EP2032268A1 - Dispensing device for dispensing a plurality of different preparations - Google Patents
Dispensing device for dispensing a plurality of different preparationsInfo
- Publication number
- EP2032268A1 EP2032268A1 EP07723139A EP07723139A EP2032268A1 EP 2032268 A1 EP2032268 A1 EP 2032268A1 EP 07723139 A EP07723139 A EP 07723139A EP 07723139 A EP07723139 A EP 07723139A EP 2032268 A1 EP2032268 A1 EP 2032268A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- dispensing device
- preparation
- cartridge
- receiving
- cartridges
- 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.)
- Granted
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/0005—Components or details
- B05B11/0078—Arrangements for separately storing several components
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
- B05B11/1081—Arrangements for pumping several liquids or other fluent materials from several containers, e.g. for mixing them at the moment of pumping
- B05B11/1084—Arrangements for pumping several liquids or other fluent materials from several containers, e.g. for mixing them at the moment of pumping each liquid or other fluent material being pumped by a separate pump
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
- B05B11/1081—Arrangements for pumping several liquids or other fluent materials from several containers, e.g. for mixing them at the moment of pumping
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B12/00—Arrangements for controlling delivery; Arrangements for controlling the spray area
- B05B12/14—Arrangements for controlling delivery; Arrangements for controlling the spray area for supplying a selected one of a plurality of liquids or other fluent materials or several in selected proportions to a spray apparatus, e.g. to a single spray outlet
- B05B12/1409—Arrangements for controlling delivery; Arrangements for controlling the spray area for supplying a selected one of a plurality of liquids or other fluent materials or several in selected proportions to a spray apparatus, e.g. to a single spray outlet the selection means being part of the discharge apparatus, e.g. part of the spray gun
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/04—Deformable containers producing the flow, e.g. squeeze bottles
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
- B05B11/1001—Piston pumps
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B05—SPRAYING OR ATOMISING IN GENERAL; APPLYING FLUENT MATERIALS TO SURFACES, IN GENERAL
- B05B—SPRAYING APPARATUS; ATOMISING APPARATUS; NOZZLES
- B05B11/00—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use
- B05B11/01—Single-unit hand-held apparatus in which flow of contents is produced by the muscular force of the operator at the moment of use characterised by the means producing the flow
- B05B11/10—Pump arrangements for transferring the contents from the container to a pump chamber by a sucking effect and forcing the contents out through the dispensing nozzle
- B05B11/1001—Piston pumps
- B05B11/1009—Piston pumps actuated by a lever
Definitions
- Dispenser device for dispensing a plurality of different ones
- the invention relates to a dispensing device for the substantially simultaneous dispensing of a plurality of mutually different preparations with a connection for the detachable fixing of portion cartridges, which in particular contain additive substances.
- a particularly suitable medium for the individualization of a product is its packaging, since this forms the direct interface between consumer and product.
- US5857591 discloses a dispensing device for simultaneously spraying two mutually different preparations.
- This document discloses a trigger pump, which simultaneously promotes preparations of separate chambers of a bottle, the delivery to the environment can be done by two spatially separate conduit systems, so that it comes only after the product delivery to a mixture of both preparations.
- US5857591 also has the disadvantage that no selection of the preparations to be dosed with one another can take place. Only the preparations in the two chambers can be sprayed in a certain mixing ratio to one another.
- a dispensing device that can deliver a particular preparation from a multichamber container is known from US5152431.
- US5152431 discloses a trigger pump rotatably mounted on the closure of a multi-chamber bottle. From an adapter plate in each case a riser extends into each of the chambers which are filled with different compositions. By rotation of the trigger pump, a suction-side supply pipe, which is connected to the pump, are communicatively coupled via the adapter plate with a riser. In this way it is possible to optionally spray a certain preparation from one of the chambers.
- Another object of the invention is to design the dispensing device such that it can be used without having to make design changes to single-chamber bottles. This object is achieved by a dispenser device having the features of claim 1.
- the product contained in the packaging is to assemble in a simple way.
- a significant advantage of the dispenser according to the invention is to be seen in the fact that the user can be provided by the use of portion cartridges a wide range of self-selectable clothing options for a product located in the packaging.
- the manufacturing costs can be kept low compared to solutions of the prior art.
- the dispenser device according to the invention can be operated with only one conveying means for dispensing the two mutually different preparations from the portion cartridges and the packaging, whereby the constructive and thus the cost can be kept low.
- the dispenser device comprises a connection to the detachable additive substance preparation contained portion cartridges are coupled.
- exactly one portion cartridge can be coupled to the connection.
- the connection in the Shape is formed that at least two portion cartridges are coupled simultaneously to the terminal.
- a conveying means is a device which is coupled to the actuating element and is suitable for conveying a preparation from the packaging material into the environment.
- the conveying means may be formed as a pump.
- the pump can be driven mechanically or electrically.
- a pump can be selected from the group of positive displacement pumps, screw pumps (Archimedean screw), bellows pumps, piston pumps, rotary lobe pumps, gear pumps, diaphragm pumps, rotary vane pumps, peristaltic pumps, toothed belt pumps, progressing cavity pumps, screw pumps, flow pumps, centrifugal pumps, axial pumps, diagonal pumps foam pumps or radial pumps.
- the conveying means may also be designed as a pressurized aerosol package, wherein the conveying means is designed as such by the pressurized propellant of the aerosol package.
- the conveying means is designed as a preferably elastically deformable container, in which the pressure increase necessary for conveying the preparation from the packaging material in the interior of the packaging means is effected by a jerky squeezing of the packaging medium jacket walls.
- the conveying means and the actuating means are designed as one device, namely the squeezable container. packaging
- a packaging means is a device which is intended to cover a preparation in such a way that it can be shipped, stored and / or sold.
- the packaging usually has a bottom and a lateral surface, through which a volume is formed for receiving a preparation. Furthermore, the packaging means regularly has an opening for dispensing the preparation from the packaging, wherein the opening can be closed by a closing means.
- the closing means and the dispensing device can preferably be designed as a component, for example in the form of a molded onto the dispensing device, provided with an internal thread coupling ring.
- a packaging material may in particular be selected from the group of bottles, containers, cans, boxes, bags etc.
- the packaging is formed squeezable.
- the packaging material may in particular be elastically shaped in such a way that after being squeezed, the packaging material again assumes its original shape prior to crushing. Due to the squeezable shaping of the packaging, it is possible to exert a sufficient pressure on the preparation contained in the packaging, which causes a release of the preparation from the packaging to the environment. This allows the packaging in particular take over the function of the actuating means and the conveying means.
- the packaging material is designed as an aerosol package.
- a can or bottle forms the pressure-resistant base body of the aerosol container in which a standing by a propellant under pressure liquid, pasty or powdery contents can be removed when operating an aerosol valve as a spray or foam.
- the packaging material has a filling volume of 100 ml-5,000 ml, preferably 125 ml-2,000 ml, more preferably 150 ml-1,500 ml, most preferably 175 ml-1,250 ml.
- an actuating means is understood to mean a device which is coupled directly or indirectly to the conveying means in such a way that the delivery of a preparation from a packaging means is effected by actuation of the actuating means by the user.
