Fungicide formulations with reduced crystal growth
Incorporating ethylene oxide-styrene oxide copolymer monoalkyl ether polymers into agrochemical compositions addresses the issue of particle growth, ensuring stability and bioavailability by inhibiting crystal growth and maintaining smaller particle sizes.
Patent Information
- Authority / Receiving Office
- CA · CA
- Patent Type
- Patents
- Current Assignee / Owner
- SYNGENTA CROP PROTECITON AG
- Filing Date
- 2020-02-24
- Publication Date
- 2026-07-07
AI Technical Summary
Agrochemical compositions experience undesirable particle growth, such as crystal growth, nucleation, or Ostwald ripening, particularly in fluctuating temperature conditions, leading to issues like separation, sedimentation, caking, nozzle blockage, and reduced bioavailability due to large particle sizes.
Incorporation of ethylene oxide-styrene oxide copolymer monoalkyl ether polymers, specifically compounds of formula (I), into agrochemical compositions to inhibit crystal growth and maintain particle stability.
Significantly reduces particle growth, preventing separation and nozzle blockage, and ensuring consistent bioavailability of agrochemicals by maintaining smaller particle sizes even under temperature fluctuations.
Abstract
Description
FUNGICIDE FORMULATIONS WITH REDUCED CRYSTAL GROWTH This invention relates to a composition comprising a compound of formula (I) and an agrochemical active ingredient selected from ADEPIDYN™ (pydiflumetofen), oxathiapiprolin, sedaxane and azoxystrobin; [Image disponible dans le document PDF, Image available in the PDF document] (I) where <semantics>R1<annotation encoding="application / x-tex">R_1< / annotation>< / semantics> is <semantics>C6−12<annotation encoding="application / x-tex">C_{6-12}< / annotation>< / semantics> alkyl or is <semantics>C6−12<annotation encoding="application / x-tex">C_{6-12}< / annotation>< / semantics> alkenyl; n is from 5 to 50; independently, each [C(R2)(H)C(R3)(H)O] unit has both R2 and R3 being hydrogen or has one of R2 and R3 being hydrogen and the other being phenyl; provided that at least one <semantics>[C(R2)(H)C(R3)(H)O]<annotation encoding="application / x-tex">[C(R_2)(H)C(R_3)(H)O]< / annotation>< / semantics> unit has one of <semantics>R2<annotation encoding="application / x-tex">R_2< / annotation>< / semantics> and <semantics>R3<annotation encoding="application / x-tex">R_3< / annotation>< / semantics> being hydrogen and the other being phenyl; and X is hydrogen or is selected from C1-4 alkyl; and to use of a compound of formula (I) to reduce particle growth (such as nucleation, crystal growth or Ostwald ripening) of an agrochemical active ingredient. Agrochemical compositions may undergo undesirable particle growth, such as crystal growth, nucleation or Ostwald ripening, when stored for periods of time (for example, in a distributor's warehouse or in a farmer's store), particularly in situations where there is an oscillating temperature (such as freeze-thaw cycling). Such behaviour may lead to adverse performance of the agrochemical compositions (including separation, sedimentation, caking within an agrochemical concentrate; blocking of spray nozzles during attempted application of the agrochemical, either in concentrated form or in a diluted form; and poor biological performance of the agrochemical, possibly due to limited availability of the agrochemical to its intended biological site due to large particle sizes, which have a smaller surface are to volume ratio than corresponding smaller particles and hence a reduced bioavailability). Surprisingly, it has now been found that certain ethylene oxide-styrene oxide copolymer monoalkyl ether polymers may reduce or overcome the crystal growth behaviour and hence the associated physical and biological problems. Certain compositions comprising an ethylene oxide-styrene oxide copolymer monoalkyl ether polymer and particular agrochemical active ingredients are novel. Compounds of formula (I) are known only as wetting agents; not as crystal growth inhibitors. Therefore, the present invention provides a composition comprising a liquid continuous phase, a compound of formula (I) and an agrochemical active ingredient selected from pydiflumetofen, oxathiapiprolin, sedaxane