Classifications

• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
  • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
  • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
  • B65D65/38—Packaging materials of special type or form
  • B65D65/46—Applications of disintegrable, dissolvable or edible materials
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
  • C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
  • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
  • C11D17/043—Liquid or thixotropic (gel) compositions

Definitions

• the present invention relates to a (preferably cold) water-soluble sachet having packaged therein a water-based composition, such as a water-based agrochemical, laundry care, dyestuff, biocide, industrial or home surface cleaning, or public health material composition.
• a water-based composition such as a water-based agrochemical, laundry care, dyestuff, biocide, industrial or home surface cleaning, or public health material composition.
• Water-soluble sachets have utility for packaging a range of materials, usually formulated compositions, and particularly formulated compositions which are hazardous (or at any rate unpleasant) to individuals with whom they come into contact or are hazardous or harmful to the environment.
• Important examples include agrochemicals compositions (e.g. insecticides, herbicides, pesticides and fungicides), laundry care products (e.g.
• water-soluble sachets for packaging certain formulated compositions also provides a convenient way of adding a measured dosage of the formulation for subsequent dilution with water in order to provide the desired final concentration of the diluted formulation.
• Agrochemical compositions for example can be packaged in water-soluble sachets, in which form they can be safely handled. The water-soluble sachet can be subsequently added to a spray tank containing water, and after dissolution of the sachet, the diluted formulation can be sprayed by the user, e.g. by a farmer.
• Polyvinyl alcohol is widely utilised for the preparation of water-soluble film for the production of sachets for packaging materials of the type discussed above (such as agrochemicals); polyethylene oxide and methyl cellulose are also widely utilised (see e.g. WO 93/22215).
• Such polymers are normally used in conjunction with a plasticiser to achieve the desired level of flexibility in the sachet film.
• Other types of polymers which are useful for providing films for sachet construction include acrylic polymers bearing neutralised acid groups (particularly carboxyl groups), the latter providing the requisite water-solubility for the acrylic films derived from the polymers.
• the packaged material in a sachet is often in the form of a water-based composition, by which is meant that the active materiai(s) of the composition, optionally with other components which may also be present in the composition, are carried in a liquid medium the principal component of which is water.
• a liquid medium the principal component of which is water.
• Preferably at least 60 wt% of the liquid carrier medium is water, more preferably at least 70 wt% (the non-aqueous component of the liquid carrier medium, if any, normally being one or more organic liquids).
• the aqueous composition may e.g. be in the form of an aqueous solution or an aqueous dispersion (such as a suspension concentrate or an oil-in-water emulsion) of the component(s) thereof.
• a type of laundry care sachet is proposed in European Patent Application EP-A-0 079 248, where a water-soluble film is coated with a protective layer of particulate inert plastics material.
• the protective layer when on the inside of the sachet protects the water-soluble film from attach from aqueous media.
• the aqueous-based composition of the sachet should be releasable into the selected aqueous environment at the appropriate time and place, by virtue of the sachet film(s) becoming dissolved and/or disintegrating in the water, (for the purpose of this specification, "water-soluble” includes “water- disintegratable”).
• water-soluble includes “water- disintegratable”
• the water of the aqueous-based composition of the sachet may in certain circumstances and for some compositions permeate through the sachet wall prior to use, e.g. during storage. Such permeation of the water of the packaged composition is clearly highly undesirable and may e.g. cause the sachet to dissolve and adhere to outer packaging thereby reducing the shelf life of the packaged product.
• a water-soluble sachet suitable for packaging a water-based composition
• the sachet having a film construction comprising a water-soluble film the binder material of which comprises a water-soluble organic polymer(s), and which film construction incorporates a water-dispersible wax(es) derived from an aqueous dispersion of the wax(es) employed in the formation of the water-soluble film.
• a water-soluble-sachet and a water-based composition packaged therein, the sachet having a film construction comprising a water-soluble film the binder material of which comprises a water-soluble organic polymer(s), and which film construction incorporates a water-dispersible wax(es) derived from an aqueous dispersion of the wax(es) employed in the formation of the water-soluble film.
