EP1421010B2 - Enveloppe soluble dans l'eau - Google Patents
Enveloppe soluble dans l'eau Download PDFInfo
- Publication number
- EP1421010B2 EP1421010B2 EP02716217A EP02716217A EP1421010B2 EP 1421010 B2 EP1421010 B2 EP 1421010B2 EP 02716217 A EP02716217 A EP 02716217A EP 02716217 A EP02716217 A EP 02716217A EP 1421010 B2 EP1421010 B2 EP 1421010B2
- Authority
- EP
- European Patent Office
- Prior art keywords
- packaging
- release
- substance
- water
- agents
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Lifetime
Links
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Images
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
- B65D81/00—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents
- B65D81/32—Containers, packaging elements, or packages, for contents presenting particular transport or storage problems, or adapted to be used for non-packaging purposes after removal of contents for packaging two or more different materials which must be maintained separate prior to use in admixture
- B65D81/3216—Rigid containers disposed one within the other
-
- 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
Definitions
- the present invention relates to improved packaging which is at least partially or substantially completely dissolvable in water for controlled release of substances, methods for controlled release using the packaging, methods for the production thereof, the use for release of a wide range of substances and novel products comprising the packaging.
- Water soluble packaging is known in the literature for dispensing substances, with partial or complete dissolution thereof leaving little or no residue.
- Such packaging materials are used in isolation as self supporting packaging or are used in combination with non soluble dispensers. These packaging materials release contained substances such as, hazardous substances, fungicides etc., concentrates such as detergents and the like on dissolution in water.
- DE 79 10 284 relates to a transportation water insoluble bag made of polyvinyl alcohol.
- the bag discloses a reinforcement band that is soluble in hot water. This reinforcement band covers a physical weakness zone that will open in a washing machine when the reinforcement band is dissolved in hot water.
- the bag is reusable by covering the physical weakness zone with a new reinforcement band.
- Encapsulation technology using water soluble capsule material is known in the pharmaceutical industry for delivery of pharmaceuticals, vitamins, supplements and the like by oral ingestion using gelatin, cellulose and derivatives as encapsulating materials.
- Gelatin, cellulose and derivatives and the like are substantially completely dissolvable in water and are approved capsule material for food and drug use. These capsules are intended for dissolving over a range of periods under different conditions within the body.
- Dissolvable gelatin sachets are known in the literature for containing and preserving powdered flavouring, colouring and other substantially dried food components as part of pre-packed food such as dehydrated noodles in a pot into which hot water is added in order to prepare the food for consumption. Failure or fracture of such sachets can lead to deterioration of contents.
- packaging comprising materials which are at least partially or substantially completely dissolvable in water-containing materials may be adapted according to the present invention to provide novel combinations of formulation and configuration suited for release of contained or enclosed substances in manner to meet the objective as hereinbefore defined.
- Controlled release packaging comprising all the features of claim 1.
- the substance to be released may be in the form of solid or liquid and is preferably selected from powders, granules, crystals, microcapsules, monoliths, suspensions, dispersions, concentrates, gels, thixotropes, non-aqueous solutions and the like and mixtures thereof.
- Solid substances may be in a desired grade or range of grades. For certain applications it is desired to provide substance in fine and course form for prolonged effect. It is an advantage of the present invention that individual doses of substance contain the desired range of solid grade and are not subject to the disadvantages of "settling" which result from transport and storage of volumes of the substance, or with combinations of substances having different particle grades.
- Substance to be released may be integral with the water-dispersible or soluble packaging material which is defined as in claim 1.
- the packaging is characterised by novel selection of features or combinations of features of packaging conformation and/or configuration, packaging material formulation and the like, in manner to provide novel selection of properties or combinations of properties. More specifically the packaging is characterised by novel selection of features or combinations relating to handling and storage, for example in manner to resist influences leading to premature release by means of package formulation conformation or configuration including sealing and reinforcing thereof; nature of comprised, contained or enclosed substances which may be viscous or non viscous fluid, non compactable flowable powder and other forms of substance which are not easily manipulated or controlled; nature and/or timing of release for example for releasing one or a combination of substances in simultaneous or subsequent fashion, or for releasing substances in manner to contact other substances in the desired locus for improved substance performance or quality for the intended use; nature of predetermined release stimulus and the like, for example being the water-containing substance itself, a physical or chemical stimulus in the desired locus or a combination thereof.
- features and properties may derive from the water-soluble or dispersible packaging material and/or from additional materials or substances formulated, conformed or configured with the water-dispersible or soluble packaging material, or from the conformation or configuration of the packaging, and are selected according to the intended use.
- the packaging may consist substantially entirely of water-dispersible or soluble packaging material or combinations thereof as hereinbefore defined or may comprise additional materials as hereinbefore defined which are at least partially dispersible or dissolvable or otherwise.
- the packaging is substantially completely dissolvable as hereinbefore defined.
- a water-containing substance is to any solid, semi-solid, liquid or gaseous (vapour) fluid which comprises water in effective dispersing or dissolving amount.
- Water may be chemically or physically releasably bound or may be freely available and may be gathered or accumulated from the substance or readily and instantly taken up by the material.
- a water-containing substance as hereinbefore defined comprises liquid- or vapour-form water, or aqueous solutions or vapour mixtures thereof with liquids or vapours such as alcohols and the like, or comprises solids or semi-solids having bound or available water.
- Water may be accumulated by the water-dispersible or soluble packaging material which at least partially disperses or dissolves to release the comprised, contained or enclosed substance into the accumulated water and the dispersed or dissolved packaging material may be retained in the locus or dispersed therefrom in the course of the intended use or otherwise.
- Reference herein to a predetermined stimulus is to any stimulus causing release of contained or enclosed substance.
- the stimulus may comprise chemical or physical stimulus for dissolving or dispersing, transforming by precipitation or morphology change, fracturing, rupturing or otherwise rendering permeable the packaging or a part thereof to release contained or enclosed substance.
- the stimulus may be the same as or different to the water-containing substance which serves to disperse or dissolve.
- Packaging materials may be dispersible or soluble in hot or cold water-containing substance and/or may release substance by dissolution or by other physical or chemical means such as exposure to heat, acid or alkali, solvents and solvent mixtures, oxidising conditions, radiant energy including UV, microwave and the like or biological degradants.
- locus is to any place, area or the like into or at which it is desired to release the substance.
- the locus may be the same as or may be different to but connecting with a locus at which the substance is to have a desired effect.
- the packaging comprises a primary and secondary component in terms of conformation, configuration or formulation adapted to dissolve and release the substance to the desired locus and to control stimulus or external influences to which the release element is subjected in manner to provide release with pre-determined timing and in pre-determined manner.
