard monomers") and monomers that give low (below 25°C) Tg homopolymers (referred to below as "soft monomers").

Preferably the monomeric material is provided by to 100% by weight of one or more hard monomers, 0 to of one or more soft monomers, and O to 40% other monomers. Generally all the monomers are ethylenically unsaturated monomers.

The hard monomers are preferably' selected from Cl-3 and C16-24 alkyl meth acrylates, C14-24 alkyl acrylates and styrenes. Suitable monomers are methyl or ethyl methacrylate, styrene, and methyl or ethyl -substituted styrenes. Methyl methacrylate and styrene WO 89/01948 PCT/GB88/00692 are particularly preferred, and best results are generally obtained when methyl methacrylate is used as the only hard monomer.

The soft monomer is generally a Cl-12 alkyl acrylate or a C3-14 alkyl methacrylate. C2-10 alkyl acrylates are preferred. If the soft monomer has a very high softening power then the amount that is used should generally be relatively low as otherwise Tg will be too low for most purposes and the rate of release too fast.

However when the soft monomer is less effective larger amounts can be used while still maintaining relatively high Tg values. For instance when the soft monomer is a C3-6 alkyl methacrylate suitable amounts are 10 to Typical monomers of this type are butyl methacrylates, for instance isobutyl methacrylate. When the carbon chain in the alkyl group is longer, especially when the soft monomer is C7-16 alkyl acrylate, the amount of soft monomer should generally be less, usually 2 to 20%. A preferred monomer of this type is 2-ethyl hexyl acrylate.

When the agricultural semiochemical is very volatile at the intended temperature of use, it may be suitable for the polymer to have Tg above 1000C. However for most agricultural semiochemicals under most conditions of use appropriate controlled release can best be achieved if Tg is not more than 1000C. Release is usually too fast if Tg is below 60°C and preferably it is above 75 or 800C. Thus best results are generally achieved for agricultural semiochemicals when Tg is about 80 to about or 100 0

C.

Particularly preferred monomer mixtures comprise 2 to 10% 2-ethyl hexyl acrylate or 20% to 50% of a butyl (generally isobutyl) methacrylate, with the balance of the monomers generally consisting essentially of methyl methacrylate or, less preferably, styrene.

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WO 89/01948 PCT/GB88/00692 11 It is, however, possible to include in the monomeric material 0 to 40% ethylenically unsaturated monomer other than the hard and soft monomers discussed above. These other monomers may be selected from, for instance, ethylene, acrylonitrile and, preferably, hydroxy alkyl (meth) acrylates and ethylenically unsaturated carboxylic acid monomers such as acrylic acid or methacrylic acid.

The amount of hydrophilic monomers such as hydroxy alkyl (meth) acrylates, methacrylic acid or acrylic acid is generally below 10% by weight. For instance the amount of acrylic acid may be from 0.1 to 5% by weight.

However larger amounts can be tolerated in some instances, provided the overall blend is water insoluble, and in particular the presence of larger amounts (up to methacrylic acid as the free acid can be useful for some particular purposes since the resultant polymer can then be solubilised by contact with alkali.

The monomeric material generally does not need to include cross linking agent and so the polymers are usually substantially linear. However they may be cross linked if desired.

When the emulsion is spread on a surface as a coating and is dried, the polymer particles it is generally preferred that they remain as discrete particles. This is generally desirable since it results Sin the surface area of polymer that is exposed to the atmosphere being substantially predetermined. If the A^ particles were fused into a film the exposed surface area of polymeric material would change and would be dependent on the thickness of the film, and thus the rate of release would change. However in some particular instances it is desirable for the polymer to be held on the surface as a film and this can be achieved by the inclusion of a plasticiser that will cause the particles to merge into one another as a film. The plasticiser

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WO 89/01948 PCT/GB88/00692 12 may alternatively be termed a coalescing agent. Another way of holding the particles on the surface is by including a binder in the composition.

The formation of the initial oil-in-water emulsion of monomers containing active ingredient may be performed in conventional manner, except that the active ingredient is dissolved in the monomers before, during or after emulsification. Conventional surfactant or surfactant blends may be used to facilitate the formation of the emulsion and to stabilise it. Conventional initiator may be included and the oil-in-water emulsion polymerisation performed in conventional manner. The particles are mainly (at least about 90% by weight) below for instance 0.05 to 1m. Accordingly the emulsion can easily be provided in a very stable form.

The composition typically contains about 30 to by weight polymer particles including semiochemical and to 70% by weight aqueous phase including surfactants, typical proportions being about 50% of each.

The composition can be stored as a stable composition and can be diluted to any desired polymer content, to a polymer content of 2 to 10% to make a sprayable composition.