and azoxystrobin; [Image disponible dans le document PDF, Image available in the PDF document] (I) where <semantics>R1<annotation encoding="application / x-tex">R_1< / annotation>< / semantics> is <semantics>C6−12<annotation encoding="application / x-tex">C_{6-12}< / annotation>< / semantics> alkyl or is <semantics>C6−12<annotation encoding="application / x-tex">C_{6-12}< / annotation>< / semantics> alkenyl; n is from 5 to 50; independently, each <semantics>[C(R2)(H)C(R3)(H)O]<annotation encoding="application / x-tex">[C(R_2)(H)C(R_3)(H)O]< / annotation>< / semantics> unit has both <semantics>R2<annotation encoding="application / x-tex">R_2< / annotation>< / semantics> and <semantics>R3<annotation encoding="application / x-tex">R_3< / annotation>< / semantics> being hydrogen or has one of R2 and R3 being hydrogen and the other being phenyl; provided that at least one <semantics>[C(R2)(H)C(R3)(H)O]<annotation encoding="application / x-tex">[C(R_2)(H)C(R_3)(H)O]< / annotation>< / semantics> unit has one of <semantics>R2<annotation encoding="application / x-tex">R_2< / annotation>< / semantics> and <semantics>R3<annotation encoding="application / x-tex">R_3< / annotation>< / semantics> being hydrogen and the other being phenyl; and X is hydrogen or is selected from <semantics>C1−4<annotation encoding="application / x-tex">C_{1-4}< / annotation>< / semantics> alkyl. This means that each unit in the moiety <semantics>[C(R2)(H)C(R3)(H)O]n<annotation encoding="application / x-tex">[C(R_2)(H)C(R_3)(H)O]_n< / annotation>< / semantics> has the formula <semantics>[C(R2)(H)C(R3)(H)O]<annotation encoding="application / x-tex">[C(R_2)(H)C(R_3)(H)O]< / annotation>< / semantics> but each unit is independently selected from the following options: <semantics>R2<annotation encoding="application / x-tex">R_2< / annotation>< / semantics> is hydrogen and <semantics>R3<annotation encoding="application / x-tex">R_3< / annotation>< / semantics> is hydrogen; or <semantics>R2<annotation encoding="application / x-tex">R_2< / annotation>< / semantics> is hydrogen and <semantics>R3<annotation encoding="application / x-tex">R_3< / annotation>< / semantics> is phenyl; or <semantics>R2<annotation encoding="application / x-tex">R_2< / annotation>< / semantics> is phenyl and <semantics>R3<annotation encoding="application / x-tex">R_3< / annotation>< / semantics> is hydrogen; provided that at least one <semantics>[C(R2)(H)C(R3)(H)O]<annotation encoding="application / x-tex">[C(R_2)(H)C(R_3)(H)O]< / annotation>< / semantics> unit has <semantics>R2<annotation encoding="application / x-tex">R_2< / annotation>< / semantics> is hydrogen and <semantics>R3<annotation encoding="application / x-tex">R_3< / annotation>< / semantics> is phenyl; or <semantics>R2<annotation encoding="application / x-tex">R_2< / annotation>< / semantics> is hydrogen and <semantics>R3<annotation encoding="application / x-tex">R_3< / annotation>< / semantics> is phenyl. The moiety <semantics>[C(R2)(H)C(R3)(H)O]n<annotation encoding="application / x-tex">[C(R_2)(H)C(R_3)(H)O]_n< / annotation>< / semantics> is a random co-polymer; or a block co-polymer. Preferably n is from 5 to 40 (more preferably from 5 to 20). Preferably X is hydrogen. Alkyl and alkenyl chains may be linear or branched. Suitably <semantics>R1<annotation encoding="application / x-tex">R_1< / annotation>< / semantics> is <semantics>C6−12<annotation encoding="application / x-tex">C_{6-12}< / annotation>< / semantics> alkyl; more suitably <semantics>R1<annotation encoding="application / x-tex">R_1< / annotation>< / semantics> is <semantics>C8−10<annotation encoding="application / x-tex">C_{8-10}< / annotation>< / semantics> alkyl; even more suitably <semantics>R1<annotation encoding="application / x-tex">R_1< / annotation>< / semantics> is <semantics>C8<annotation encoding="application / x-tex">C_8< / annotation>< / semantics> alkyl. Suitably the compound of formula (I) is a compound of formula (Ia) [Image disponible dans le document PDF, Image available in the PDF document] (Ia) where, independently, in each C(R4)(H)C(R5)(H)O unit R4 is hydrogen and R5 is phenyl; or R4 is phenyl and R5 is hydrogen; r is from 1 to 25; and s is from 1 to 25; and R1 is as above or below. Preferably