- the packaging may comprise any suitable material which is capable of being formed into packaging, and which is dispersible or dissolvable in water-containing substance to leave only a part thereof as residue or to leave substantially no residue.
- the water-dispersible or soluble packaging material comprises a natural or synthetic polymer or mixtures thereof selected from: Polyvinyl alcohol (PVA), polyethyleneoxide, chemically modified cellulose or cellulose ethers and other cellulose derivatives, modified starches, polyvinylpyrrolidone, polyacrylamide or gelatine or derivative thereof.
- PVA Polyvinyl alcohol
- polyethyleneoxide polyethyleneoxide
- chemically modified cellulose or cellulose ethers and other cellulose derivatives modified starches
- polyvinylpyrrolidone polyacrylamide or gelatine or derivative thereof.
- Chemically modified cellulose and cellulose ethers include alkyl- and/or hydroxyalkyl substituted cellulose or cellulose ether with 1 to 4 carbon atoms in the alkyl chain preferably methyl cellulose (ether), hydroxyethyl cellulose, hydroxyethylmethyl cellulose, hydroxyethylethyl cellulose, hydroxypropyl cellulose (having the chemical name cellulose hydroxypropylether), hydroxypropylmethyl cellulose (HPMC, having the chemical name cellulose hydroxypropylmethylether), hydroxybutylmethyl cellulose and the like.
- Modified starches include destructurised starch, cross-linked granular starches, chemically modified starches including alkyl substituted starches, amino starches and oxidised starches, dextrin and maltodextrins.
- Water-dispersible or soluble packaging material is suitably selected or adapted according to independent mechanical properties or combinations thereof ("soft” or “hard” and/or self-supporting or non self-supporting, resilient to premature fracture or otherwise and the like) and/or independent chemical properties and combinations thereof (slow or rapid, complete or partial dissolving, responsive to desired release stimulus and the like), requirements of non-toxicity (for environment, human or animal health or food-related uses and the like).
- water dispersible or soluble packaging material(s) may be provided having desired combination of properties by varying or selecting the moisture content, pH, moisture retention, swelling properties, gel strength, gel point, viscosity, concentration, reacting substituent groups (cross-linking) and sensitivity to a number of external stimuli such as temperature, pH, solvents and solvent mixtures, oxidising conditions, radiant energy such as UV or microwave, biological degradation by moulds and bacteria and the like.
- external stimuli such as temperature, pH, solvents and solvent mixtures, oxidising conditions, radiant energy such as UV or microwave, biological degradation by moulds and bacteria and the like.
- Formulations and formulation techniques are known for example as disclosed in Hard Capsules, ed. Ridgeway, WO 98/27151 (Warner Lambert ) the contents of which are incorporated herein by reference.
- Preferred packaging materials include gelatin, starch or cellulose or derivatives and mixtures thereof which are substantially completely soluble in water. Natural or synthetic gelatin and HPMC are found to have particularly useful properties.
- the packaging of the present invention may be of any desired conformation and configuration suited to contain or enclose a solid or fluid substance as defined in the claims.
- the conformation or configuration may be selected according to control requirements, storage requirements (stackable or able to be stored in space efficient manner i.e. cubes), use (adapted to be configured to locate in or in association with a support means of an environment), dispensable (adapted to be releaseably attached to a dispensing line, hook, rack or the like for convenient access), and the like.
- the packaging as hereinbefore defined may provide a primary structure or region of packaging material for strengthening, reinforcing, retaining package integrity during release or other such purpose, such as a skeleton, frame work, fibres, mesh, ribbing, webbing, seal or the like integral with or at least partially (co)-continuous with a secondary structure of substantially continuous packaging material in desired configuration.
- the packaging may comprise primary packaging material having secondary points of weakness in the form of packaging material formulated for rapid or easy dissolving or fracture, or of flaws or water entraining features such as moulding or embossing in the form of non-penetrating perforations, tear-off strip lines and the like.
- Primary and secondary structures and layers and point of weakness packaging material as hereinbefore defmed may be comprised of the same or different packaging materials and combinations thereof as hereinbefore defmed, having same or different properties such as thickness and the like.
- Different packaging materials include at least one packaging material being a water-dispersible or soluble packaging material which may be the same as or different to at least one being a packaging material adapted for release as hereinbefore defined.
- the packaging may comprise means for locating or positioning within the locus into which a contained substance is to be released in manner to secure it at the optimum position for storing, or for timing or activating the release stimulus for example for the operation of dissolving water in the locus on the release element, or to maintain the packaging in desired position in manner to withstand influences such as impact force during handling and storage and the like.
- Such locating means may comprise packaging material as hereinbefore defined adapted to engage a suitable support, for example may comprise an elongate substantially resilient or flexible portion adapted to be tied or hooked onto or located around a suitable projection or received within a recess of an effective support in the environment in which the packaging is contained, or may comprise resiliently deformable projections extending in opposing directions from the containing or enclosing packaging material as hereinbefore defined and adapted to be deformed to locate between opposing retaining means, surfaces and the like of an effective support means and be retained by resilience.
- the packaging comprises a specific configuration, conformation or formulation adapted to absorb or dispel external influences to which the packaging may be subjected and which may lead to premature release of contained or enclosed substance.
- the packaging may confer a protective shape on contained or enclosed fluid substance to minimise turbulence in storage and handling and/or may comprise packaging material of thickness, strength, resilience, flexibility and the like adapted to withstand external influences.
- Packaging as hereinbefore defined may be adapted to be self-supporting.
- packaging as hereinbefore defined comprises means to aid rapid release of contained or enclosed substance.
- the packaging comprises means to enhance the response thereof to release stimulus, by means of formulation or of additional components incorporated in or contained within the packaging.
- response enhancing means are adapted to cause release by expanding on contact with water-containing substances, for example comprise swelling or expanding agents (maize starch), effervescent agents (sodium bicarbonate and citric acid), disintegrants (Explotab TM available from Penwest Pharmaceuticals or Primojel TM available from Avebe), dispersing agents (sodium starch glycolate, sodium alginate, carboxymethylcellulose sodium salt and the like) or contained gases, such as air at a positive overpressure and the like, stimulus sensitising agents, for example adapted to cause release on change of pH (change in degree of acid or alkali conditions or transition therebetween), change in temperature, subjecting to microwave, UV, solvents and solvent mixtures and the like.
- Response enhancing means may be integral with packaging packaging material or contained in open or closed porosity therein to provide increased surface area and weak points as hereinbefore defined for release for example by dissolving action on contact with water, and to provide expansion of contained air on change of temperature, contact of effervescent agents with water, microwaves, UV, solvents and solvent mixtures and the like.
- a method for the production of packaging as defined in claim 13.
- the manufacture may be carried out in a single operation or in desired sequence, depending on the intended use, substance to be released and form of packaging.
- the production method may be adapted to confer any features of formulation conformation, configuration and the like as hereinbefore defined.