• a water-soluble sachet in fully or partially sealed form, for packaging a water-based composition, said sachet having a film construction as defined above.
• a method of making a sachet as defined above which method comprises preparing a water-soluble film from an aqueous solution or dispersion of a water-soluble organic polymer(s) in admixture with an aqueous dispersion of a wax(es) and forming a sachet whose film construction comprises said water-soluble film.
• wax is used to generically classify many materials that are either natural or synthetic, and of petroleum, mineral, vegetable, or animal origin. They are normally solid at ambient temperature with a relatively low melting point, and capable of softening when heated and hardening when cooled (e.g. having a melting point of > 50°C, and usually within the range of 50 to 90°C. They are themselves insoluble in water. Waxes obtained from natural sources include animal waxes, vegetable waxes, mineral waxes and petroleum waxes.
• Examples of such materials include petroleum waxes such as paraffin waxes of various melting points and grades and microcrystalline wax; animal waxes such as beeswax; vegetable waxes such as carnuba wax and candelilla wax; and mineral waxes such as maston wax.
• petroleum waxes such as paraffin waxes of various melting points and grades and microcrystalline wax
• animal waxes such as beeswax
• vegetable waxes such as carnuba wax and candelilla wax
• mineral waxes such as maston wax.
• the wax(es) to be used in the invention should be water-dispersible, i.e. capable of being dispersed into water using e.g. surfactant(s) and high energy agitation.
• aqueous dispersions of waxes are usually available commercially, and are known as aqueous wax emulsions.
• Particularly preferred waxes are paraffin waxes (i.e. hydrocarbon or hydrocarbon-mixture waxes) and carnuba wax (often being used in combination).
• aqueous wax emulsion of this type is "Michelman" ML270-E which is an aqueous wax emulsion (average particle size of about 1 ⁇ m) of a mixture of paraffin and carnuba waxes, often delivered at about 40% w/w solids.
• the wax emulsion may be diluted with water if necessary before use in the invention.
• the aqueous wax emulsion is employed as a means for incorporating the wax(es) into the water-soluble film construction of the sachet.
• this is effected by admixture of an aqueous solution or dispersion (usually latex) of a water-soluble organic polymer(s) to be used as a film-forming binder(s) for the sachet with an aqueous emulsion of the wax(es).
• an aqueous solution or dispersion usually latex
• a water-soluble organic polymer(s) to be used as a film-forming binder(s) for the sachet
• an aqueous emulsion of the wax(es) e.g. latex
• the film-forming polymeric binder is in dispersion (e.g. latex) form at this stage, it should be capable of being converted to an aqueous solution at a subsequent stage, e.g. by bearing sufficient acid groups if an acrylic polymer, usually carboxylic acid groups, which will provide water- solubility by neutralisation with a base).
• this admixture will be a simple admixture, although
• the aqueous wax emulsion which is admixed with the aqueous solution (or dispersion) of the water-soluble film-forming polymer (as mentioned above), in a further embodiment of the invention is already in admixture with an acrylic polymer latex, usually in a wax/acrylic polymer weight ratio within the range of 99/1 to 50/50 (more preferably 90/10 to 70/30).
• This acrylic polymer may itself be water-soluble, e.g. by bearing neutralizable acid groups (usually carboxyl) at a sufficiently high level such that the polymer can subsequently become solubilized if desired by appropriate neutralisation with a base.
• this acrylic polymer need not be water-insoluble, e.g.
• the acrylic polymer may have a glass transition temperature (Tg) ranging from -20°C to 100°C, more preferably 10 to 50°C.
• the utility of this further embodiment is to further upgrade the quality of the water- soluble film of the sachet e.g. by improving its blocking resistance, improving film flexibility under low humidity conditions, and increasing solubility in cold water (when the further polymer is itself water-soluble).
• the acrylic polymer latex that is already in admixture with the wax emulsion before admixture with the water-soluble polymer(s) to be used as the film forming binder(s) for the sachet is present in small amount compared to the weight of the water-soluble film-forming polymer binder(s) itself.