r is from 1 to 10 (more preferably from 3 to 7). Preferably s is from 1 to 10 (more preferably from 3 to 7). Suitably n is an average (mean, median or modal) value. In another aspect, the present invention provides a novel use of a compound of formula (I) as defined above or below to reduce particle growth (such as nucleation, crystal growth or Ostwald ripening) in a composition comprising a liquid continuous phase and an agrochemical active ingredient. The composition may be a solution of an agrochemical (such as a soluble concentrate (SL) or an emulsifiable concentrate (EC)); a suspension of a solid (at room temperature) agrochemical in a liquid continuous phase (either water (SC) or oil (OD)); an emulsion where droplets comprising an agrochemical are dispersed in a liquid continuous phase (either water (EW) or oil (EO)); or may be a suspoemulsion (SE). The composition may further comprise a surfactant. It is possible that the presence of a surfactant may increase the likelihood of the nucleation, crystal growth or Ostwald ripening behaviour which the compound of formula (I) is used to reduce. Surfactants are compounds which reduce the surface tension of water. Examples of surfactants are ionic (anionic, cationic or amphoteric) and nonionic surfactants. The noun "agrochemical" and term "agrochemically active ingredient" are used herein interchangeably, and include herbicides, insecticides, nematicides, molluscicides, fungicides, plant growth regulators and safeners; preferably herbicides, insecticides and fungicides. An agrochemical, or a salt of an agrochemical, selected from those given below, may be suitable for the present invention. Suitable herbicides include pinoxaden, bicyclopyrone, mesotrione, fomesafen, tralkoxydim, napropamide, amitraz, propanil, pyrimethanil, dicloran, tecnazene, toclofos methyl, flamprop M, 2,4-D, MCPA, mecoprop, clodinafop-propargyl, cyhalofop-butyl, diclofop methyl, haloxyfop, quizalofop-P, indol-3-ylacetic acid, 1-naphthylacetic acid, isoxaben, tebutam, chlorthal dimethyl, benomyl, benfuresate, dicamba, dichlobenil, benazolin, triazoxide, fluazuron, teflubenzuron, phenmedipham, acetochlor, alachlor, metolachlor, pretilachlor, thenylchlor, alloxydim, butroxydim, clethodim, cyclodim, sethoxydim, tepraloxydim, pendimethalin, dinoterb, bifenox, oxyfluorfen, acifluorfen, fluazifop, S-metolachlor, glyphosate, glufosinate, paraquat, diquat, fluoroglycofen-ethyl, bromoxynil, ioxynil, imazamethabenz-methyl, imazapyr, imazaquin, imazethapyr, imazapic, imazamox, flumioxazin, flumiclorac-pentyl, picloram, amodosulfuron, chlorsulfuron, nicosulfuron, rimsulfuron, triasulfuron, triallate, pebulate, prosulfocarb, molinate, atrazine, simazine, cyanazine, ametryn, prometryn, terbuthylazine, terbutryn, sulcotrione, isoproturon, linuron, fenuron, chlorotoluron, metoxuron, iodosulfuron, mesosulfuron, diflufenican, flufenacet, fluroxypyr, aminopyralid, pyroxsulam, XDE-848 Rinskor and halauxifen-methyl. Suitable fungicides include isopyrazam, mandipropamid, azoxystrobin, trifloxystrobin, kresoxim methyl, mefenoxam, famoxadone, metominostrobin and picoxystrobin, cyprodanil, carbendazim, thiabendazole, dimethomorph, vinclozolin, iprodione, dithiocarbamate, imazalil, prochloraz, fluquinconazole, epoxiconazole, flutriafol, azaconazole, bitertanol, bromuconazole, cyproconazole, difenoconazole, hexaconazole, paclobutrazole, propiconazole, tebuconazole, triadimefon, trtiticonazole, fenpropimorph, tridemorph, fenpropidin, mancozeb, metiram, chlorothalonil, thiram, ziram, captafol, captan, folpet, fluazinam, flutolanil, carboxin, metalaxyl, bupirimate, ethirimol, dimoxystrobin, fluoxastrobin, orysastrobin, metominostrobin, prothioconazole, adepidyn, bixafen, fludioxinil, fluxapyroxad, prothioconazole, pyraclostrobin, revysol, solatenol and xemium. Suitable insecticides include thiamethoxam, imidacloprid, acetamiprid, clothianidin, dinotefuran, nitenpyram, fiprinil, abamectin, emamectin, tefluthrin, emamectin benzoate, bendiocarb, carbaryl, fenoxycarb, isoprocarb, pirimicarb, propoxur, xylylcarb, asulam, chlorpropham, endosulfan, heptachlor, tebufenozide, bensultap, diethofencarb, pirimiphos methyl, aldicarb, methomyl, cyprmethrin, bioallethrin, deltamethrin, lambda