- the packaging may be formed by any known means for forking packaging materials as hereinbefore defined. Suitable means include any means for forming thermoplastic materials including residue free sealing one or more sheets, deforming one or more sheets by action of heat, solvents such as water, vacuum, pressure and the like, extruding, shaping from solution or molten, for example by dipping or spraying onto a former, casting, embossing etc.
- Substance(s) may be comprised, contained or enclosed within the packaging material by any known mechanical or chemical means including coforming the material and substance for example by fusing, blending or mixing into a molten packaging material or a solution thereof, or sealing the packaging material about the substance(s) for example by softening the packaging material with water or a sensitising agent and self bonding to unsoftened or similarly softened packaging material, bonding or welding with solvent, glue and the like with or without application of heat or pressure.
- any known mechanical or chemical means including coforming the material and substance for example by fusing, blending or mixing into a molten packaging material or a solution thereof, or sealing the packaging material about the substance(s) for example by softening the packaging material with water or a sensitising agent and self bonding to unsoftened or similarly softened packaging material, bonding or welding with solvent, glue and the like with or without application of heat or pressure.
- Preferably sealing is by techniques as disclosed in patent publications in the name of Capsugel, specifically by contacting edges of packaging material with a melting point depression sealing fluid such as organic solvents for example alkyl substituted C 1-5 alcohols, water, a polymer solution or emulsion, a solution of a proteolytic enzyme producing a protein solution and the like, and applying thermal energy or the like to cause fusion, for example as disclosed in relation to sealing of capsules in EP 0 152 517 , EP 0 180 543 , EP 0 116 744 , and EP 0 116 743 , the contents of which are incorporated herein by reference.
- a melting point depression sealing fluid such as organic solvents for example alkyl substituted C 1-5 alcohols, water, a polymer solution or emulsion, a solution of a proteolytic enzyme producing a protein solution and the like, and applying thermal energy or the like to cause fusion, for example as disclosed in relation to sealing of capsules in EP 0 152 517 , EP 0
- Points of weakness as hereinbefore defined may be provided in the packaging material by known means, for example embossing or moulding in the shape of the packaging by necking and the like, by laser exposure or by pre-determined orientation or ordering of molecules within the chemical structure of the packaging.
- Packaging as hereinbefore defined may be adapted to contain any desired quantity or volume of solid or liquid substance.
- the form and configuration of package is selected in part with reference to the desired volume and the nature of the substance to be contained or enclosed.
- the packaging is adapted to contain volumes of up to 10 litres of substance, for example in the range 0.1 ml up to 10 litres. Sub ranges for envisaged applications are preferably in the range of 0.1-5 ml, 5-50 ml, 50-500 ml, 500 ml - 5 litres and 5-10 litres.
- the packaging may be adapted to have a volume substantially equal to that of the substance to be contained or greater than, e.g. up to three times the volume of the substance to be contained.
- the packaging volume may be selected according to ease of filling with substances.
- packaging is adapted to contain or enclose a single measure dose of one or more substances to be released.
- Packaging may be adapted for clustering or may include a clustering element.
- Packaged substance may be clustered or aggregated by means of self adhesion, clustering attachment and the like in the case that a single measure exceeds the volume of substance which it is possible to contain or enclose or in the event that dosing is according to preference, or in the case that a selection of substances are to be released simultaneously or in controlled sequence.
- Packaging may comprise multiple compartments to segregate substances prior to release, or to provide sequential release.
- Packaging as hereinbefore defined may include an identification element, for example may be printed, moulded directly or indirectly for example by forming flexible packaging material tightly about a contained substance having moulded protrusions, or embossed, laser-marked or the like to indicate the nature or origin of the contents, the mode of use, or to incorporate features of design.
- Printing is preferably by means of inks, dyes and the like which are completely dissolvable in water and which are adapted to be printed from non aqueous solutions or from aqueous solutions.
- Packaging as hereinbefore defined may be adapted to release substances substantially instantaneously on contact with water-containing substances as hereinbefore defined or in a controlled period of the order of minutes for immediate use, quarter or a half hour period for example when it is desired to prime the packaging and evacuate the environment for release, hours or days for example where it is desired to prime the packaging for release during a period at which it is inconvenient or impossible to access the locus, or on response to a stimulus, for example where it is desired to release substances in the event of natural or artificial water release, such as to coincide with rain or intentional or unintentional water release that is part of any chemical, mechanical, construction, manufacturing or the like process.
- the packaging may be provided with additional agents adapted to enhance barrier properties for example to confer or enhance impermeability to oxygen and the like.
- Packaging may be provided as one piece or as a plurality of pieces to be assembled at the time of filling with substrate, for example using conventional or modified capsule technology.
- Packaging may be of any desired thickness, for example in the range 0.01 - 10 mm. It is a particular advantage of the present invention that minimal thickness for example in the range 0.01 - 1.0 mm may be attained with resilience to unintentional rupture, and that maximum thickness for example in the range 2 - 10 mm may be attained with desired precision of timing of release, by means of the selection of properties and features of formulations of packaging material, conformations such as solid mass of packaging material or configurations such as structures and points of weakness of packaging of the invention as hereinbefore defined.
- packaging material as hereinbefore defined may be adapted to maintain the integrity of the packaging prior to release of substances and to dissolve or disperse simultaneously with release or to subsequently disperse or dissolve over a prolonged period whilst still contained within the desired locus in contact with water-containing substance, during the period that the substance which has been released is effective, or thereafter.
- Packaging may be provided within an additional film or container if it is important to keep the surface free from contamination.
- Packaging or substance to be contained may comprise an additional indicating element, for example a component which indicates when dissolution is complete or when the substance has achieved its desired effect.
- a colorant within the substance is detectable in the aqueous locus once dissolution is sufficiently advanced to release substance.
- the colorant may be associated with the substance whereby the colour disappears once substance is consumed in use.
- the method provides advantages of reducing splash or spillage risk with hazardous substances during dilution, containing hazardous powder substances prior to dissolution and preventing the risk of inhalation, avoiding the need for safe disposal of used packaging material for hazardous substances and the like, providing pre-metered dosing in prescribed quantities as individual packages, convenient handling, minimising wastage of substance dregs, package disposal and the like.
- the method for controlled release as hereinbefore defined may be for any desired use for which it is intended to release a substance into an environment with any of the advantages as hereinbefore mentioned.
- the packaging may be located directly in the desired locus or may be transported to the desired locus by suitable means, maintained out of contact with water-containing substance.
- the packaging of the invention may be adapted to sink or float in water when added to a reservoir of water at the desired locus, or to initially sink or float and subsequently after a pre-determined interval float or sink prior to or at the time of release of contents, for example as indicating means or to maximise or minimise water content prior to release and the like.