The invention can also be applied to the provision of controlled release compositions of other active ingredients that exert their activity by vapour phase transmission across an atmosphere. For instance the active ingredient can be a vapour phase pesticide but preferably it is a fragrance. The fragrance may be formulated in known manner from appropriate blends of perfumes to form whatever type of fragrance is required for the intended use. The amount of active ingredient may be 5 to 60%, often 20 to 50%, by weight based on polymer plus fragrance.

SWO 89/01948 PCT/GB88/00692 13 The emulsion may be used as the fragrance composition, as a room freshener, but often a fragrant article is made by impregnating or coating a substrate with the emulsion composition. For instance a room freshener may be made by coating or impregnating a porous paper or other substrate with the defined emulsions and Tg will be selected having regard to the volatility of the particular fragrance blend, the rate of release that is required and the temperature at which the freshener is to be used. For instance when prolonged release, over 20 days or more, is required it is often convenient to have a relatively high Tg polymer Tg=80-120 0 C, often 80-100°C) in order to get sufficiently slow.release of many fragrance blends that are commercially available. This is especially the case when the freshener is to be used in a relatively warm environment, where temperatures of 20 or 25 0 C or higher are typical. For instance the polymer may be a homopolymer of polymethyl methacrylate and an emulsion of 20 this homopolymer may be coated on to or impregnated into a permeable or porous support and the aqueous phase may then be evaporated to leave a dry solid article that serves as a long-lasting room freshener, even at high temperatures.

Another use of the fragrance emulsion compositions t is as an additive to fabric softeners or other washing liquids since the polymer particles may then become entrapped on the clothes or other fabrics being washed or softened and may give a long lasting fragrance effect to them. To improve substantivity of the polymer particles to the fabrics or other surfaces; it is desirable for the particles to be cationic. This can be achieved by inclusion of cationic monomer (for instance 'dialkylaminoalkyl (meth) acrylate as an acid addition or quaternary salt) in the monomer blend and/or by the use WO 89/01948 PCT/GB88/00692 14 of cationic surfactant or stabiliser in the emulsion.

For such purposes the polymer typically will have Tg in the range 40 to 110°C, often 50 or 60 0 °C up to 100 0

C,

often below 90 0

C.

Another use of the fragrance compositions is for the formation of a fragrant coherent film, which is preferably easily removable when its fragrance properties have faded. Such a film can be achieved by spreading the emulsion on a surface if the polymer is of low Tg or if the aqueous phase includes a film-forming binder, provided the resultant film of this binder does not significantly interfere with the release characteristics from the particles.

Often it is preferred for the particles themselves to form the coherent film, for instance without the presence of added binder, so that the film can be made merely by spreading a coating of the emulsion and drying the coating to form the coherent and adherent film. The presence of a plasticiser (or coalescing agent) of a type known for forming a film from particles that would otherwise be discrete may be used when, as is preferred, Tg is such that a film would not otherwise be formed, for instance Tg above A surprising feature of the invention is that if the volatile active ingredient is present in relatively large amounts above 20% and often above 35% based on polymer plus active ingredient), it can serve as the plasticiser even when the polymer has a high Tg up to 105°C). For instance the composition may coat on to the surface initially as a film but as the fragrance or other active ingredient volatilises, the film gradually loses its coalescence and reverts to individual particles which can then be dusted or wiped off the surface.

A water washable permanent film can be achieved by including methacrylic acid or other hydrophilic monomer WO 89/01948 PCT/GB88/00692 since this will make the film more hydrophilic and therefore more removable by washing with aqueous detergent.

The following are some examples. In these, each polymer latex is made by conventional oil-in-water emulsion polymerisation. About two thirds of the water together with emulsifier, sequestrant, monomer and active ingredient are blended in a Silverson emulsifier to form a smooth white emulsion. The remainder of the water, emulsifier and sequestrant is heated to 85°C, and is mixed with the emulsified aqueous monomer phase and with initiator over two hours, while maintaining the temperature at 85 0 C with agitation, and the temperature is then maintained for a further one hour after which it is cooled to ambient temperature. The resultant emulsion is filtered to remove coarse particles.

Example 1 Spiroketal is used as the active ingredient in a variety of polymers. Each emulsion is sprayed into an environment held at 35 0 C and the rate of loss of spiroketal from the polymer particles is measured at various times from 3 to 17 days.