- the actuating means may in particular be designed as a hinged lever, for example in the form of a trigger, wherein the operation is carried out regularly by a substantially horizontal movement of the free end of the lever.
- actuating means as a pump dispenser, which usually has a vertical movement and actuation kinetics.
- the packaging is formed squeezable. Due to the squeezable shaping of the packaging, it is possible to exert a sufficient pressure on the preparation contained in the packaging, which causes a release of the preparation from the packaging to the environment. In this way, the packaging can take over in particular the function of the actuating means and the conveying means.
- the receiving means may comprise a plurality of portion cartridges with mutually different preparations and filling volume.
- the receiving means has a capacity between 2-20 portion cartridges, preferably between 2-15 portion cartridges, more preferably between 2-10 portion cartridges, most preferably between 2-6 portion cartridges.
- the receiving means may be embodied in a particularly preferred embodiment of the invention as a revolver-like drum having a plurality of concentrically arranged around the drum rotation axis cartridge chambers for receiving each one portion cartridge.
- the portion cartridges may in this case be permanently or detachably connected to the receiving drum.
- the take-up drum can be prefabricated with portion cartridges whose additive compositions are, for example, adapted to a particular intended use. However, it is also conceivable that the user the Pick-up drum equipped according to a given application situation.
- the receiving means is designed as a magazine with a cartridge chamber for receiving a plurality of portion cartridges.
- the portion cartridges are in this case arranged substantially straight above or next to each other.
- the receiving means as a blister pack, the cavities of the blister forming the portion cartridges and the blister strip the actual receiving means.
- the receiving means can comprise viewing windows or be formed from an at least partially transparent material.
- a portion cartridge is a packaging means, for the purpose of being coupled to the connection of the dispensing device, for a preparation which contains at least one additive substance and which is different from the preparation in the packaging means.
- the individually packaged in a portion cartridge, portionable additive product units are releasably fixed by a suitable form-fitting, non-positive or cohesive connection to the connection of the dispenser.
- a suitable form-fitting, non-positive or cohesive connection to the connection of the dispenser.
- Particularly preferred types of connection are snap-in connections, screwed, plug-in or press-fit connections as well as adhesive connections.
- the portion cartridges can be individually coupled by the user to the port. It is particularly convenient the portion cartridges that can be coupled to the port, the dispenser or the packaging for the user removed, in particular individually removable, to order.
- receiving means may be provided on or at which the portion cartridges are detachably fixed to the dispenser or the packaging means, so that the user can remove them from the receiving means on the dispenser or bottle and couple them to the connection for use of a particular portion cartridge.
- a plurality of portion cartridges may be arranged in a receiving means, wherein the coupling of a portion cartridge to the port is then carried out by a relative movement of the receiving means relative to the terminal, so that for changing a Portion cartridge this no longer needs to be removed from the dispenser.
- a portion cartridge can have a viewing window or be made of an at least partially transparent material.
- the portion cartridge is preferably formed from a shape or volume stable material.
- a portion cartridge may have a filling volume which allows a single dose of the additive-containing preparation. This means that almost all of the content of the portion cartridge is added to the conveyed from the packaging preparation by pressing the actuator. However, it is also conceivable that a portion cartridge has a filling volume which permits a multiple dosing of the additive-containing preparation, wherein only a part of the contents of the portion cartridge is added to the conveyed from the packaging preparation by operating the actuating element.
- the portion cartridge may comprise a closure which is designed so that by the subsequent operation of the Conveying and the resulting from the flow in the suction line or pressure line negative pressure at least a portion of the preparation is dispensed from the portion cartridge.
- the closure may for example be designed as a membrane or silicone valve.
- the closure may be shaped such that, due to the surface tension or viscosity of the preparation, leakage is prevented.
- a portion cartridge has a filling volume of 1 ml to 200 ml, preferably 2 ml to 100 ml, more preferably 2.5 ml to 50 ml, most preferably 3 ml to 25 ml.
- the portion cartridges have a volume ratio of 1: 5000 to 1:20 to the packaging, preferably between 1: 2500 and 1:25, particularly preferably between 1: 1750 and 1:50.
- a portioned cartridge coupled to the port of the dispensing device may be connected directly to the conveying means, whereby a precise adjustment of the pressure conditions, an exact dosage of the preparation from the portion cartridge is possible. Furthermore, the preparation of the portion cartridge and the packaging are only immediately in or after the Conveyance means brought together, whereby the risk of possible undesirable effects by the reaction of the two preparations, for example in the form of deposits or gelling, which could cause clogging of leads, is reduced.
- a portion cartridge indirectly, i. is formed via an existing with the funding supply line.
- a release of the preparation contained in the portion cartridge is then carried out for example by a Venturi effect, which causes a negative pressure in the connection of the portion cartridge by the flow of a fluid in the supply line to the conveyor.
- the portion cartridge may contain a preparation which forms an emulsion or suspension with the preparation contained in the packaging.
- the portion cartridge may contain a solid in the form of a powder, the powder acting as an abrasive, for example.
- the contents of the portion cartridges may consist of one or more identical or different products or additives such as, fragrances, cleaning substances, dyes, enzymes, hygroscopic substances and the like.
- a fragrance-neutral cleaning liquid each time a product is dispensed from the packaging, a fragrance from another portion cartridge can be added. This prevents on the one hand the olfaktometrische adaptation to a particular fragrance, on the other hand, a fragrance can be selected according to the requirements of a specific application space (toilet, living room, kitchen). This does not require the more Use of several specially perfumed cleaning substances, which is also desirable in terms of environmental protection and resource conservation.
- the pH of the mixed preparation can be adjusted.
- a low pH value when using the dispenser device according to the invention for cleaning bath surfaces of calcium deposits, while, for example, in the solution of fatty deposits by selecting the corresponding portion cartridge, a high pH value can be selected.
- a preparation is a liquid, pasty, gelatinous or pulverulent, fodable substance or a mixture of substances.
- the preparation may be present as a solution, mixture, emulsion or suspension of several substances.
- additive is understood as meaning a substance or substance mixture which is suitable for achieving or influencing a property of the product by mixing with the product contained in the container, in particular improving, producing, highlighting, attenuating, accelerating a temporal process or to slow down, to initiate, inhibit or catalyze a reaction.
- additive should also be understood to mean a substance or a substance mixture which is suitable for achieving or influencing a property of the container, in particular fragrance and / or active substance delivery, adsorption or absorption on or in the container.
- the additive may, for example, one or more substances from the group of fragrances, bleaching agents, cleaning substances, solvents, surfactants, dyes, enzymes, hygroscopic substances, flame retardants, hardeners, leveling agents, wetting agents, dispersants, foaming agents, defoamers, deaerators, corrosion inhibitors, biocides, water softeners , Preservatives, emulsifiers, stabilizers, vitamins, minerals and the like
- fragrance compounds for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons, can be used in the context of the present invention.
- Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, allylcyclohexyl propionate, styrallyl propionate and benzyl salicylate.
- the ethers include, for example, benzyl ethyl ether, to the aldehydes, for example, the linear alkanals with 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, to the ketones such as the ionone, oc-lsomethylionon and methyl cedryl ketone , the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, the hydrocarbons mainly include the terpenes such as limonene and pinene.