- the method may be for release of agrochemical substances including pest or plant growth control agents, plant disease control agents, soil improvement agents and the like.
- pest growth control agents include insecticides, miticides, rodenticides, molluscicides, slugicides, vermicides (nematocides, antihelminthics), soil fumigants, pest repellents and attractants such as pheromones etc., and biological control agents such as microorganisms, predators and natural products
- plant growth control agents include herbicides, defoliants, desiccants, fruit drop and set controllers, rooting compounds, sprouting inhibitors, growth stimulants and retardants, moss and lichen controllers and plant genetic controllers or agents
- plant disease control agents include fungicides, viricides, timber preservatives and bactericides
- soil improvements agents include fertilisers, trace metal additives, bacterial action control stimulants and soil consolidation agents.
- the method may be for farming, greenhouse, horticultural, forestry and like applications on industrial or domestic scale by means of spraying, dusting, drilling and like techniques.
- the advantages of the method include advantages as hereinabove defined and may include further advantages of safe handling including reduced risk of contamination or carry over and no skin contact with active substance, convenience and ease of use, without measuring, decanting or re-sealing of part used sachets, dispensing with the need to dispose of contaminated packaging, precise dose control, avoiding user exposure to dust particles, providing solubility in cold water, providing greater flexibility in selection of dose amounts and with commercially available granules, reducing the risk of product deterioration once opened, optimising particle size for dissolution and use of minimal packaging. Further advantages include non clogging with spray nozzles and the like, no need for using a stirrer, no residue remaining, leak proof robust packaging and low cost per dose per unit area.
- the method is also suited for release of environmental treatment agents such as water purification agents, disinfectants, waste treatment agents and the like, including control agents for water borne viruses, bacterium, organisms and insects which carry disease, natural and industrial contaminants including water borne plant growth control agents, soil run off dispersant agents, cooling and recycled water neutralising agents and the like.
- environmental treatment agents such as water purification agents, disinfectants, waste treatment agents and the like, including control agents for water borne viruses, bacterium, organisms and insects which carry disease, natural and industrial contaminants including water borne plant growth control agents, soil run off dispersant agents, cooling and recycled water neutralising agents and the like.
- Advantages are as given above for agricultural use and include advantages of employing approved substances for use in purifying drinking water, and providing high quality of water which is not contaminated by particles or undissolved solid packaging material or residue, and speed of purifying action.
- Substances may be released into water or the desired locus in desired concentration suited for the desired effect, for example in lower amounts to render safe for consumption or in higher amounts to create
- the method may be used for handling safe-to-the-point-of-use substances, for example hazardous substances including caustics, chemical reagents, drain clearing substances and the like which may be used in diluted form, which are relatively safe although unpleasant in powdered, non-aqueous or concentrate form but which become hazardous in solution.
- a unit dose packaging may be provided which is safe to handle and which ensures correct dilution, and safety to the point of use. This may provide advantages as aboved defined in addition to further advantages such as eliminating the need to transport bulk substances in hazardous diluted form, by providing a means for the safe dilution by the end user.
- the method may be used for releasing detergents and their components in the form of solids or liquids such as concentrates, including domestic and industrial detergents for cleaning premises, objects and clothing and for personal hygiene using any known detergents or cleaning agents.
- the advantages include those given above, and additionally include aesthetic advantages by which the packaging leaves no deposit on the hands and is more pleasant to handle than powders or tablets, is structurally of high integrity preventing break up or spillage risk of the substance, has a reduced risk of product deterioration once a primary pack is opened and associated extended shelf life, has potentially more efficient and effective delivery of key ingredients, is easier to manufacture, formulate and use and gives a reduced risk of concentrate damage to clothes, skin and other articles, and renders optional the use of bags or devices from which to release the substance, additionally having the advantages of minimising the required amount of softening agents, bleaches, brighteners, dispersants, effervescent and other solubilising agents including phosphates.
- the method may also be used to release food components including flavours and fragrances in the form of dried or powdered solids, liquids and volatiles, texturising agents, colorants, moisture absorbers such as rice, corn flour, salt and the packaging material itself, oils and fats, dried dairy products and other food products which deteriorate in the presence of oxygen, seasoning and herbs and the like.
- food components including flavours and fragrances in the form of dried or powdered solids, liquids and volatiles, texturising agents, colorants, moisture absorbers such as rice, corn flour, salt and the packaging material itself, oils and fats, dried dairy products and other food products which deteriorate in the presence of oxygen, seasoning and herbs and the like.
- the method for releasing food substances has advantages as indicated above and additional advantages in terms of precise dose control providing sizes linked to standard culinary measures for example, separation of ingredients without using packs that need to be opened by the user, for example in instant food packs, environmentally friendly avoiding non edible secondary packaging, microwaveable, no risk of contamination with secondary packaging fragments, clean and easy handling, edible packaging, no susceptible residue in hot water, sealing from air, preserving freshness and shelf life, taste and smell masking until required, for example to avoid contaminating other food components or the like, preservation of vitamins, colour, purity of flavour and the like.
- packaging may be used to minimise deterioration of substances due to contact in storage by separating and simultaneously may provide for improved dispersibility and contact on release by positioning food components in manner for optimum contact on release.
- novel products comprising packaging as hereinbefore defined.
- novel products include products adapted for the specific methods as hereinbefore defined with the associated advantages.
- the products may be provided for filling with substance(s) for release or may be provided containing the substance(s).
- the products may comprise packaging having features of conformation, configuration and formulation as hereinbefore defined.
- Figure 1 in each case packaging in the form of conformation and configurations typically obtained by dipping from molten or solutions of packaging materials.
- Figures 1a to 1g capsules comprising water-dispersible or soluble multiple layers and/or multiple sections of material in the form of peripheral shells (11) and linking portions (12, 13).
- Figure 1a shows a capsule having central monolayer of rapid dissolve packaging material and peripheral bilayers of rapid-slow and slow-rapid dissolve packaging material respectively, adapted to provide a weak link or point of weakness as hereinbefore defined.
- Figure 1b is shown a capsule having central and peripheral monolayers of rapid dissolve and slow dissolve packaging materials respectively and peripheral bilayer of rapid-slow dissolve packaging material, as an alternative to the configuration of Figure 1a . Variations of these configurations are envisaged and may be determined according to the desired ease of manufacture and desired release characteristics.
- the capsule of Figure 1a may be manufactured for example by forming peripheral shells (11a inner, 11d outer) by dipping a former to a first depth into respective solutions of or molten slow and rapid dissolve packaging material respectively, then forming shell (11a outer) by dipping to a greater depth into a solution of or molten rapid dissolve packaging material, simultaneously creating portion (11b) and finally filling and overlap capping the portion (11b) with shell (11d outer), simultaneously creating seal (11c).