The release rates of Spiroketal from the formulations, each containing 2.0% w/w Spiroketal, were monitored as follows: Approximately lml of the formulation was weighed accurately on to a 9cm diameter filter paper in a shallow petri-dish which was lined with polyethene. The petri-dishes were placed in a ventilated oven at 35 0 C and were left exposed for predetermined time intervals. The filter papers and polythene liner were then removed and soxhlet extracted for 5 hours using ethyl acetate. The extracts were made up to volume and analysed for Spiroketal content using gas chromatography. Controls i L WO 89/01948 PCT/GB88/00692 16 were analysed for total Spiroketal content after zero exposure time.

The results for different monomer below.

blends are shown '41 Test 1 2 3 4 5 6 Monomer wt Methyl Methacrylate 95 78 90 56 2-Ethyl Hexyl Acrylate 5 10 Iso-Butyl Methacrylate 22 15 44 38 Styrene 85 62 Tg °C 92 92 92 80 80 Release 3 days 27 31 40 50 56 88 days 37 45 91 69 87 100 17 days 47 93 76 92 100 This demonstrates that, for this particular semiochemical, rather similar results are obtained with weight percent 2-ethyl hexyl acrylate or 22 weight percent isobutyl methacrylate copolymerised with methyl methacrylate but that when the methyl methacrylate is changed to styrene faster release may occur even though Tg is unchanged. The same trend exists at higher amounts of the soft monomer and therefore lower Tg values.

Example 2 1,7-Dioxaspiro undecane ('Spiroketal') is the principle component of the sex pheromone of the Olive fly Dacus oleae. 2% formulations were prepared using methyl methacrylate and 2-ethylhexylacrylate monomers at WO89/01948 PCT/GB88/00692 17 ratios of 100:0, 95:5 and 90:10 respectively and release rates were tested as in Example 1.

The results, showing the loss of Spiroketal, are shown below.

ri-: Polymer Ratio (MMA:2-EHA) Time (Days) 100:0 95:5 90:10 2 20 22.5 43 20 29 57 20 37.5 69 20 45 74 20 51 79 For comparison, a 2% emulsion of Spiroketal in water (no polymer present) when subjected to the above conditions gave complete loss of Spiroketal in less than 2 hours.

Example 3 Trimedlure, the sec-butyl ester of trans-4 (or 5) chloro 2 methylcyclohexanecarboxylic acid, is a synthetic attractant for the male Mediterranean fruit fly, Ceratitis capitata.

Formulations were prepared using methyl methacrylate and 2-ethylhexyl acrylate monomers at ratios of 95:5 and 90:10 respectively.

The release rate of Trimedlure from the two formulations, each containing 5% w/w Trimedlure, were measured by a technique similar to that of example 1.

Results showing loss of Trimedlure, are given below.

WO 89/01948 PCT/GB88/00692 18 I-a it Polymer Ratio (MMA:2-EHA) Time (Days) 95:5 (Tg 92 0 C) 90:10 (Tg 80 0

C)

2 7.5 11 4 13.5 19 6 18 24,5 8 20.5 26.5 10 22.5 12 23.5 31.5 14 24.5 32.5 For comparison, a 5% w/w emulsion of Trimedlure in water (no polymer), when subjected to test conditions, showed an 80% loss of Trimedlure in 4 hours.

Example 4 1:1 7,11-Hexadecadienyl acetate is the sex attractant secreted by the female Pink Bollworm Pectinophora gossy-piella. This perhomone is well-known to be degraded by oxidants and/or ultra-violet light.

Consequently, a UV absorber (Tinuvin 328) and a hindered amine light stabiliser (Tinuvin 770DF) were included in the formulation to give the necessary protection.

Formulations were prepared using methylmethacrylate and 2-ethylhexyl-acrylate monomers at ratios of 95:5, and 0:100 respectively.

The release rates of pheromone from the three formulations, each containing 2% w/w pheromone and UV light stabilisiers were monitored with time, both exposed to ahd shielded from sunlight.

The results, showing of pheromone remaining, are summarised below: WO 89/01948 PCT/GB88/00692 Polymer Ratio (MMA:2-EHA) Time (days) 95:5 (Tg 92°C) 90:10 (Tg 80°C) O:100 (Tg -70 0

C)

Exposed Shielded Exposed Shielded Exposed Shielded to from to from to from Sunlight Sunlight Sunlight Sunlight Sunlight Sunlight 1 80 90 65 78 35 32 2 62 80 50 64 9 9 4 36 63 26 47 6 21 51 15 33 8 14 40 10 24 10 9.5 30 6 16 12 7.5 21 4 11 14 6 16 2 7 16 10 4 For comparison, an emulsion of the same pheromone releases at least 80% within about 4 hours.