cyhalothrin, cyhalothrin, cyfluthrin, fenvalerate, imiprothrin, permethrin, halfenprox, chlorantraniliprole, oxamyl, flupyradifurone, sedaxane, inscalis, rynaxypyr, sulfoxaflor and spinetoram. Suitable plant growth regulators include paclobutrazole, trinexapac-ethyl and 1-methylcyclopropene. Suitable safeners include benoxacor, cloquintocet-mexyl, cyometrinil, dichlormid, fenchlorazole-ethyl, fenclorim, flurazole, fluxofenim, mefenpyr-diethyl, MG-191, naphthalic anhydride and oxabetrinil. The various editions of The Pesticide Manual [especially the 14th and 15th editions] also disclose details of agrochemicals, any one of which may suitably be used in the present invention. Suitably the agrochemical is present in the composition at a concentration of from 0.5% to 50.0% (more suitably from 1.0% to 30%; more suitably from 3.0% to 20.0%; most suitably from 5.0% to 15.0%) by weight. Suitably the agrochemical is in suspended form in the continuous phase. Suitably, the agrochemical is ADEPIDYN™ (pydiflumetofen), oxathiapiprolin, sedaxane or azoxystrobin. Suitably the continuous phase is aqueous. A further agrochemical may be present in the composition of the present invention. Suitably the further agrochemical is present in the composition at a concentration of from 0.5% to 50.0% (more suitably from 1.0% to 30%; more suitably from 3.0% to 20.0%; most suitably from 5.0% to 15.0%) by weight. Suitably the first agrochemical is in suspended form in the continuous phase whilst the further agrochemical is present in an emulsified form. When more than one agrochemical is present, preferably ADEPIDYNTM (pydiflumetofen) is in suspended form whilst propiconazole is present as an emulsion; or oxathiapiprolin is in suspended form whilst mefenoxam is present as an emulsion. In such a situation, suitably the continuous phase is aqueous and the composition is a suspoemulsion. Suitably the compound of formula (I) is present in the composition at a concentration of from 0.1% to 10.0% (more suitably from 0.3% to 5.0%; more suitably from 0.5% to 2.0%; most suitably from 0.5% to 1.0%) by weight. The following examples demonstrate the crystal growth associated with compositions according to the present invention. Unless otherwise stated, all concentrations and ratios are by weight. Particle size distribution is reported as the number of particles that fall into each of the various size ranges, given as a percentage of the total number of all sizes in the sample of interest. Hence, DV95 (for instance) reports cumulative data; 95 means up to 95% percent of the total particles are smaller than a given number. For example if DV 95=7µm, it means that 95% of the particles are smaller than 7µm and 5% bigger than 7µm. Break-ThruTM DA647 and Break-ThruTM DA675 are examples of compounds of formula (I). Break-ThruTM DA647 is Oxirane, phenyl, polymer with oxirane, monooctyl ether (CAS Number: 83653-00-3); it is also known as TEGOTM XP 11010 (from Degussa). Break-ThruTM DA675 is Oxirane, 2-phenyl-, polymer with oxirane, mono(3,5,5-trimethylhexyl) ether (CAS Number: 303150-42-7); it is also known as TEGOTM VISCOPLUS 3030 and TEGOTM VISCOPLUS 3060 (from Degussa). Example 1 This example provides data relating to suspoemulsions (SEs) comprising ADEPIDYN™ (pydiflumetofen) suspended in water and propiconazole present as an oil-in- water emulsion. All the SE formulations were prepared and analysed for particle size using conventional processes familiar to those skilled in the art. Table 1 provides, for each SE, a list of ingredients plus particle size data obtained during Freeze-Thaw (F / T) storage of the SE samples; a Freeze-Thaw cyclic stress test for physical storage of samples was used, whereby every 24hours the storage freezer / oven / temperature was changed from -10°C to 45°C (and then back again 24 hours later). Under such extreme temperature change, stressed material may induce significant particle growth of active ingredients but, as Table 1 shows, this can be mitigated by the presence of a compound of formula (I). Table 1 [Image disponible dans le document PDF, Image available in the PDF document] Conclusion: Formulations ADE-1 and ADE-2 are extremely similar compositions, with the key difference being that ADE-2 contains Break-ThruTM