- the capsule of Figure 1b may be manufactured for example by forming shells (11e inner, 11d) as for 11a inner and 11d outer above, then forming shell (11e outer) by dipping the inner to a lesser depth in slow dissolve packaging material, and filling and overlap capping shell (11d) simultaneously forming seal (11c).
- Figures 1c and 1d show capsules peripheral shells which are shrunk fit about (shaped or moulded) substance and have therebetween secondary points of weakness in the form of an easy dissolving region (12) having an area adapted to peel back, for example on swelling in the form of an unsealed abutment of the two peripheral shells (11d).
- Figures 1e and 1f show capsules comprising an easy dissolving packaging material band (13) bridging a gap between shells (11d). Solid or liquid ingredients are enclosed within the capsule (11d, 11d) and released via the easy dissolving region (13) on rapid dissolution in water.
- Figures 1g relates to the present invention and shows a capsule comprising a rapid dissolve monolayer peripheral shell (11f) enclosing substance and inner secondary peripheral shell (11d), abutting or overlap sealed to the capsules remote peripheral shell (11d).
- the capsule may be suited to enclose two same or different substances with staged release, with rapid release of one substance via the rapid dissolve shell (11f) and subsequent release of the second substance by slow dissolve of capsule (11d, 11d).
- Figures 1h and 1i are shown packaging in the form of a primary dipped bag or wallet (14) which is filled and sealed, with a separate cap portion (15) or by self-sealing by crimping (16) as illustrated.
- Crimping may optionally provide a release feature in the form of a primary structure as a point of strength portion to prevent premature release or as a secondary point of weakness portion which is for example adapted for rapid dissolving in water to release contents of the bag with subsequent dissolution of the bag or wallet.
- Figures 2a and 2b are shown a sachet in the form of secondary structure packaging material (21) located around a primary structure mesh bag of slow dissolving reinforcing packaging material (22) which may be fused or otherwise with the packaging material (21).
- Packaging material (21) is sealed at the edges.
- This packaging is suited for delivery of graded substances whereby rapid dissolving of packaging material (21) releases fine particles from within the primary structure mesh bag (22), large particles being released later on slow dissolving of mesh bag (22).
- the sachet may comprise packaging material (21) as flexible or rigid packaging material or a combination thereof which may be flat or formed, for example by vacuum. This configuration may also be employed in other embodiments according to the present disclosure using any packaging material as desired.
- FIG 3a In Figure 3a is shown water-soluble capsule (31) in the form of a first capsule portion, retained by means of a resiliently deformable capsule shell (32) on a support means (33) in locus (34).
- a resiliently deformable capsule shell (32) By locating the water soluble capsule (31) on support means (33) external influences of locus (34) leading to premature release are minimised.
- the shell (31) dissolves releasing contents, with subsequent dissolution of the locating shell (32).
- a capsule which may be made of water soluble packaging material adapted to be located by means of resiliently deformable wings (36), thereby locating a capsule in position and potentially damaging external influences within the locus.
- FIGs 4a - 4c are shown configurations of packaging constructed of packaging material (41) with soluble seal or crimp (42).
- Packaging may be constructed by means including flow wrapping or extruding to form a seamed or seamless tube with seamed sectioning along the length, as shown in Figures 4b(i) and 4b(ii) .
- Figures 5a and 5b are shown clustering elements comprising water soluble packaging material (52) according to the invention and clustered water-soluble packaging in the form of capsules (51). On contact with water the clustered capsules dissolve rapidly to release their contents with subsequent dissolution of the clustering element which serves to aid withstanding external influences leading to premature release prior to contact with water.
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Abstract
Claims (23)
- Conditionnement à libération contrôlée sous la forme d'une gélule comprenant un matériau de conditionnement qui est sensiblement complètement dispersible ou soluble dans une quantité efficace d'une substance contenant de l'eau et
qui est adapté pour contenir ou enfermer une ou plusieurs substances,
dans lequel
le conditionnement est adapté pour libérer les substances contenues ou enfermées en réponse à un stimulus prédéterminé, d'une manière prédéterminée, sur un site voulu, avec dispersion ou dissolution sensiblement simultanée ou ultérieure, partielle ou complète, des substances,
dans lequel le conditionnement comprend
au moins un composant primaire et un composant secondaire adaptés pour dissoudre et libérer la substance sur le site voulu de façon à permettre une libération à un moment prédéterminé et d'une manière prédéterminée, de sorte que les au moins composants primaire et secondaire réalisent des régions de structure à couches multiples (11a, 11e) et uniques (11b, 11d)
et
l'un des composants primaire ou secondaire a des points de faiblesse (12) dans la forme du matériau de conditionnement formulé pour une dissolution ou fracture rapide ou lente, ou des amorces de rupture ou des caractéristiques entraînant l'eau, telles qu'un moulage ou un gaufrage sous la forme de perforations non pénétrantes pour amorcer la dissolution du conditionnement
et
dans lequel le matériau de conditionnement comprend une coque périphérique (11f) monocouche à dissolution rapide, enfermant une substance et une coque périphérique (11d) secondaire intérieure, ladite coque périphérique (11f) étant en butée ou scellée à chevauchement avec la coque périphérique (11d) de conditionnement distante, avec libération rapide d'une substance via la coque (11f) à dissolution rapide et libération ultérieure de la seconde substance par dissolution lente du conditionnement (11d). - Conditionnement selon la revendication 1, dans lequel la substance à libérer est sous la forme d'un solide ou d'un liquide et est de préférence sélectionnée parmi les poudres, les granules, les cristaux, les microcapsules, les monolithes, les suspensions, les dispersions, les concentrés, les gels, les thixotropes, les solutions non aqueuses et analogues, ainsi que leurs mélanges, dans une qualité ou une gamme de qualités voulue.
- Conditionnement selon l'une quelconque des revendications 1 à 2, qui est sensiblement complètement soluble.
- Conditionnement selon l'une quelconque des revendications 1 à 3, qui est dispersible ou soluble dans une substance contenant de l'eau comprenant, tout solide, semi-solide, liquide ou fluide gazeux (vapeur) qui comprend de l'eau en quantité efficace à la dispersion ou à la dissolution, eau qui peut être liée de façon chimiquement ou physiquement libérable ou qui peut être librement disponible et qui peut être rassemblée ou accumulée depuis la substance ou facilement et instantanément capturée par le matériau de conditionnement.
- Conditionnement selon l'une quelconque des revendications 1 à 4, adapté pour libérer la substance contenue ou enfermée, en réponse à un stimulus prédéterminé comprenant tout stimulus chimique ou physique, pour dissoudre ou disperser, transformer par précipitation ou changer la morphologie, fracturer, rompre ou autre moyen permettant de rendre perméable le conditionnement ou une partie de celui-ci.