- fragrance oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
- the general description of the perfumes that can be used generally represents the different substance classes of fragrances.
- a fragrance must be volatile, whereby besides the nature of the functional groups and the structure of the chemical compound, the molecular weight also plays an important role plays. For example, most odorants have molecular weights up to about 200 daltons, while molecular weights of 300 daltons and above are more of an exception. Due to the different volatility of fragrances, the smell of a perfume or fragrance composed of several fragrances changes during evaporation, whereby the odor impressions in "top note”, “middle note” or “body note” ) and “base note” (end note or dry out).
- the top note of a perfume or fragrance does not consist solely of volatile compounds, while the base note consists for the most part of less volatile, ie adherent fragrances.
- the base note consists for the most part of less volatile, ie adherent fragrances.
- more volatile fragrances can be bound to certain fixatives, preventing them from evaporating too quickly.
- the subsequent classification of the fragrances in "more volatile” or “adherent” fragrances so nothing about the olfactory impression and whether the corresponding fragrance is perceived as a head or middle note, nothing said.
- the product smell can be influenced in this way for agents according to the invention immediately upon opening the brand-new composition as well as the use fragrance, for example when used in a dishwashing machine.
- fragrance impressions can of course be the same, but can also differ.
- adhesive odoriferous substances is advantageous, while also more volatile odoriferous substances can be used for product scenting.
- Adhesive-resistant fragrances which can be used in the context of the present invention are, for example, the essential oils such as angelica root oil, aniseed oil, arnica blossom oil, basil oil, bay oil, bergamot oil, champa blossom oil, fir pine oil, pinecone oil, elemi oil, eucalyptus oil, fennel oil, pine needle oil, galbanum oil, geranium oil, ginger grass oil, guaiac wood oil, gum balm oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil , Calamus oil, chamomile oil, camphor oil, kanga oil, cardamom oil, cassia oil, pine oil, Kopa ⁇ vabalsamöl, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, tangerine oil, lemon balm oil, musk oil, myrrh oil, clove oil, neroli oil, n
- fragrances can be used in the context of the present invention as adherent fragrances or fragrance mixtures, ie fragrances.
- These compounds include the following compounds and mixtures thereof: ambrettolide, ⁇ -amylcinnamaldehyde, anethole, anisaldehyde, anisalcohol, anisole, methyl anthranilate, acetophenone, benzylacetone, benzaldehyde, ethyl benzoate, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol , Bornyl acetate, ⁇ -bromostyrene, n-decyl aldehyde, n-dodecyl aldehyde, eugenol, eugenol methyl ether, eucalyptol,
- the more volatile fragrances include in particular the lower-boiling fragrances of natural or synthetic origin, which can be used alone or in mixtures.
- Examples of more readily volatile fragrances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linayl acetate and propionate, menthol, menthone, methyl-n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
- the plastic particles are loaded at a temperature of 15 to 30 ° C, preferably from 20 to 25 ° C, with the selected perfume.
- the particles are mixed with the appropriate amount of perfume and mixed.
- the temperature should be below the melting or decomposition temperature of the plastic and also below the flash point of the perfume oil.
- the fragrance is absorbed by adhesion, diffusion and / or capillary forces of the polymeric carrier material or of other perfume carrier materials contained in the particle, these being able to swell slightly in the course of this process.
- agents according to the invention may contain, in addition to the ingredients required for scenting and deodorization, further active substances. Accordingly, other product groups which contain further preferred substances in addition to the abovementioned constituents according to the invention can be distinguished from the agents which serve exclusively for scenting. dyes
- a first of these optionally usable preferred substances are the dyes.
- all dyes are generally suitable, which are known to the skilled person as suitable for coloring plastics or as soluble in perfume oils. It is preferable to select the dye according to the fragrance used; For example, lemon fragrance particles are preferably yellow in color, while for apple or herb fragrance particles, a green color is preferred.
- Preferred dyes have a high storage stability and insensitivity to the other ingredients of the agents and to light. If the agents according to the invention are used in connection with textile or dishwashing, the dyes used should have no pronounced substantivity towards textile fibers, glass, plastic dishes or ceramics in order not to stain them.
- Suitable dyes and dye mixtures are commercially available under various trade names and are offered, inter alia, by the companies BASF AG, Ludwigshafen, Bayer AG, Leverkusen, Clariant GmbH, DyStar Textile dyes GmbH & Co. Germany KG, Les Colorants Wackherr SA and Ciba Specialty Chemicals.
- Suitable fat-soluble dyes and dye mixtures include, for example, Solvent Blue 35, Solvent Green 7, Solvent Orange 1 (Orange au Gras-W-2201), Sandoplast Blue 2B, Grease Yellow 3G, Iragon® Red SRE 122, Iragon® Green SGR 3, Solvent Yellow 33 and Solvent Yellow 16, but other dyes may be included.
- the dye additionally has an indicator function in addition to its aesthetic effect.
- the consumer of the current state of consumption of the deodorant is displayed, so that he receives in addition to the lack of fragrance impression, which may for example be based on a habituation effect on the part of the user, another reliable indication when the deodorant is to be replaced by a new one.
- the indicator effect can be achieved in various ways: On the one hand, a dye can be used, which escapes from the particles during the period of application. This can be effected, for example, by the ingredients contained in the dishwashing detergent.
- a dye must be used, which adheres well to the particles or only slowly diffuses out of them to ensure that the discoloration is not too early, namely, when the fragrance is not consumed, is completed.
- a color change can also be caused by a chemical reaction or thermal decomposition.
- compositions according to the invention are substances such as antimicrobial agents, germicides, fungicides, antioxidants or corrosion inhibitors, with the aid of which additional benefits, such as, for example, disinfection or corrosion protection, can be realized.
- compositions of the invention may contain antimicrobial agents.
- antimicrobial agents Depending on the antimicrobial spectrum and mechanism of action, a distinction is made between bacteriostats and bactericides, fungistatics and fungicides, etc.
- Important substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenolmercuric acetate.
- the compositions may contain antioxidants.
- This class of compounds includes, for example, substituted phenols, hydroquinones, catechols and aromatic amines, as well as organic sulfides, polysulfides, dithiocarbamates, phosphites and phosphonates. If the agents according to the invention are used in dishwashing machines, then these agents for protecting the product or the machine can contain corrosion inhibitors, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art.
- silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole.
- cleaner formulations often contain active chlorine-containing agents which can markedly reduce the corrosion of the silver surface. In chlorine-free cleaners are particularly oxygen and nitrogen-containing organic redox-active compounds, such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds used.
- salt and complex inorganic compounds such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
- the transition metal salts which are selected from the group of manganese and / or cobalt salts and / or - complex, particularly preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
- zinc compounds can be used to prevent corrosion on the items to be washed.
- redox-active substances in the compositions according to the invention.
- These substances are preferably inorganic redox-active substances from the group of manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and / or complexes, wherein the metals preferably in one of the oxidation states II, III, IV, V or VI are present.
- the metal salts or metal complexes used should be at least partially soluble in water.
- the counterions suitable for salt formation comprise all customary mono-, di- or tri-positively negatively charged inorganic anions, eg. As oxide, sulfate, nitrate, fluoride, but also organic anions such. Stearate.