DA647, which is absent in ADE-1; as Table 1 reveals, surprisingly the presence of Break-ThruTM DA647 significantly reduces the rate of particle growth (crystal growth). Example 2 This example provides data relating to fungicide suspoemulsions (SEs) comprising OXTP (oxathiapiprolin) suspended in water and MFX (mefenoxam) present as an oil-in- water emulsion. All the SE formulations were prepared and analysed for particle size using conventional processes familiar to those skilled in the art. Table 2 provides for each SE a list of ingredients plus particle size data obtained during storage of the SE samples. Table 2. OXTP / MFX Formulation and particle size growth over storage at 54°C [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] Conclusion: Formulations OXTP-1 to OXTP-5 are extremely similar compositions, with the key difference being that Formulations OXTP-2 to OXTP-5 contain Break-ThruTM DA647 or DA675, which are absent in Formulation OXTP-1; as Table 2 reveals, surprisingly the presence of Break-ThruTM DA647 or DA675 significantly reduces the rate of particle growth (crystal growth). Example 3 This example provides data relating to fungicide suspension concentrates (SCs) comprising sedaxane suspended in water. All the SC formulations were prepared and analysed for particle size using conventional processes familiar to those skilled in the art. Table 3 provides for each SC a list of ingredients plus particle size data obtained during storage of the SC samples. Table 3. Sedaxane Formulation compositions and their particle size growth. [Image disponible dans le document PDF, Image available in the PDF document] Conclusion: Formulations SDX-1 to SDX-3 are extremely similar compositions, with the key difference being that they contain different dispersants; Formulation SDX-3 contains Break-ThruTM DA675, which is absent in Formulations SDX-1 and SDX-2, having been replaced by dispersants of different chemistry; as Table 3 reveals, surprisingly the presence of Break-ThruTM DA675 significantly reduces the rate of particle growth (crystal growth). Example 4 This example provides data relating to fungicide suspension concentrates (SCs) comprising azoystrobin suspended in water. All the SC formulations were prepared and analysed for particle size using conventional processes familiar to those skilled in the art. Table 4 provides for each SC a list of ingredients plus particle size data obtained during storage of the SC samples. Table 4. Azoxystrobin Formulation compositions and their particle size growth over storage at 50°C for 4 weeks. [Image disponible dans le document PDF, Image available in the PDF document] [Image disponible dans le document PDF, Image available in the PDF document] Conclusion: Formulations AZ-1 to AZ-3 are extremely similar compositions, with the key difference being that they contain different dispersants; Formulation AZ-3 contains Break-ThruTM DA675, which is absent in Formulations AZ-1 and AZ-2, having been replaced by dispersants of different chemistry; as Table 4 reveals, surprisingly the presence of Break-ThruTM DA675 significantly reduces the rate of particle growth (crystal growth). 5
Claims
<pat:ClaimStatement>CLAIMS< / pat:ClaimStatement> <pat:Claims com:id="claims"> <pat:Claim com:id="CLM-00001"> <pat:ClaimNumber>1< / pat:ClaimNumber> <pat:ClaimText>1. A composition comprising a liquid continuous phase, a compound of formula (I) and an agrochemical active ingredient selected from pydiflumetofen, oxathiapiprolin and sedaxane; [Image disponible dans le document PDF, Image available in the PDF document] (I) where <semantics>R1<annotation encoding="application / x-tex">R_1< / annotation>< / semantics> is <semantics>C8−10<annotation encoding="application / x-tex">C_{8-10}< / annotation>< / semantics> alkyl; n is from 5 to 50; independently, each <semantics>[C(R2)(H)C(R3)(H)O]<annotation encoding="application / x-tex">[C(R_2)(H)C(R_3)(H)O]< / annotation>< / semantics> unit has both <semantics>R2<annotation encoding="application / x-tex">R_2< / annotation>< / semantics> and <semantics>R3<annotation encoding="application / x-tex">R_3< / annotation>< / semantics> being hydrogen or has one of R2 and R3 being hydrogen and the other being phenyl; provided that at least one [C(R2)(H)C(R3)(H)O] unit has one of R2 and R3 being hydrogen and the other being phenyl; and X is hydrogen or is selected from C1-4 alkyl. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00002"> <pat:ClaimNumber>2< / pat:ClaimNumber> <pat:ClaimText>2. A composition as claimed in claim 1 where X is hydrogen. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00003"> <pat:ClaimNumber>3< / pat:ClaimNumber> <pat:ClaimText>3. A composition as claimed in claim 1 or 2, where n is from 5 to 40. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00004"> <pat:ClaimNumber>4< / pat:ClaimNumber> <pat:ClaimText>4. A composition as claimed in claim 1 where the compound of formula (I) is a compound of formula (Ia) [Image disponible dans le document PDF, Image available in the PDF document] (Ia) where, independently, in each <semantics>C(R4)(H)C(R5)(H)O<annotation encoding="application / x-tex">C(R_4)(H)C(R_5)(H)O< / annotation>< / semantics> unit <semantics>R4<annotation encoding="application / x-tex">R_4< / annotation>< / semantics> is hydrogen and <semantics>R5<annotation encoding="application / x-tex">R_5< / annotation>< / semantics> is phenyl; or R4 is phenyl and R5 is hydrogen; r is from 3 to 7; and s is from 3 to 7. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00005"> <pat:ClaimNumber>5< / pat:ClaimNumber> <pat:ClaimText>5. A composition as claimed in any one of claims 1 to 4, wherein a further agrochemical active ingredient is present, and wherein the agrochemical active ingredient is in suspended form in the continuous phase whilst the further agrochemical active ingredient is present in an emulsified form. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00006"> <pat:ClaimNumber>6< / pat:ClaimNumber> <pat:ClaimText>6. A composition as claimed in claim 5, wherein the agrochemical active ingredient is pydiflumetofen which is in suspended form, and the further agrochemical active ingredient is propiconazole, which is present in an emulsified form. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00007"> <pat:ClaimNumber>7< / pat:ClaimNumber> <pat:ClaimText>7. Use of a compound of formula (I) to reduce particle growth in a composition comprising a liquid continuous phase and an agrochemical active ingredient [Image disponible dans le document PDF, Image available in the PDF document] (I) where <semantics>R1<annotation encoding="application / x-tex">R_1< / annotation>< / semantics> is <semantics>C8−10<annotation encoding="application / x-tex">C_{8-10}< / annotation>< / semantics> alkyl; n is from 5 to 50; independently, each <semantics>[C(R2)(H)C(R3)(H)O]<annotation encoding="application / x-tex">[C(R_2)(H)C(R_3)(H)O]< / annotation>< / semantics> unit has both <semantics>R2<annotation encoding="application / x-tex">R_2< / annotation>< / semantics> and <semantics>R3<annotation encoding="application / x-tex">R_3< / annotation>< / semantics> being hydrogen or has one of R2 and R3 being hydrogen and the other being phenyl; provided that at least one [C(R2)(H)C(R3)(H)O] unit has one of R2 and R3 being hydrogen and the other being phenyl; and X is hydrogen or is selected from C1-4 alkyl. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00008"> <pat:ClaimNumber>8< / pat:ClaimNumber> <pat:ClaimText>8. Use as claimed in claim 7 where X is hydrogen. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00009"> <pat:ClaimNumber>9< / pat:ClaimNumber> <pat:ClaimText>9. Use as claimed in claim 7 or 8 where n is from 5 to 40. < / pat:ClaimText> < / pat:Claim> <pat:Claim com:id="CLM-00010"> <pat:ClaimNumber>10< / pat:ClaimNumber> <pat:ClaimText>10. Use as claimed in claim 7 where the compound of formula (I) is a compound of formula (Ia) [Image disponible dans le document PDF, Image available in the PDF document] (Ia) where, independently, in each <semantics>C(R4)(H)C(R5)(H)O<annotation encoding="application / x-tex">C(R_4)(H)C(R_5)(H)O< / annotation>< / semantics> unit <semantics>R4<annotation encoding="application / x-tex">R_4< / annotation>< / semantics> is hydrogen and <semantics>R5<annotation encoding="application / x-tex">R_5< / annotation>< / semantics> is phenyl; or R4 is phenyl and R5 is hydrogen; r is from 3 to 7; and s is from 3 to 7. < / pat:ClaimText> < / pat:Claim> < / pat:Claims>