- Conditionnement selon l'une quelconque des revendications 1 à 5, dans lequel le stimulus est ou non le même que la substance contenant de l'eau qui sert à disperser ou dissoudre, les matériaux étant dispersibles ou solubles dans une substance contenant de l'eau chaude ou froide et/ou pouvant libérer la substance par dissolution ou par d'autres moyens physiques ou chimiques tels que l'exposition à de la chaleur, à un acide ou à une base, à des solvants et mélanges de solvants, à des conditions oxydantes, à une énergie rayonnante y compris les UV, les micro-ondes et analogues ou à des agents de dégradation biologique.
- Conditionnement selon l'une quelconque des revendications 1 à 6 pour libérer une substance sur un site comprenant tout emplacement, zone ou analogue dans lequel, ou au niveau duquel, il est souhaitable de libérer la substance, site qui peut être ou non le même que le lieu que celui la substance doit avoir un effet voulu, mais qui est en connexion avec ledit lieu.
- Conditionnement selon l'une quelconque des revendications 1 à 7, dans lequel le matériau de conditionnement hydrodispersible ou hydrosoluble comprend un polymère naturel ou synthétique ou un mélange de tels polymères, sélectionné parmi le poly(alcool vinylique) (PVA), le poly(oxyde d'éthylène), la cellulose chimiquement modifiée ou des éthers de cellulose chimiquement modifiée et d'autres dérivés de la cellulose, des amidons modifiés, la polyvinylpyrrolidone, le polyacrylamide ou la gélatine, ou leurs dérivés.
- Conditionnement selon l'une quelconque des revendications 1 à 8, comprenant des moyens (36) pour localiser ou positionner au sein du site dans lequel une substance contenue doit être libérée de manière à la garder dans la position optimale pour le stockage, ou pour programmer ou activer le stimulus de libération, par exemple, pour le fonctionnement de l'eau dissolvante dans le site sur l'élément à libérer, ou pour maintenir le conditionnement dans une position voulue de façon qu'il résiste aux influences telles qu'une force d'impact au cours de la manipulation et du stockage.
- Conditionnement selon l'une quelconque des revendications 1 à 9, dans lequel les moyens de localisation (36) comprennent une portion allongée, sensiblement résiliente ou flexible, adaptée pour être attachée ou ancrée ou située autour d'une projection convenable ou reçue dans un évidement d'un support efficace de l'environnement dans lequel le conditionnement est contenu, ou peut comprendre des projections déformables de manière résilientes et s'étendant dans des directions opposées à partir du matériau de conditionnement tel que précédemment défini et adaptées pour être déformées pour se loger entre des moyens de retenue opposés, des surfaces et analogues, d'un moyen support efficace et à y être retenues par résilience.
- Conditionnement selon l'une quelconque des revendications 1 à 10, comprenant une conformation, configuration ou formulation adaptée pour absorber ou dissiper des influences externes auxquelles le conditionnement peut être soumis et qui peuvent conduire à une libération prématurée de la substance contenue ou enfermée.
- Conditionnement selon l'une quelconque des revendications 1 à 11, comprenant des moyens pour augmenter la réponse du conditionnement à un stimulus de libération, au moyen d'une formulation ou de composants additionnels incorporés ou contenus dans le conditionnement, sélectionnés parmi des moyens adaptés pour provoquer la libération par dilatation au contact avec des substances contenant de l'eau, par exemple comprenant des agents de gonflement ou de dilatation, des agents effervescents, des désintégrants, des agents de dispersion ou des gaz contenus, tels que l'air à une surpression positive et analogues, des agents sensibilisant au stimulus, par exemple adaptés pour provoquer la libération lors d'un changement de pH, un changement de température, l'exposition à des micro-ondes, à des UV, à des solvants et mélanges de solvants, et analogues.
- Procédé pour la production d'un conditionnement à libération contrôlée comprenant la formation d'un conditionnement à partir d'un matériau de conditionnement tel que défini précédemment dans l'une quelconque des revendications 1 à 12, comprenant la formation du matériau de conditionnement et l'introduction d'une ou plusieurs substances à libérer de façon à être contenues ou enfermées dans ledit conditionnement.
- Procédé selon la revendication 13, dans lequel la formation des matériaux de conditionnement est sélectionnée parmi le scellement d'une ou plusieurs feuilles sans résidu, la déformation d'une ou plusieurs feuilles sous l'action de la chaleur, des solvants tels que l'eau, du vide, de la pression et analogues, l'extrusion, la conformation à partir de solutions ou de masses fondues, par exemple par trempage ou pulvérisation sur un conformateur, coulage, gaufrage.
- Procédé selon l'une quelconque des revendications 13 et 14, dans lequel la ou les substances peuvent être contenues ou enfermées au sein du matériau de conditionnement par des moyens mécaniques ou chimiques sélectionnés parmi le coformage du matériau et de la substance par fusion, homogénéisation ou mélange dans un matériau de conditionnement fondu ou une solution de celui-ci, scellement du matériau de conditionnement autour, de la ou des substances par ramollissement du matériau de conditionnement avec de l'eau ou un agent de sensibilisation et auto-liaison à du matériau de conditionnement non ramolli ou ramolli de façon similaire, liaison ou soudage avec un solvant, une colle et analogues, avec ou sans application de chaleur ou de pression, mise en contact des bords du matériau de conditionnement avec un fluide de scellement abaissant le point de fusion tel qu'un solvant organique, de l'eau, une solution ou une émulsion polymère, une solution d'une enzyme protéolytique produisant une solution de protéines et analogues, et l'application d'énergie thermique ou analogue pour provoquer la fusion.
- Procédé selon l'une quelconque des revendications 13 à 15, dans lequel le conditionnement inclut un élément d'identification qui, par exemple, peut être imprimé, moulé, gaufré ou marqué au laser pour indiquer la nature ou l'origine des contenus, le mode d'utilisation ou pour incorporer des caractéristiques de modèle.
- Procédé selon l'une quelconque des revendications 13 à 16, dans lequel le conditionnement ou la substance devant être contenu comprend un élément indicateur supplémentaire, par exemple un composant qui indique quand la dissolution est complète ou quand la substance a atteint l'effet voulu.
- Procédé pour la libération contrôlée d'une substance tel que défini ci-dessus, employant un conditionnement dispersible ou soluble dans l'eau tel que défini dans l'une quelconque des revendications 1 à 12, comprenant le positionnement du conditionnement sur un site à des fins de libération voulues et la soumission à un stimulus de libération, par exemple la mise en contact avec une substance contenant de l'eau en quantité efficace sur le plan de la dispersion ou de la dissolution, pendant une durée efficace pour activer la libération comme défini ici et la libération de la substance dans le site, le conditionnement étant simultanément ou ultérieurement sensiblement dissous en totalité dans la substance contenant de l'eau.