- Metal complexes in the context of the invention are compounds which consist of a central atom and one or more ligands and optionally additionally one or more of the above-mentioned.
- Anions exist.
- the central atom is one of the o.g. Metals in one of the above Oxidation states.
- the ligands are neutral molecules or anions that are mono- or polydentate;
- the term "ligand" within the meaning of the invention is e.g. in "Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart / New York, 9th edition, 1990, page 2507" explained in more detail.
- the charge of the central atom and the charge of the ligand (s) do not add up to zero, either one or more of the above may be provided, depending on whether there is cationic or anionic charge excess.
- Anions or one or more cations e.g. As sodium, potassium, ammonium ions, for the charge balance.
- Suitable complexing agents are e.g. Citrate, acetylacetonate or 1-hydroxyethane-1, 1-diphosphonate.
- metal salts and / or metal complexes are selected from the group MnSO 4 , Mn (II) citrate, Mn (II) stearate, Mn (II) acetylacetonate, Mn (II) - [I-
- these metal salts or metal complexes are generally commercially available substances that can be used for the purpose of silver corrosion protection without prior purification in the compositions of the invention.
- SO production contact method
- V 2 O 5, VO 2, V 3 O 4 pentavalent and tetravalent vanadium (V 2 O 5, VO 2, V 3 O 4) suitable, as is the titanyl sulfate by diluting a Ti (SO 4) 2 solution resulting, TiOSO. 4
- the metal salts and / or metal complexes mentioned are present in the compositions according to the invention, preferably in an amount of 0.05 to 6% by weight, preferably 0.2 to 2.5% by weight, based on the total composition without the container, contain
- bleaching agents and bleach activators may be present in the compositions according to the invention in addition to other constituents.
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- Dishwashing detergent tablets may also contain bleaches from the group of organic bleaches.
- Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
- Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
- Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [Phthaloiminoperoxyhexanoic acid (PAP)], o-
- the agents according to the invention may contain bleach activators in order to achieve an improved bleaching action during cleaning at temperatures of 60 ° C. and below.
- bleach activators compounds which under perhydrolysis conditions aliphatic peroxycarboxylic acids having preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally substituted perbenzoic acid, are used. Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
- polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoyl-succinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate and 2,5- Diacetoxy-2,5-dihydrofuran.
- TAED tetraacety
- bleach activators preferably used in the context of the present application are compounds from the group of cationic nitriles, in particular cationic nitriles of the formula
- R 1 is -H, -CH 3, a C 2 - 24 alkyl or alkenyl group, a substituted C 2-24 -alkyl or -alkenyl radical having at least one substituent from the group -Cl, -Br, - OH, -NH 2
- -CN 1 is an alkyl or alkenylaryl radical having a Ci -24 - alkyl group, or represents a substituted alkyl or Alkenylarylrest with a Ci- 24 alkyl group and at least one further substituent on the aromatic ring
- R 2 and R 3 are independently selected from -CH 2 -CN, -CH 3 , -CH 2 -CH 3 , -CH 2 -CH 2 -CH 3 , -CH (CH 3 ) -CH 3> -CH 2 -OH, -CH 2 -CH 2 -OH, - CH (OH) -CH 3 , -CH 2 -CH 2 -CH 2 -OH
- R 5 is -N (+) - (CH 2 ) -CN X »
- bleach catalysts can also be incorporated into the compositions.
- These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes can also be used as bleach catalysts.
- Preferred agents in the context of the present application contain one or more surfactants from the groups of anionic, nonionic, cationic and / or amphoteric surfactants.
- Preferred anionic surfactants in acid form are one or more substances from the group of carboxylic acids, sulfuric acid half esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids.
- the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical.
- the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
- Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the past century led directly to the alkali salts (soaps), today only large amounts of water are used for cleavage, which cleaves the fats into glycerol and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage.
- hexanoic acid caproic acid
- heptanoic acid enanthic acid
- octanoic acid caprylic acid
- nonanoic acid pelargonic acid
- decanoic acid capric acid
- undecanoic acid etc.
- fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated species 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-oct
- Sulfuric acid semi-esters of longer-chain alcohols are also anionic surfactants in their acid form and can be used in the context of the present invention.
- Their alkali metal salts, in particular sodium salts, the fatty alcohol sulfates are industrially available from fatty alcohols, which are reacted with sulfuric acid, chlorosulfonic acid, sulfamic acid or sulfur trioxide to the respective alkyl sulfuric acids and subsequently neutralized.
- the fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters.
- alkyl ether sulfuric acids whose salts, the alkyl ether sulfates, have a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
- Alkyl ether sulfuric acids like the alkyl sulfuric acids, are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.
- Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form.
- Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons.
- Another process for producing alkanesulfonic acids is sulfoxidation in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation.
- This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals.
- the reaction with unreacted paraffin provides an alkyl radical and the alkylpersulfonic acid which decomposes into an alkylperoxysulfonyl radical and a hydroxyl radical.
- the reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid.
- this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.
- Olefinsulfonates are produced industrially by reaction of ⁇ -olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.
- Alkyl benzene sulfonates as powerful anionic surfactants have been known since the 1930's. At that time, alkylbenzenes were prepared by monochlorination of kogasin fractions followed by Friedel-Crafts alkylation, which were sulfonated with oleum and neutralized with sodium hydroxide solution. In the early 1950's propylene was tetramerized into branched ⁇ -dodecylene to produce alkylbenzenesulfonates and the product was reacted via a Friedel-Crafts reaction using aluminum trichloride or hydrogen fluoride to tetrapropylenebenzene, which was subsequently sulfonated and neutralized. This economic possibility of producing tetrapropylene benzene sulfonates (TPS) led to the breakthrough of this class of surfactants, which subsequently displaced soaps as the major surfactant in detergents and cleaners.
- TPS t
- Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins.
- large-scale petroleum fractions are separated with molecular sieves in the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both ⁇ - and i-olefins.
- ABSS alkylbenzenesulfonic acid
- anionic surfactant in acid form according to the invention are C ⁇ -i ⁇ -. preferably Cg- 13- alkylbenzenesulfonic acids. It is within the scope of the present invention further preferably, C 8- i 6 - to use 13 -alkylbenzenesulfonic acids preferably Cg derived from alkylbenzenes having a tetralin content below 5 wt .-%, based on the alkylbenzene.
- alkylbenzenesulfonic acids whose alkylbenzenes were produced by the RF method, so that the Cs-i ⁇ - employed, preferably C 9- I 3 - alkylbenzenesulfonic acids have a content of 2-phenyl isomer below 22 wt .-% , based on the alkylbenzenesulfonic acid.
- anionic surfactants in their acid form may be used alone or in admixture with each other.
- the anionic surfactant in acid form before addition to the / the carrier material (s) further, preferably acidic, ingredients of detergents and cleaners in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, in each case based on the weight of the mixture to be reacted, mixed.
- anionic surfactants partially or fully neutralized. These salts can then be present as solution, suspension or emulsion in the granulation liquid, but also as a solid component of the solid bed.
- anionic surfactants in addition to the alkali metals (here in particular according to claim and K salts), ammonium and mono-, di- or triethanolalkonium ions.