• the acrylic polymer (in admixture with the wax) in this embodiment is present in an amount of 0.01 to 30 wt.%, more preferably 0.3 to 5 wt %, based on the weight of the water-soluble organic polymer(s) used as the film-forming binder(s) of the sachet.
• water-soluble organic polymer(s) which is used as the film- forming binder(s) to provide the water-soluble film construction of the sachet.
• examples of such polymers include polyethylene oxide, methyl cellulose and, especially, polyvinylalcohol (PVOH).
• the PVOH is generally partially or fully alcoholysed or hydrolysed, for example 40-100%, especially 80-100% (and often specifically 88%), alcoholysed or hydrolysed polyvinyl acetate.
• the resulting PVOH film may be a laminate of two or more thicknesses of film, a surface modified film or a co-extruded film.
• PVOH films include M7030 (a monolayer film), L7030 (a laminate film), M7031 (a monolayer film), L7031 (a laminate film) and M9500 (also referred to as PXP2841 , a monolayer film) all available from Chris Craft Industrial Products Inc. of South Holland, Illinois, USA.
• suitable polymers for this purpose include, in particular (as mentioned above), acrylic polymers bearing sufficient acid groups (usually carboxyl groups) for rendering the polymer water-soluble on neutralisation with a base.
• Such polymers are made from a monomer charge containing 5 to 40 wt %, more usually 8 to 15 wt % of olefinically unsaturated carboxylic acid-bearing monomer(s) (examples of such carboxyiic acid-bearing monomers being acrylic acid, methacrylic acid, ⁇ -carboxyethyl acrylate, maleic acid, and maleic anhydride), 40 to 95 wt%, more preferably 75 to 90 wt % of non- acid (meth)acrylate ester monomers containing 1 to 12 carbon atoms in the alcoholic ester-forming moeity, preferably C1 - C10 alkyl or hydroxyalkyl acrylates or methacrylates (examples of such monomers being methyl methacrylate, e
• a particularly preferred water-soluble acrylic polymer system for providing the water-soluble film-forming binder of the sachet is described in pending PCT International Application WO 97/00282 full reference to which is incorporated herein.
• S is defined as at least one acid-functional addition copolymer which is soft in character by virtue of having a Tg ⁇ 20°C
• H is defined as at least one acid-functional addition copolymer which is hard in character by virtue of having a Tg > 40°C
• the components S and H are present in a relative weight ratio of S to H within the range of from 90/10 to 65/35 and the acid-functionalities of S and H are at least partly neutralised such as to render the resulting film water-soluble.
• Tg of a copolymer herein is meant the glass transition temperature of the copolymer; as is well known, the Tg of a polymer is the temperature at which it changes from a glassy, brittle state to a plastic, rubbery state.
• Tg may be determined experimentally, e.g. by using differential scanning calorimetry (DSC), taking the peak of the derivative curve as Tg, or calculated from the well known Fox equation.
• DSC differential scanning calorimetry
• a copolymer of type S will often be derived from monomers comprising the following amounts (based on the total weight of monomers used) of acid-functional monomer(s), soft monomer(s), and hard monomer(s):
• acid-functional monomer(s) 5 to 40 wt.%, more usually 8 to 15 wt.%, particularly 8 to 14 wt.%.
• soft monomer(s) 40 to 85 wt.%, more usually 55 to 70 wt.%, particularly 60 to 70 wt.%.
• hard monomer(s) 5 to 50 wt.%, more usually 15 to 35 wt.%, particularly 20 to 30 wt.%.
• the above amounts of soft and hard monomers exclude acid-functional monomers whether hard or soft : these are included in the acid-functional monomer range).
• Examples of monomers combinations for making the soft copolymers are : acrylic acid/ethyl acrylate/methyl methacrylate; acrylic acid/n-butyl acrylate/ethyl acrylate/methyl methacrylate; acrylic acid/n-butyl acrylate/methyl methacrylate; methacrylic acid/ethyl acrylate/n- butylacrylate/methyl methacrylate; acrylic acid/methacrylic acid/n-butyl acrylate/ethyl acrylate/methyl methacrylate; and acrylic acid/methacrylic acid/ethyl acrylate/methyl methacrylate.