- Procédé selon la revendication 18 pour la libération de substances agrochimiques y compris des agents de la maîtrise de la croissance des nuisibles ou des plantes, des agents de la maîtrise des maladies des plantes, des agents améliorant les sols, et analogues, pour des applications d'agriculture, de culture en serre, d'horticulture, de sylviculture et analogues, à l'échelle industrielle ou domestique au moyen d'une pulvérisation, d'un saupoudrage, d'un enfouissage et de techniques analogues.
- Procédé selon la revendication 18 pour la libération d'agents de traitement environnementaux tels que des agents de purification de l'eau, des désinfectants, des agents de traitement de déchets et analogues, y compris des agents de contrôle vis-à-vis des virus, bactéries, organismes et insectes transportés par l'eau et qui sont des vecteurs de maladies et de contaminants naturels et industriels, y compris des agents de contrôle de la croissance des plantes transportés par l'eau, des agents de dispersion des ruissellements des sols, des agents de neutralisation de l'eau de refroidissement et recyclée, et analogues.
- Procédé selon la revendication 18 pour le traitement et la libération de substances sûres jusqu'au point d'utilisation, par exemple de substances dangereuses, notamment les agents caustiques, les réactifs chimiques, les substances de débouchage de tuyaux d'évacuation et analogues qui peuvent être utilisés sous une forme diluée, qui sont relativement sûrs bien que déplaisants à l'état pulvérulent, non aqueux ou concentré, mais qui deviennent dangereux en solution.
- Procédé selon la revendication 18 pour libérer des détergents ou autres agents de nettoyage sous la forme de solides ou de liquides, tels que des concentrés, notamment des détergents domestiques et industriels pour nettoyer les locaux, les objets ou l'habillement, ou pour l'hygiène personnelle, utilisant tout détergent ou agent de nettoyage connu.
- Procédé selon la revendication 18 pour la libération de composants alimentaires, notamment des parfums et des effluves sous la forme de solides séchés ou pulvérisés, de liquides et de produits volatils, des agents texturants, des colorants, des absorbeurs d'humidité tels que le riz, la farine de maïs, le sel et le matériau de conditionnement lui-même, des huiles et des graisses, des produits laitiers séchés et d'autres produits alimentaires qui se détériorent en présence d'oxygène, des épices, des herbes et analogues.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE60223691T DE60223691T3 (de) | 2001-08-16 | 2002-01-22 | Wasserlösliche verpackung |
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US31287901P | 2001-08-16 | 2001-08-16 | |
| PCT/IB2002/000230 WO2003016165A1 (fr) | 2001-08-16 | 2002-01-22 | Enveloppe soluble dans l'eau |
| US312879P | 2010-03-11 |
Publications (3)
| Publication Number | Publication Date |
|---|---|
| EP1421010A1 EP1421010A1 (fr) | 2004-05-26 |
| EP1421010B1 EP1421010B1 (fr) | 2007-11-21 |
| EP1421010B2 true EP1421010B2 (fr) | 2012-01-18 |
Family
ID=23213412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP02716217A Expired - Lifetime EP1421010B2 (fr) | 2001-08-16 | 2002-01-22 | Enveloppe soluble dans l'eau |
Country Status (10)
| Country | Link |
|---|---|
| EP (1) | EP1421010B2 (fr) |
| JP (1) | JP3936699B2 (fr) |
| KR (1) | KR20040021698A (fr) |
| CN (1) | CN100351151C (fr) |
| BR (1) | BR0211947A (fr) |
| CA (1) | CA2454432A1 (fr) |
| DE (1) | DE60223691T3 (fr) |
| ES (1) | ES2294123T5 (fr) |
| MX (1) | MXPA04001395A (fr) |
| WO (1) | WO2003016165A1 (fr) |
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| PL202692B1 (pl) * | 2002-07-03 | 2009-07-31 | Obrist Closures Switzerland | Pojemnik rozpuszczalny w wodzie |
| GB2401848A (en) * | 2003-05-20 | 2004-11-24 | Reckitt Benckiser | Two-compartment water-soluble container |
| MY137973A (en) | 2003-10-31 | 2009-04-30 | Obrist Closures Switzerland | A tamper-evident closure |
| GB2429691B (en) * | 2005-09-06 | 2007-09-26 | Monosol Af Ltd | Closable, water-soluble or water-dispersible bags |
| GB0608433D0 (en) | 2006-04-28 | 2006-06-07 | Obrist Closures Switzerland | Closure with RFID device |
| HUE052058T2 (hu) | 2007-04-20 | 2021-04-28 | Zenon Tech Partnership | Membrán által tartott biofilm berendezés és eljárás |
| US20080263797A1 (en) * | 2007-04-30 | 2008-10-30 | Berger Maggie V | Single-use toilet brush head |
| KR20100049577A (ko) * | 2007-07-05 | 2010-05-12 | 다우 글로벌 테크놀로지스 인크. | 검출 기능을 가진 용해성 필름 |
| GB2450940B (en) | 2007-07-13 | 2011-11-30 | Obrist Closures Switzerland | Tamper-evident closure |
| GB2450939B (en) | 2007-07-13 | 2012-02-01 | Obrist Closures Switzerland | Tamper-Evident closure |
| GB0721330D0 (en) | 2007-10-31 | 2007-12-12 | Obrist Closures Switzerland | Tamper Evident closure |
| GB0806190D0 (en) | 2008-04-04 | 2008-05-14 | Obrist Closures Switzerland | A closure |
| EP2451961A1 (fr) * | 2009-07-07 | 2012-05-16 | Novozymes A/S | Procédé de traitement d'un substrat par une enzyme |
| DE202009012547U1 (de) * | 2009-09-17 | 2010-02-11 | Rapp, Günther | Reinigungsprodukt, insbesondere für die Scheibenwaschanlage eines Kraftfahrzeugs |
| JP2011140333A (ja) * | 2010-01-08 | 2011-07-21 | Tsukioka:Kk | 即席食品収容容器 |