- the analogous representatives of mono-, di- or trimethanolamine or those of the alkanolamines of higher alcohols can also be quaternized and present as a cation.
- cationic surfactants can be used with advantage as an active substance.
- the cationic surfactant can be added directly to the mixer in its delivery form, or can be sprayed onto the solid carrier in the form of a liquid to pasty cationic surfactant formulation.
- Such cationic surfactant preparation forms can be prepared, for example, by mixing commercial cationic surfactants with auxiliaries, such as nonionic surfactants, polyethylene glycols or polyols.
- auxiliaries such as nonionic surfactants, polyethylene glycols or polyols.
- lower alcohols such as ethanol and isopropanol can be used, and the amount of such lower alcohols in the liquid cationic surfactant preparation should be below 10% by weight for the reasons mentioned above.
- Suitable cationic surfactants for the compositions according to the invention are all customary substances, with cationic surfactants having textile-softening action being clearly preferred.
- compositions according to the invention may contain as cationic active substances with textile-softening action one or more cationic, textile-softening agents of the formulas X 1 XI or XII:
- the agents additionally contain nonionic surfactant (s) as the active substance.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
- Preferred ethnic oxyl lying alcohols include for example, C 2 - 1 4 alcohols containing 3 EO or 4 EO, n-alcohol with 7 EO, C 13 i5-alcohols with 3 EO, 5 EO, 7 EO or 8 EO , C 12-18 - alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of Ci2- 14 -alcohol with 3 EO and Ci 2- i 8 -alcohol with 5 EO.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- nonionic surfactants which can also be employed are alkyl glycosides of the general formula RO (G) x , in which R is a primary straight-chain or methyl-branched, especially methyl-branched, 2-position aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1, 2 to 1, 4.
- nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters.
- Nonionic surfactants of the amine oxide type for example N-coconut alkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
- the amount of this nonionic Surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half thereof.
- surfactants are polyhydroxy fatty acid amides of the formula XIII,
- RCO is an aliphatic acyl group having 6 to 22 carbon atoms
- R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms
- [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula XIV,
- R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms
- R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxy Alkyl radical having 1 to 8 carbon atoms
- Ci -4 -Alky ⁇ - or phenyl radicals are preferred
- [Z] is a linear polyhydroxyalkyl radical whose alkyl chain is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this radical.
- [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
- the ratio of anionic surfactant (s) to nonionic surfactant (s) is between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5, and most preferably between 5: 1 and 1: 2.
- containers according to the invention which contain surfactant (s), preferably anionic (s) and / or nonionic surfactant (s), in amounts of from 5 to 80% by weight, preferably from 7.5 to 70% by weight. %, particularly preferably from 10 to 60% by weight, in particular from 12.5 to 50% by weight, based in each case on the weight of the enclosed solids.
- Dishwashing compositions according to the invention therefore preferably contain only certain nonionic surfactants, which are described below.
- As surfactants only weakly foaming nonionic surfactants are usually used in automatic dishwashing detergents. Representatives from the groups of anionic, cationic or amphoteric surfactants, however, have less importance.
- nonionic surfactants are preferably alkoxylated, preferably ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol used, in in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as they are usually present in oxo-alcohol radicals.
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- Preferred ethnic oxyl lying alcohols include, for example, C 2- i 4 alcohols containing 3 EO or 4 EO, n-alcohol with 7 EO, C 3- I 5 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12 8 -I - alcohols containing 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 2 - 14 linear alcohol with 3 EO and C 2 i 8 alcohol containing 5 EO.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow rank ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- nonionic surfactants having a melting point above room temperature, preferably a nonionic surfactant having a melting point above 20 0 C.
- a nonionic surfactant having a melting point above 20 0 C Preferably used nonionic surfactants have melting points above 25 0 C.
- particularly preferably used nonionic surfactants have melting points between 25 and 6O 0 C, in particular between 26.6 and 43.3 ° C.
- Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas exhibit. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
- Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
- Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
- the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
- non-ionic surfactant is selected from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 6-2 alcohol), preferably a C-i ⁇ -alcohol and at least 12 moles, preferably at least 15 mol and in particular at least 20 mole Gained ethylene oxide.
- C 6-2 alcohol straight chain fatty alcohol having 16 to 20 carbon atoms
- C-i ⁇ -alcohol preferably a C-i ⁇ -alcohol and at least 12 moles, preferably at least 15 mol and in particular at least 20 mole Gained ethylene oxide.
- the so-called “narrow rank ethoxylates" are particularly preferred.
- the nonionic surfactant solid at room temperature preferably additionally has propylene oxide units in the molecule.
- such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
- Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
- the alcohol or alkylphenol part of such nonionic surfactant molecules preferably makes more than 30 Wt .-%, more preferably more than 50 wt .-% and in particular more than 70 wt .-% of the total molecular weight of such nonionic surfactants.
- More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
- Non-ionic surfactants that can be used with particular preference are available, for example, under the name Poly Tergent ® SLF-18 from Olin Chemicals.
- a further preferred surfactant can be defined by the formula
- R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof
- R 2 is a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x is values between 0.5 and 1, 5 and y is a value of at least 15.
- nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula
- R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5. If the value x ⁇ 2, each R 3 in the above formula may be different.
- R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
- R 3 H, -CH 3 or -CH 2 CH 3 are particularly preferred.
- Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
- each R 3 in the above formula may be different if x ⁇ 2.
- the alkylene oxide unit in the square bracket can be varied.
- the value 3 for x has been selected here by way of example and may well be greater, with the range of variation increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
- R 1 O [CH 2 CH (R 3 ) O] ⁇ CH 2 CH (OH) CH 2 OR 2 simplified.
- R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
- Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assume values of 6 to 15.
- Agents according to the invention can be used to increase the washing, or
- Cleaning performance contain enzymes, in principle, all the enzymes established in the art for this purpose can be used. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are basically of natural origin; Starting from the natural molecules, improved variants are available for use in detergents and cleaners, which are preferably used accordingly. Agents according to the invention preferably contain enzymes in total amounts of 1 ⁇ 10 -6 to 5 percent by weight based on active protein. The protein concentration can be determined by known methods, for example the BCA method (bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid) or the biuret method.
- BCA method bicinchoninic acid, 2,2'-biquinolyl-4,4'-dicarboxylic acid
- subtilisin type those of the subtilisin type are preferable.
- these are the subtilisins BPN 1 and Carlsberg, the protease PB92, the subtilisins 147 and 309, the alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and the subtilases, but not the subtilisins in the narrower sense Proteases TW3 and TW7.
- Subtilisin Carlsberg in a developed form under the trade names Alcalase ® from Novozymes A / S, Bagsvaerd, Denmark.
- subtilisins 147 and 309 are sold under the trade names Esperase ®, or Savinase ® from Novozymes. From the protease from Bacillus lentus DSM 5483 derived under the name BLAP ® variants are derived.