• soft and hard monomers for copolymers of type H are as described supra in respect of the soft and hard monomers for copolymers of type S.
• a copolymer of type H will often be derived from monomers comprising the following amounts (based on the total weight of monomers used) of acid functional monomer(s), soft monomer(s), and hard monomer(s) : acid-functional monomer(s) : 5 to 40 wt.%, more usually 8 to 15 wt.%, particularly 8 to 14 wt.%. soft monomer(s) : 0 to 50 wt.%, more usually 10 to 40 wt.%, particularly 25 to 40 wt.%. hard monomer(s) : 40 to 90 wt.%, more usually 50 to 80 wt.%, particularly 50 to 65 wt.%. (The above levels of soft and hard monomers exclude acid-functional monomers whether hard or soft : these are included in the acid-functional monomer range).
• Examples of monomer combinations for making the hard copolymers can be the same as those described supra for soft copolymers, but of course using different (i.e. appropriate) amounts of hard and soft monomers.
• With regard to the neutralisation of the acid-functional groups in acrylic polymers can be the same as those described supra for soft copolymers, but of course using different (i.e. appropriate) amounts of hard and soft monomers.
• the required degree of neutralisation can be brought about by the use of an appropriate base or basic salt so as to convert the desired proportion of acid-functional groups to anionic salt groups together with the corresponding presence of cations derived from the base of basic salt.
• Bases which could be used are non-volatile (i.e. permanent) bases such as the Group IA or II metal bases or basic salts, e.g. hydroxides, bicarbonates or carbonates (as appropriate) and particularly the hydroxides of Na, K and Li, and non-volatile water-soluble organic bases such as triethanolamine and 2-methyl-2-amino-1-propanol.
• Volatile bases which could be used are ammonia and volatile aliphatic amines such as triethylamine, diethanolamine and the like. However, it is preferred in most cases to use non-volatile (i.e. permanent or fixed) bases (since volatile bases might be lost during film formation and storage of the films - leading to impaired water-solubility), with the most preferred permanent base being NaOH. Nevertheless, the use of volatile bases such as (in particular) ammonia may be advantageous in some cases.
• Water-soluble acrylic polymers including acrylic polymer combinations, as with PVOH polymers discussed above, may provide resulting sachet film constructions of the monolayer type or the laminate type. It would also be possible in principle to employ a laminate construction of two quite different polymer types, e.g. a PVOH film laminated with an acrylic film.
• the wax may be incorporated into one or both of the laminate films. If incorporated into only one film, it is usually incorporated in the outer layer of the resulting sachet, although incorporation into only the inner layer is also possible.
• any technique may be used to make a water-soluble film as described above, for example calendering, extrusion or, more preferably, casting.
• a solution or dispersion of the polymer system, together with any desired additive(s) e.g. the wax
• any desired additive(s) e.g. the wax
• Laminate films may be formed by techniques such as sequential casting, co-extrusion, and lamination of two preformed films.
• the sachet film is preferably self-supporting.
• a wax-containing water-soluble film, whether in monolayer or laminate form, which is used for the film construction of an invention sachet should preferably contain from 1 to 30 wt.%, more preferably 3 to 10 wt.% of wax, based on the total dry weight of the film (and as mentioned above, in the case of a laminate film, the wax may be present in one or both of the two films and usually in at least the outer film).
• the water-soluble film used for making the invention sachet may also include (besides wax) if desired materials such as slip aids, colourants, wetting agents (surfactants), fillers (e.g. silica or starch), chelating agents, and (where necessary) plasticisers (such as glycerol e.g. in the case of polyvinyl alcohol film).
• the aqueous-based composition packaged in the water-soluble sachet is, in particular, an agrochemical composition comprising a water-soluble, agrochemically active ingredient, water, and optionally other components, such as electrolytes, thickeners, chelating agents, antifreeze agents, antifoam agents, buffers, dyes, emetics, preservatives, odourants, perfumes, safeners, organic solvents, stabilisers, synergists and wetting agents.