Example The emulsion polymerisation is conducted using an oil phase of 3 parts by weight methyl methacrylate and 2 parts by weight of a conventional room freshener fragrance blend. In order to determine the persistence of fragrance in this formulation, a series of experiments were performed in comparison with the same fragrance in the absence of the polymer matrix.

A 9cm Whartman No.l filter paper was placed in a shallow 10cm diameter Petri dish lined with polythene.

0.3g of the fragrance alone was spotted on to the paper and allowed to soak in.

In a separate dish 1.5g of the polymeric matrix containing the fragrance was spotted (as emulsion) onto WO 89/01948 PCT/GB88/00692 the filter paper to give the same concentration of active fragrance in both cases.

The Petri dishes were then placed on the floor of a fume cupboard in order to provide a constant passage of air over the paper. The samples were removed periodically and rated by a panel of testers for fragrance intensity on a scale of 0-5, where 5 intense odour and O barely detectable.

The results given in the table below show the data obtained over a 4 week period.

Exposure Fragrance Intensity Fragrance Intensity Time (Days) Control Polymer O 5 4 2 4 4 2 4 9 1 4 12 0O 3 23 0 3 28 O 2 This clearly demonstrates the long lasting fragrance effect of the compositions of the invention.

Example 6 A product was prepared according to the method given in Example 5 except that a "Floral Type" fragrance was utilised. The emulsion was then painted around the rim of a plant pot and allowed to dry. The sample was noted to be adherent to the surface of the vase whilst the fragrance was present.

When the fragrance had been exhausted from the polymer particles, after a period of about 10-14 days, the polymer deposit had become a dusty powder which could WO 89/01948 PCT/GB88/00692 21 be easily wiped off, prior to a further application of the product.

Other formulations can be prepared where some of the methyl methacrylate is replaced by methacrylic acid.

This gives the advantage that when the fragrance has been fully dissipated, again in about 10 days, the polymer can be easily removed-by washing with dilute alkali, since this converts the polymer into its water-soluble form.

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Claims (17)

1. A controlled release composition comprising an active ingredient releasably contained within polymer particles characterised in that the active ingredient is a volatile active ingredient that exerts its activity by vapour phase transmission across an atmosphere, the particles are emulsion polymerised particles having a particle size at least 90% by weight below lpm and consisting of a polymer matrix with active ingredient distributed throughout the matrix, the composition is an oil-in-water emulsion of the polymer particles and has been formed by oil-in-water e emulsion polymerisation of water insoluble monomeric material in which the active ingredient is dissolved and at least 60% by weight (based on total monomeric material) is selected from one or more alkyl (meth) acrylates and blends of one or more alkyl (meth) acrylates with one or more styrenes, and the water insoluble monomeric material is selected such that the polymer has a Tg value which is between 0. and 120*C and which is such that the active ingredient is, at a preselected temperature, released into the atmosphere at a preselected rate.

2. A composition according to claim 1 in which the water insoluble monomeric material comprises 40 to 100% by weight of one or more hard monomers selected from Cl-3 and C16-24 alkyl methacrylates, C14-24 alkyl acrylates and styrenes, 0 to 60% by weight of one or more soft monomers selected from Cl-12 alkyl acrylates and C3-14 alkyl methacrylates, and 0 to 40% other ethylenically unsaturated monomers.

3. A composition according to claim 2 in which the soft monomers comprise 2 to 20% by weight C7-10 alkyl acrylate or 10 to 60 by weight C3-6 alkyl methacrylate. St. r*\ C C. -23-

4. A composition according to claim 2 in which the soft monomer is selected from 2-ethyl hexyl acrylate and butyl methacrylates. A composition according to claim 2 in which the hard monomer is selected from methyl methacrylate and styrene.

6. A composition according to any preceding claim which is a storage stable composition that can be diluted to form a sprayable composition.

7. A composition according to any preceding claim in which the active ingredient is an agricultural semiochemical.

8. A composition according to claim 7 in which the polymer has Tg of 60 to 100 0 C.

9. A composition according to claim 7 in which the polymer has Tg 80 to 100 0 C. A composition according to claim 7 in which the polymer is formed from 2 to 10% by weight 2-ethyl hexyl acrylate or 20 to 50% by weight butyl methacrylate with the balance consisting essentially of methyl methacrylate.

11. A composition according to claim 7 in which the semiochemical is a spiroketal, trimedlure or other synthetic or natural pheromone.

12. A composition according to claim 1 in which the volatile active ingredient is a fragrance.

13. A composition according to claim 12 in which the polymer is formed wholly or mainly of methyl methacrylate. B. n r Trpys( p14 l' 911010,imdat 123,a: \22694all.res,23 -24-

14. A composition according to claim 12 in which the particles are cationic due to the use of cationic emulsifier or cationic monomer. A composition according to claim 6 in which the polymer particles remain as discrete particles when the composition is spread as a coating and is dried.