- proteases are, for example, under the trade names Durazym ®, relase ®, Everlase® ®, Nafizym, Natalase ®, Kannase® ® and Ovozymes ® from Novozymes, under the trade names Purafect ®, Purafect ® OxP and Properase.RTM ® by the company Genencor, that under the trade name Protosol® ® from Advanced Biochemicals Ltd., Thane, India, under the trade name Wuxi ® from Wuxi Snyder Bioproducts Ltd., China, under the trade names Proleather® ® and protease P ® by the company Amano Pharmaceuticals Ltd., Nagoya, Japan, and the enzyme available under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
- amylases which can be used according to the invention are the ⁇ -amylases from Bacillus licheniformis, from B. amyloliquefaciens or from ⁇ . stearothermophilus and their improved for use in detergents and cleaners further developments.
- the enzyme from B. licheniformis is available from Novozymes under the name Termamyl ® and from Genencor under the name Purastar® ® ST. Development products of this ⁇ - amylase are available from Novozymes under the trade names Duramyl ® and Termamyl ® ultra, from Genencor under the name Purastar® ® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase ®.
- the ⁇ -amylase of ⁇ . amyloliquefaciens is sold by Novozymes under the name BAN ®, and variants derived from the ⁇ -amylase from B. stearothermophilus under the names BSG ® and Novamyl ®, also from Novozymes.
- the ⁇ -amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948);
- fusion products of said molecules can be used.
- Another commercial product is, for example, the amylase LT® .
- compositions according to the invention may contain lipases or cutinases, in particular because of their triglyceride-cleaving activities, but also in order to generate in situ peracids from suitable precursors.
- lipases or cutinases include, for example, the lipases originally obtainable from Humicola lanuginosa (Thermomyces lanuginosus) or further developed, in particular those with the amino acid exchange D96L. They are for example marketed by Novozymes under the trade names Lipolase ®, Lipolase Ultra ®, LipoPrime® ®, Lipozyme® ® and Lipex ®.
- the cutinases can be used, which were originally isolated from Fusarium solani pisi and Humicola insolens.
- lipases are available from Amano under the designations Lipase CE ®, Lipase P ®, Lipase B ®, or lipase CES ®, Lipase AKG ®, Bacillis sp. Lipase® , Lipase AP® , Lipase M- AP® and Lipase AML® are available.
- Lipases or cutinases can be used, the initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii.
- Detergents according to the invention may contain cellulases, depending on the purpose, as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously supplement each other in terms of their various performance aspects.
- These performance aspects include in particular Contributions to the primary washing performance, to the secondary washing performance of the agent (anti-redeposition effect or grayness inhibition) and to avivage (tissue effect), up to the exercise of a "stone washed" effect.
- EG endoglucanase
- Novozymes under the trade name Celluzyme ®.
- the products Endolase® ® and Carezyme ® available also from Novozymes based on the 50 kD EG and 43 kD EG possible from H. insolens DSM 1800. Further commercial products of this company are Cellusoft® ® and Renozyme ®.
- the 20 kD EG cellulase from Melanocarpus available from AB Enzymes, Finland, under the trade names Ecostone® ® and Biotouch ®, can be used.
- Suitable mannanases are available, for example under the name Gamanase ® and Pektinex AR ® from Novozymes, under the name Rohapec ® B1 L from AB Enzymes and under the name Pyrolase® ® from Diversa Corp., San Diego, CA, USA , The obtained from B. subtilis .beta.-glucanase is available under the name Cereflo ® from Novozymes.
- detergents or cleaners according to the invention may contain oxidoreductases, for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or Manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases).
- oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or Manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases).
- oxidoreductases for example oxidases, oxygenases, catalases, peroxidases, such as halo, chloro, bromo, lignin, glucose or Manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases).
- organic, particularly preferably aromatic, compounds which interact with the enzymes in order to enhance the activity of the relevant oxidoreductases (enhancers) or to ensure the flow of electrons (mediators) at greatly varying redox potentials between the oxidizing enzymes and the soils.
- the enzymes used in agents of the invention are either originally from microorganisms, such as the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and / or are produced by biotechnological methods known per se by suitable microorganisms, such as transgenic expression hosts of the genera Bacillus or filamentous fungi.
- the purification of the relevant enzymes is conveniently carried out by conventional methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, exposure to chemicals, deodorization or suitable combinations of these steps.
- the agents of the invention may be added to the enzymes in any form known in the art. These include, for example, the solid preparations obtained by granulation, extrusion or lyophilization or, especially in the case of liquid or gel-form detergents, solutions of the enzymes, advantageously as concentrated as possible, sparing in water and / or added with stabilizers.
- the enzymes can be encapsulated for both the solid and liquid dosage forms, for example by spray drying or extrusion of the enzyme solution together with one, preferably natural Polymer or in the form of capsules, for example those in which the enzymes are entrapped as in a solidified gel or in those of the core-shell type, in which an enzyme-containing core with a water, air and / or chemical impermeable protective layer is covered.
- further active ingredients for example stabilizers, emulsifiers, pigments, bleaches or dyes, may additionally be applied.
- Such capsules are applied by methods known per se, for example by shaking or rolling granulation or in fluid-bed processes.
- such granules for example by applying polymeric film-forming agent, low in dust and storage stable due to the coating.
- a protein and / or enzyme contained in an agent according to the invention can be protected against damage, for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage.
- damage for example inactivation, denaturation or decomposition, for example by physical influences, oxidation or proteolytic cleavage, in particular during storage.
- inhibition of proteolysis is particularly preferred, especially if the agents also contain proteases.
- Compositions according to the invention may contain stabilizers for this purpose; the provision of such means constitutes a preferred embodiment of the present invention.
- One group of stabilizers are reversible protease inhibitors. Frequently, benzamidine hydrochloride, borax, boric acids, boronic acids or their salts or esters are used, including in particular derivatives with aromatic groups, such as ortho-.meta or para-substituted phenylboronic acids, or their salts or esters. Furthermore, peptide aldehydes, that is oligopeptides with reduced C-terminus are suitable. As a peptidic Protease inhibitors include ovomucoid and leupeptin; An additional option is the formation of fusion proteins from proteases and peptide inhibitors.
- enzyme stabilizers are aminoalcohols, such as up to Ci 2, such as succinic acid, other dicarboxylic acids or salts of said acids, mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids. End-capped fatty acid amide alkoxylates can also be used as stabilizers.
- Lower aliphatic alcohols but especially polyols such as glycerol, ethylene glycol, propylene glycol or sorbitol are other frequently used enzyme stabilizers.
- di-glycerol phosphate protects against denaturation by physical influences.
- calcium salts are used, such as calcium acetate or calcium formate and magnesium salts.
- Polyamide oligomers or polymeric compounds such as lignin, water-soluble vinyl copolymers or, such as cellulose ethers, acrylic polymers and / or polyamides stabilize the enzyme preparation, inter alia, against physical influences or pH fluctuations.
- Polyamine N-oxide containing polymers act simultaneously as enzyme stabilizers and as dye transfer inhibitors.
- Other polymeric stabilizers are the linear Cs-Ci 8 polyoxyalkylenes.
- Alkylpolyglycosides can stabilize in accordance with the also the enzymatic components of the agent according to the invention and even increase their performance.
- Crosslinked N-containing compounds perform a dual function as soil release agents and as enzyme stabilizers.
- Reducing agents and antioxidants such as sodium sulfite or reducing sugars enhance the stability of the enzymes to oxidative degradation.