• an agrochemical composition comprising a water-soluble, agrochemically active ingredient, water, and optionally other components, such as electrolytes, thickeners, chelating agents, antifreeze agents, antifoam agents, buffers, dyes, emetics, preservatives, odourants, perfumes, safeners, organic solvents, stabilisers, synergists and wetting agents.
• the water-soluble agrochemically active ingredient is, for example, a herbicide such as a paraquat salt (for example paraquat dichloride or paraquat bis(methylsulphate)), a diquat salt (for example diquat dibromide or diquat alginate) or glyphosate or a salt or ester thereof (such as glyphosate isopropylammonium, glyphosate sesquisodium or glyphosate trimesium (also known as sulfosate)), an insecticide or a fungicide.
• a herbicide such as a paraquat salt (for example paraquat dichloride or paraquat bis(methylsulphate)), a diquat salt (for example diquat dibromide or diquat alginate) or glyphosate or a salt or ester thereof (such as glyphosate isopropylammonium, glyphosate sesquisodium or glyphosate trim
• An electrolyte can be included in to the composition to increase its ionic strength.
• the electrolyte concentration in the aqueous composition may be greater than the electrolyte concentration in the water in which the sachet is to be dissolved.
• the electrolyte normally would help to improve the insolubility of the material from which the sachet is made in the composition.
• Preferred electrolytes are ammonium sulphate, sodium sulphate, potassium sulphate, copper sulphate, ammonium nitrate, sodium nitrate, magnesium sulphate, potassium nitrate, sodium chloride and potassium chloride.
• Adjuvants or co-formulants may also be comprised in the composition.
• Suitable adjuvants include neutral or anionic surfactants [such as a soap, a salt of an aliphatic monoester of sulphuric acid (for example, sodium lauryl sulphate), a salt of a sulphonated aromatic compound (for example, sodium dodecylbenzenesulphonate) or an alkyl glucoside] or polysaccharides.
• Suitable wetters include an alkyl glycoside, a salt of a sulphonated aromatic compound (for example, sodium dodecylbenzenesulphonate), an alcohol ethoxylate or a diglucamide.
• Suitable thickeners include various grades of xanthan gum.
• the agrochemical composition may also comprise a chelating or sequestering agent for calcium ions.
• a suitable chelating or sequestering agent is ethylene- diaminetetraacetic acid.
• the agrochemical composition may also comprise an adhesive, an antifoaming agent, a buffer, a deodorant, a dye, an emetic, a preservative, an odourant, a perfume, a safener, a further solvent, a stabiliser, a synergist, a thickener or a wetting agent.
• the water-soluble sachet can be formed and filled using standard techniques (such as thermoforming or vertical form-fill-sealing).
• the packaged agrochemical composition is mixed with water (for example in an agrochemical sprayer) to give a sprayable solution of the water-soluble agrochemically active ingredient.
• a packaged aqueous-based composition (in particular a packaged aqueous agrochemical composition) of the present invention can be part of a bag-in-bag arrangement (for example an arrangement wherein the packaged aqueous-based composition of the present invention is enclosed within a second water-soluble sachet holding only the packaged aqueous-based composition of the present invention [the second sachet presenting a further barrier to contain the agrochemical composition]), part of an arrangement where two water-soluble sachets are joined at a common seal or part of an arrangement where seals of two water-soluble sachets are joined by a hinge of water-soluble film.
• a bag-in-bag arrangement for example an arrangement wherein the packaged aqueous-based composition of the present invention is enclosed within a second water-soluble sachet holding only the packaged aqueous-based composition of the present invention [the second sachet presenting a further barrier to contain the agrochemical composition]
• water-soluble sachets can be packaged in a non water-soluble outer bag acting as secondary packaging (e.g. made from a polyethylene/ aluminium foil/paper laminate).