16. A composition according to claim 12 which forms a coherent film when it is spread as a coating and dried, and the film is removable by washing or wiping.

17. A composition according to claim 12 in which the fragrance acts as a plasticiser such that the polymer forms a film, and volatilisation of the fragrance results in the film becoming removable by wiping.

18. A method of making a controlled release composition containing an active ingredient releasably contained within polymeric particles, in which the active ingredient is a volatile active ingredient that exerts ,its activity by vapour phase transmission across an atmosphere and the particles are emulsion polymerised particles having a particle size at least 90% by weight below lpm and consist of a polymeric matrix throughout which the active ingredient is distributed, characterised r Iin that the method comprises determining the desired rate of release of active ingredient from the particles at a preselected temperature, selecting water insoluble monomeric material in which the active ingredient is soluble and which, when polymerised by oil-in-water emulsion polymerisation, will form particles that provide this desired rate of release and that have Tg of between 0 and 120°C and of which at least, based on the total weight of monomer, is selected from one or more alkyl (meth) acrylates and 61 911010,immdat123,a:\22694aU.res,24 1 t~ c_ blends of one or more alkyl (meth) acrylates with one or more styrenes, and forming the particles by oil-in-water emulsion polymerisation of the water insoluble monomeric material in which the active ingredient is dissolved.

19. An article coated or impregnated with a composition according to any of claims 1, 7 or 12. A composition according to claim 1 or a method for the use thereof substantially as hereinbefore described with reference to the Examples.

21. A method of applying a volatile active ingredient comprising spraying a composition according to any one of claims 1 to 11. kil ,1 DATED this 10th day of October, 1991. ALLIED COLLOIDS LIMITED By Its Patent Attorneys DAVIES COLLISON I s,~i I) pli" .r i 911010,immdat 123,a:\22694afl.res,25 _CI-LIIILI_-LLLIII~ i i INTERNATIONAL SEARCH REPORT International Application No PCT/GB 88/00692 I. CLASSIFICATION OF SUBJECT MATTER (it several classification symools aDply, indicate all) According to International Patent Classification (IPC) or to both National Classification and IPC IPC-: C 08 F 2/44; A 01 N 25/18 II. FIELDS SEARCHED Minimum Documentation Searched 7 Classification System Classification Symbols 4 IPC C 08 F; A 01 N Documentation Searched other than Minimum Documentation to the Extent that such Documents are included In the Fields Searched III. DOCUMENTS CONSIDERED TO BE RELEVANT' Category i Citation of Document, "1 with indication, where appropriate, of the relevant passages i2 Relevant to Claim No. "1 X US, A, 3400093 FEINBERG) 1,2,5,7, 3 September 1968 17 see column 7, line 36- column 9, line 26 cited in the application A FR, A, 1598644 ARIES) 1,11,15, 14 August 1970 17,18 see page 7, line 13 page 8, line 21 Special categories of cited documents: 10 later document published after the international filing date document defining the general late of the art which is not or priority date and not in conflict with the application but cited to understand the principle or theory underlying the considered to be of particular relevance invention earlier document but published on or after the international document of prticular relevance; the claimed invention filing date cannot be considered novel of cannot be considered to document which may throw doubts on priority claim(s) or involve an inventive step which is cited to establish the publication date of another document of particular relevance; the claimed invention citation or other special reason (as specified) cannot be considered to involve an inventive atep when the document referring to an oral disclosure, use, exhibition or document is comoined with one or more other such docu- other means ments, such combination being obvious to a person skilled document oublished prior to the International filing date but In the art. later then the priority date claimed document member of the same patent family IV. CERTIFICATION Date of the Actual Completion of the International Search 28th November 1988 International Searching Authority EUROPEAN PATENT OFFICE Form PCT/ISAI210 (second sheet) (January 1985) Date of Mailing of this International Search Report i 9 DEC 198 4*66 it' P -r ANNEX TO THE INTERNATIONAL SEARCH REPORT ON INTERNATIONAL PATENT APPLICATION NO. GB 8800692 SA 23908 This annex lists the patent family members relating to the patent documents cited in the above-mentioned international search report. The members are as contained in the European Patent Office EDP file on 08/12/88 The European Patent Office is in no way liable for these particulars which are merely given for the purpose of information. Patent document Publication Patent family Publication cited in search report date member(s) date US-A- 3400093 None FR-A- 1598644 06-07-70 None SFor more details about this annex see Official Journal of the European Patent Office, No. 12/82