- the effect of peptide-aldehyde stabilizers can be enhanced by combination with boric acid and / or boric acid derivatives and polyols and further enhanced according to the additional use of divalent cations, such as calcium ions.
- agents according to the invention are preferred which additionally contain enzymes and / or enzyme preparations, preferably solid and / or liquid protease preparations and / or amylase preparations, in amounts of from 1 to 5% by weight, preferably from 1.5 to 4.5 and in particular from 2 to 4 wt .-%, each based on the total agent.
- salts from the group of inorganic salts a wide number of different salts can be used.
- Preferred cations are the alkali and alkaline earth metals, preferred anions are the halides and sulfates. From a manufacturing point of view, the use of NaCl or MgCl 2 in the granules according to the invention is preferred.
- Fig. 4 packaging system with receiving means for portion cartridges on the
- Fig. 9 dispenser device with two separate funding and a
- Fig. 13 recording magazine with portion cartridges in the cross-sectional view
- Fig. 14 receiving blister with portion cartridges in the plan
- Fig. 15 packaging system with receiving means for portion cartridges in a vertically operated pump dispenser in the cross-sectional view
- Figs. 1 and 2 disclose the technically simplest embodiments of the invention.
- 1 shows a dispensing device 2 with a pump 6 integrated in the dispensing device 2.
- the pump 6 is coupled to an actuating means 5, which is designed as a hinged lever. Actuation of the actuating means 5 by pulling the free end of the lever toward the dispenser device causes a pumping stroke of the pump 6.
- the coupling of the actuating means 5 with the pump 6 is carried out by the person skilled in the art with the mechanical or electrical coupling means which are well known in the prior art.
- a suction line 10 is connected on the pressure side.
- the suction line 10 is connected to the riser 7 or passes into the riser 7.
- a terminal 8 is formed, which is communicatively connected to the suction line 10. As shown in Fig. 3, it is also possible that the port 8 is directly connected to the suction side of the pump 6.
- the end facing away from the suction line 10 of the terminal 8 opens into a receptacle 16, in which a portion cartridge 12 is horizontally inserted and coupled by means of the mouthpiece 23 to the terminal 8, so that in a pumping stroke of the pump 6 located in the portion cartridge 12 preparation 13 is discharged at least partially through the suction line 10 and the pressure line 9 to the environment.
- the delivery of the preparation 13 is essentially carried out by the negative pressure or flow in the suction line 10 which occurs during a pumping stroke, as a result of which the preparation 13 is entrained from the portioning cartridge 12.
- the amount of entrained preparation 13 per pump stroke of the pump 6 can be influenced in particular by the fluidic design of the connection 8 and the flow properties of the preparation 13.
- FIG. 2 shows the dispensing device 2 known from FIG. 1 with a receptacle 16 into which a portion cartridge 12 can be fixed vertically.
- the vertical positioning of the portion cartridge 12 has the advantage that at the terminal 8 preparation 13 is always pending, as long as the portion patron 12 is filled with a preparation 13. Further, the level, especially in a transparent configuration of the lateral surface of the cartridge 12 is easy to read, especially if the cartridge 12 has a corresponding scale on the lateral surface.
- the receptacle 16 and the port 8 is connected directly to the pump 6, so that the release of preparation 13 from the portion cartridge 12 not known from Fig. 1 by a Venturi effect of caused by the riser 7 conveyed fluid.
- a mixing of the preparations 13 and 4 is thus not already in the suction line 10, but only shortly before or in the pump 6. This may be advantageous in that as a result of a possible reaction of the two preparations 13 and 4, no unwanted reaction products can flow back through the riser 7 into the packaging 3.
- Unintentional mixing of the preparations 13 and 4 with one another can also be achieved by an arrangement of valves, as shown by way of example in FIG. 7.
- a check valve 18 is arranged in the upper region of the riser 7 that automatically blocks the passage of the conveyed preparation 4 counter to the conveying direction of the preparation 4 and thus prevents a backflow of already mixed with preparation 13 fluid into the packaging 3.
- a further check valve 17 in the connection 8 or in the portion cartridge 12, whereby additionally an unwanted mixing of the preparation 13 located in the portion cartridge 12 with the preparation 4 is prevented.
- the dispenser device 2 known from FIG. 1 or FIG. 2 can be placed in a sealed manner on a packaging means 3 and thus forms a corresponding packaging means system 1 for dispensing at least two preparations 13 and 4 at the same time.
- the packaging material 3 is formed as a bottle and the dispensing device 2 as a trigger spray head.
- the riser 7 of the dispensing device 2 passes through the filling volume of the bottle 3 and flows into the pumpable preparation 4. When pumping the preparation 4 is subsequently conveyed through the riser 7, the suction line 10, the pump 6 and the pressure line 9 in the area.
- the portion cartridges 12 are arranged in a receiving means 11 that is formed like a drum and rotatably arranged in the trigger spray head 2, that by rotation of the drum 11 each have a portion cartridge 12 is coupled to the suction side arranged connection 8. As shown in FIG. 4, it is also conceivable to couple the receiving means 11 or the portion cartridges 12 to a connection 8 arranged on the pressure side. In both cases, the mixing of the preparation 13 takes place by means of the negative pressure in the connection 8 caused by the flow in the suction line 10 or pressure line 9.
- the dispenser device 2 can also be provided for use with multi-chamber packages.
- the bottle 3 has a first chamber 3a and a second chamber 3b, wherein the first chamber 3a is filled with a first preparation 4a and the second chamber 3b is filled with a second preparation 4b.
- a first riser 7a and a second riser 7b are respectively immersed.
- the riser pipes 7a and 7b are communicatively connected to the suction pipe 10.
- FIG. 6 shows the dispensing device 2 with a rotatably mounted receiving drum 11 for portion cartridges 12 in the cross-sectional view.
- the dispenser device 2 has a receptacle 16, in which the receiving drum 12 can be positioned.
- axle elements 14 At the end faces of the receptacle 16 opposite pins are formed as axle elements 14, which form a rotatable connection with the bearings 15 of the portion cartridge 12.
- axle elements 14 it is also conceivable to arrange the axle elements 14 on the portion cartridge 11 and the bearings for receiving the axle elements 14 on the receptacle 16 of the dispensing device 2.
- FIG. 9 A further embodiment of the dispenser device 2 according to the invention is shown in FIG. 9.
- the dispenser device 2 in this case has two pumps 6a, 6b on, wherein the first pump 6a is connected via a first suction line 10a to the terminal 8 and the second pump 6b via the second suction line 10b communicating with the riser 7.
- Both pumps 6a, 6b are coupled to the actuating element 5.
- On the pressure side of the pumps 6a, 6b open the pressure lines 9a, 9b in a common mixing chamber 27, in which the fluid streams from the portion cartridge 12 and the packaging 3 are merged.
- a pressure line 9 connects the mixing chamber 27 with the environment.
- a preferred embodiment of a receiving means 11 for portion cartridges 12 is the revolver-type receiving drum shown in FIG.
- the receiving drum 11 is a substantially cylindrical body with cartridge chambers 25 arranged concentrically around the bearing 15 for receiving the portion cartridges 12.