• PVOH polyvinyl alcohol
• Aqueous PVOH solutions were prepared for example as follows:
• a solution in water at 15% w/w active component was prepared where the active component is:
• PVOH 'Mowiol 40-88', 88% hydrolysed, M. Wt. 127K, ex- Aldrich
• Glycerol Glycerol analar
• ex-BDH Starch 'Avedex 36LAC14U', ex-Avebe Ltd
• Aqueous solutions of PVOH/wax were prepared for example as follows: To obtain films of DFT of about 80 ⁇ m, two coats are cast each of about 40 ⁇ m DFT. When a wax containing film containing 10% w/w wax is required, on total film weight, the wax is combined in the second coat only at a level of 20% w/w. The wax emulsion is reduced to 15% w/w solids content by dilution with water. This is then added to the above PVOH solution with stirring at room temperature.
• Preparation of Water-Soluble Films for Sachets Films of about 80 ⁇ m DFT were made for the construction of these sachets. This was achieved by casting 2 layers of formulation, each being of about 40 ⁇ m DFT. The first coat was allowed to dry before application of the second coat.
• PVOH/wax formulation (16.6% w/w wax) was applied on top of the first coat (wet film thickness of 270 ⁇ m). This was again dried at 80°C for 1 hour. A final laminate coating was obtained at about 80 ⁇ m DFT containing 8.3% w/w wax, in which the contained wax is believed to have stratified to the coating/air interface during drying.
• the prepared films on polypropylene were cut to 240mm x 200mm.
• the polypropylene backing was then carefully removed.
• the film was folded in half lengthways.
• the wax-containing film formed the outer film of the sachet.
• the 2 shorter sides of the sachet were heat-sealed using a Hulme-Martin heat sealer.
• the heat setting was 6.5 and the cool setting was 8.5.
• the resulting sachet had the fold as the bottom edge.
• the sachet was filled with 70ml of saturated magnesium sulphate.
• the final side was then heat-sealed. This gives a sachet of approximate dimensions of 200mm x 120mm.
• the above water soluble sachets were contained in secondary outer packaging for storage; a laminate of polythene/aluminium foil/paper (90 micron DFT) was prepared with the polythene forming the inner side of the resulting package. Sheets of this material were cut to 210mm x 200mm. Two such sheets were placed together on top of each other and three sides heat-sealed. A water-soluble sachet was then placed inside this outer packing and the final side of the outer packing was heat-sealed.
• Example 1 Water Soluble Sachets with No Outer Packaging
• Example 2 Water Soluble Sachets Contained in Outer Packaging Three films were studied, each in duplicate 2a PVOH
• the solubility of the films was determined by mounting the film in a 35mm slide frame and immersing the slide mount into 500 cm 3 of water (distilled or tap), in a 600 cm 3 beaker, maintained at 10°C.
• the slide mount is stirred at 400 rpm using a 2.5cm length magnetic stirrer bar.
• the breakthrough time was defined as the time taken for the film sample to break free of the slide frame and dissolution time was measured as the time taken for complete dissolution of the film such that no trace of film remained when filtered through a 150 micron mesh sieve.
• the film is considered insoluble for this purpose.

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• Chemical & Material Sciences (AREA)
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• Mechanical Engineering (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
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• Compositions Of Macromolecular Compounds (AREA)
• Detergent Compositions (AREA)
• Agricultural Chemicals And Associated Chemicals (AREA)
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• 1996
  • 1996-11-13 GB GBGB9623562.7A patent/GB9623562D0/en active Pending
• 1997
  • 1997-10-16 DE DE69717852T patent/DE69717852T2/de not_active Expired - Lifetime
  • 1997-10-16 KR KR1019990704192A patent/KR20000053223A/ko not_active Application Discontinuation
  • 1997-10-16 AT AT97909459T patent/ATE229459T1/de not_active IP Right Cessation
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  • 1997-10-16 WO PCT/GB1997/002889 patent/WO1998021118A1/en active IP Right Grant
  • 1997-10-16 AU AU47140/97A patent/AU4714097A/en not_active Abandoned
  • 1997-10-16 PT PT97909459T patent/PT942875E/pt unknown
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