| KR101311697B1 (ko) * | 2010-12-13 | 2013-09-26 | 조건환 | 수소생성사탕용기 |
| KR101237957B1 (ko) * | 2010-04-15 | 2013-02-27 | 조건환 | 연질피막 수소보관용기 및 그 제조 방법 |
| USD630093S1 (en) | 2010-06-11 | 2011-01-04 | Obrist Closures Switzerland Gmbh | Closure |
| US8684619B2 (en) | 2010-10-26 | 2014-04-01 | The Procter & Gamble Company | Cleaning device having plural and customizable cleaning surfaces |
| AU2010366243A1 (en) * | 2010-12-20 | 2013-06-27 | General Electric Company | Water soluble package films for acidic product and method for adding acidic product to water system |
| KR101306944B1 (ko) * | 2011-03-18 | 2013-09-10 | 정웅섭 | 다기능 젤라틴 캡슐 |
| CN102205772A (zh) * | 2011-03-30 | 2011-10-05 | 莫雄勋 | 一种水溶性生物降解型工艺礼品及其使用方法 |
| ITMI20120601A1 (it) * | 2012-04-13 | 2013-10-14 | Getters Spa | Composizione essiccante per dispositivi elettronici sensibili all'umidità |
| US9394092B2 (en) * | 2012-04-16 | 2016-07-19 | Monosol, Llc | Powdered pouch and method of making same |
| CN103239420B (zh) * | 2013-05-14 | 2014-09-03 | 海南卫康制药(潜山)有限公司 | 笼状结构片剂及其制备方法 |
| US20150074916A1 (en) * | 2013-09-18 | 2015-03-19 | John Miller | Method and aparatus for applying nanoparticle surface treatments inside a container |
| USD739106S1 (en) | 2013-09-23 | 2015-09-15 | The Procter & Gamble Company | Cleaning pad |
| US9670440B2 (en) * | 2013-10-07 | 2017-06-06 | Monosol, Llc | Water-soluble delayed release capsules, related methods, and related articles |
| CN105722768B (zh) * | 2013-10-07 | 2019-02-19 | 蒙诺苏尔有限公司 | 水溶性延迟释放胶囊、相关方法和相关制品 |
| CN105707068B (zh) * | 2016-01-26 | 2018-05-18 | 刘圣泉 | 一种用于无人机喷撒的农药及制备方法 |
| DE102016115927A1 (de) | 2016-08-26 | 2018-03-01 | Brauns-Heitmann GmbH & Co Kommanditgesellschaft | Färbesystem für textile Materialien |
| CN108872558B (zh) * | 2018-04-26 | 2020-03-31 | 烟台芥子生物技术有限公司 | 利用可溶解膜进行化学反应的方法及包括可溶解膜的检测试剂盒 |
| KR102080785B1 (ko) * | 2018-05-11 | 2020-02-24 | 김성준 | 장내 미생물 표적 채취용 캡슐 |
| CN108587204A (zh) * | 2018-05-14 | 2018-09-28 | 重庆路维康交通科技有限公司 | 一种沥青混合料的温拌再生剂及其制备和使用方法 |
| JP7195837B2 (ja) * | 2018-09-20 | 2022-12-26 | 株式会社フジシール | 角錐包装体 |
| CN109777634A (zh) * | 2019-01-25 | 2019-05-21 | 关汉杰 | 一种遇水发泡胶囊及其制备方法 |
| KR102236214B1 (ko) * | 2019-03-11 | 2021-04-05 | 경북대학교 산학협력단 | 지반 고결 시스템 |
| US20200345039A1 (en) * | 2019-05-02 | 2020-11-05 | Verily Life Sciences Llc | Reformatted insect food product for aquatic environments |
| DE102020120706A1 (de) | 2020-08-05 | 2022-02-10 | Rovema Gmbh | Schlauchbeutel zur Verpackung einer Pflanze |
| US11484806B2 (en) | 2020-08-14 | 2022-11-01 | Moose Creative Management Pty Limited | Buoyancy assisted toy packaging |
| KR20230025209A (ko) | 2021-08-13 | 2023-02-21 | 삼성전자주식회사 | 반도체 패키지 |
| CN113477494A (zh) * | 2021-08-20 | 2021-10-08 | 刘海霞 | 一种染料的环保使用方法 |
| CN114772051B (zh) * | 2022-04-08 | 2024-02-20 | 汕头市佳宏纸制品有限公司 | 一种高强度防水自降解纸袋 |
| CN118890960A (zh) * | 2022-05-11 | 2024-11-01 | 阿萨达股份公司 | 单剂量消毒剂 |
| CN119660972A (zh) * | 2024-12-12 | 2025-03-21 | 山东省高速养护集团有限公司 | 用于合流制排口污水的好氧微生物在线培养及投加设备 |
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2002
- 2002-01-22 DE DE60223691T patent/DE60223691T3/de not_active Expired - Lifetime
- 2002-01-22 CN CNB028160363A patent/CN100351151C/zh not_active Expired - Fee Related
- 2002-01-22 KR KR10-2004-7002192A patent/KR20040021698A/ko not_active Ceased
- 2002-01-22 JP JP2003521106A patent/JP3936699B2/ja not_active Expired - Fee Related
- 2002-01-22 CA CA002454432A patent/CA2454432A1/fr not_active Abandoned
- 2002-01-22 MX MXPA04001395A patent/MXPA04001395A/es active IP Right Grant
- 2002-01-22 BR BR0211947-1A patent/BR0211947A/pt not_active IP Right Cessation
- 2002-01-22 ES ES02716217T patent/ES2294123T5/es not_active Expired - Lifetime
- 2002-01-22 EP EP02716217A patent/EP1421010B2/fr not_active Expired - Lifetime
- 2002-01-22 WO PCT/IB2002/000230 patent/WO2003016165A1/fr not_active Ceased
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| Publication number | Priority date | Publication date | Assignee | Title |
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| EP0479404A2 (fr) † | 1990-10-03 | 1992-04-08 | Unilever Plc | Film pour emballage et sachet |
| EP0607316B1 (fr) † | 1991-10-16 | 1997-02-26 | Rhone-Poulenc Agriculture Ltd. | Emballage etanche |
| WO2001044433A1 (fr) † | 1999-12-13 | 2001-06-21 | Henkel Kommanditgesellschaft Auf Aktien | Doses de lessive, produit vaisselle ou detergent a liberation controlee de la substance active |
| WO2001060340A1 (fr) † | 2000-02-16 | 2001-08-23 | Bioprogress Technology International Inc. | Capsule d'administration de substance |
Also Published As
| Publication number | Publication date |
|---|---|
| MXPA04001395A (es) | 2004-05-27 |
| DE60223691T3 (de) | 2012-07-19 |
| JP3936699B2 (ja) | 2007-06-27 |
| DE60223691D1 (de) | 2008-01-03 |
| KR20040021698A (ko) | 2004-03-10 |
| ES2294123T3 (es) | 2008-04-01 |
| CN1543421A (zh) | 2004-11-03 |
| CN100351151C (zh) | 2007-11-28 |
| EP1421010B1 (fr) | 2007-11-21 |
| BR0211947A (pt) | 2004-09-21 |
| WO2003016165A1 (fr) | 2003-02-27 |
| ES2294123T5 (es) | 2012-06-29 |
| EP1421010A1 (fr) | 2004-05-26 |
| DE60223691T2 (de) | 2008-10-30 |
| CA2454432A1 (fr) | 2003-02-27 |
| JP2005500211A (ja) | 2005-01-06 |
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