- the outer circumferential surface of the receiving drum can have transparent regions 28 or recesses.
- FIG. 11 shows a portion cartridge 12 inserted into the receiving drum 11, which is completely filled with a preparation 13.
- the portion cartridge 12 is detachably connected to the take-up drum 11.
- the cartridge 12 can be fixed positively and / or non-positively in the cartridge chamber 25 whereby a replacement of a spent portion cartridge 12 is made possible.
- the portion cartridge has an end face on a mouthpiece 23, through which the cartridge 12 can be coupled to the terminal 8 of the dispenser.
- a vent valve is provided on the mouthpiece opposite end side of the portion cartridge 12.
- the opening of the mouthpiece 23 is sealed by a closure 24.
- the closure may for example be formed as a membrane which is configured such that it is destroyed by the negative pressure generated by the pump 6 in the connection 8 and the preparation 13 is conveyed out of the portion cartridge 12. It is also conceivable to carry out the closure 24 as a silicone valve that is opened by the negative pressure mentioned above and that closes again when normal pressure is reached.
- portion cartridges 12 are formed by cavities in the receiving drum 11 and thus insoluble connected to the receiving drum 11.
- the portion cartridges are sealed by a closure 24.
- the receiving drum 11 may have pressure compensation valves 22.
- FIG. 12 Another embodiment of the receiving means 11 for portion cartridges 12 is shown in FIG. 12.
- the portion cartridges 12 are not, as in the case of the receiving drum known from FIG. 10, arranged on a circular path arranged concentrically with respect to the axis of rotation, but are positioned one above the other like a magazine.
- the receiving means 11, as shown in FIG. 14, as a blister pack, the portion cartridges 12 being configured as cavities of the blister.
- a perforation 13 may be provided at the edge of the blister pack 13, in which, for example, a gear of a transport and guide mechanism of the dispenser 2 engages the actuation of the actuating element 5, the release of the contents of a Blisterkavmaschine 12 and the transport of a unused cavity of the blister 11 causes the connection 8.
- Fig. 15 shows a packaging system 1 with a receiving drum 11 for portion cartridges 12 a vertically operated pump dispenser 5. The pump is not driven unlike the dispenser shown in FIG. 1 is not by a substantially horizontal but by a vertical actuation kinematics.
- dispenser devices and configurations are known, for example, in soap dispensers or foam dispensers in which the product delivery is effected by a vertical depression of the dispenser head.
- the receiving drum 11 for the portion cartridges 12 is in this case arranged vertically rotatable in the dispenser head 5 and moves with the dispenser head 5 during its operation.
- FIG. 16 shows a dispenser device 2 according to the invention for an aerosol package.
- the pressurized by a propellant with a preparation 4 container 3 is separated by a valve 17 from the environment.
- the valve 17 is opened, so that the pressurized preparation 4 is discharged to the environment.
- FIG. 17 An example of a corresponding configuration is shown in FIG. 17, in which the dispenser device known from FIG. 1 or FIG. 2 is arranged on a preferably elastically deformable container 3.
- the container 3 is designed so that by compressing the lateral surface, which is indicated by the arrows in the figure, a pressure in the container 3 is formed, which promotes the preparation 4 through the riser 7 and the pressure line 7 into the environment and at least one partial delivery at a portioning cartridge 12 fixed in the receptacle 16 and coupled to the connection 8 the preparation 13 in the fluid flow of the pressure line 9 causes.
- the dispenser device 1 overhead for example, to apply the preparations 3,14 under the edge of a toilet, that riser 7 can also be designed short, ie it does not protrude substantially from the dispenser 2 in the packaging 3 into it.
Abstract
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL07723139T PL2032268T3 (en) | 2006-06-23 | 2007-03-09 | Dispensing device for dispensing a plurality of different preparations |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE102006029345A DE102006029345A1 (en) | 2006-06-23 | 2006-06-23 | Dispensing device for dispensing a plurality of mutually different preparations |
PCT/EP2007/002057 WO2007147457A1 (en) | 2006-06-23 | 2007-03-09 | Dispensing device for dispensing a plurality of different preparations |
Publications (2)
Publication Number | Publication Date |
---|---|
EP2032268A1 true EP2032268A1 (en) | 2009-03-11 |
EP2032268B1 EP2032268B1 (en) | 2013-01-09 |
Family
ID=38038590
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP07723139A Not-in-force EP2032268B1 (en) | 2006-06-23 | 2007-03-09 | Dispensing device for dispensing a plurality of different preparations |
Country Status (6)
Country | Link |
---|---|
US (1) | US8348098B2 (en) |
EP (1) | EP2032268B1 (en) |
DE (1) | DE102006029345A1 (en) |
ES (1) | ES2399922T3 (en) |
PL (1) | PL2032268T3 (en) |
WO (1) | WO2007147457A1 (en) |
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DE102011076561B4 (en) * | 2011-05-26 | 2018-12-13 | Henkel Ag & Co. Kgaa | Device for mixing and dispensing multicomponent hair cosmetic preparations and associated portion pack |
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US9038819B2 (en) | 2012-06-22 | 2015-05-26 | L&F Innoventions, LLC | Wearable cleaning articles and container |
US20140054323A1 (en) | 2012-08-23 | 2014-02-27 | Gojo Industries, Inc. | Horizontal pumps, refill units and foam dispensers with integral air compressors |
CN104936707B (en) | 2012-08-31 | 2018-11-02 | 约翰逊父子公司 | Fluid application system |
US9655479B2 (en) | 2013-01-15 | 2017-05-23 | Gojo Industries, Inc. | Two-liquid dispensing systems, refills and two-liquid pumps |
US10667540B2 (en) | 2013-07-15 | 2020-06-02 | Societe Des Produits Nestle S.A. | Self-foaming ready to drink beverages |
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AU2013407260B2 (en) * | 2013-12-11 | 2017-08-10 | Colgate-Palmolive Company | Dispensing container |
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AU2015269207B2 (en) | 2014-06-06 | 2017-10-05 | S.C. Johnson & Son. Inc. | A fluid dispensing system and methods relating thereto |
US11033692B2 (en) * | 2015-04-15 | 2021-06-15 | Philip Morris Products S.A. | Flavoring element for an inhalation device |
US9867507B2 (en) * | 2015-10-27 | 2018-01-16 | Colgate-Palmolive Company | Dispenser |
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2007
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- 2007-03-09 WO PCT/EP2007/002057 patent/WO2007147457A1/en active Application Filing
- 2007-03-09 ES ES07723139T patent/ES2399922T3/en active Active
- 2007-03-09 US US12/306,304 patent/US8348098B2/en not_active Expired - Fee Related
- 2007-03-09 EP EP07723139A patent/EP2032268B1/en not_active Not-in-force
Non-Patent Citations (1)
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Also Published As
Publication number | Publication date |
---|---|
US8348098B2 (en) | 2013-01-08 |
PL2032268T3 (en) | 2013-06-28 |
DE102006029345A1 (en) | 2007-12-27 |
WO2007147457A1 (en) | 2007-12-27 |
EP2032268B1 (en) | 2013-01-09 |
ES2399922T3 (en) | 2013-04-04 |
US20090277928A1 (en) | 2009-11-12 |
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