US20100025399A1

US20100025399A1 - Packaging unit

Info

Publication number: US20100025399A1
Application number: US12/160,825
Authority: US
Inventors: Hans-Georg Mühlhausen; Markus Nachtsheim
Original assignee: Henkel AG and Co KGaA
Current assignee: Henkel AG and Co KGaA
Priority date: 2006-01-19
Filing date: 2006-11-08
Publication date: 2010-02-04
Also published as: DE502006008584D1; ATE492483T1; DE102006002864A1; EP1973791A1; EP1973791B1; WO2007082566A1; ES2357149T3

Abstract

A packaging unit has a container (1) for holding a product, a closure (2) and an opening or closure cylinder (14) for dispensing product from the container (1). The closure (2) closes the opening (14). The packaging unit has at least one receiving means (3), for a plurality of additive portions (6, 11, 21) of in each case less than 50 ml, which may be blister packs. The additive (16) held in the additive portions (6, 11, 21) may be one or more aromatic, colorant or surfactant. The receiving means (3) for additive portions (6, 11, 21) can be fixed releasably to the packaging unit.

Description

The invention relates to a package consisting of a container for products and a device arranged on this container for accommodating additive portions.

BACKGROUND OF THE INVENTION

There has long been a requirement to be able to individualize products for specific customer requirements or to allow customers to individualize them to a certain extent. One particularly suitable medium for individualizing a product is its packaging, as this forms the immediate interface between consumer and product.
It is thus desirable to combine means for individualizing or further functionalizing a product directly with the package for a product.
In particular when perfuming products such as for example cleaning agents, detergents and the like, it is at present still conventional to sell the entire sales unit with one specific fragrance. However, a user often wants a cleaning product to release a different fragrance for different areas of application. It is, for example, desirable for a cleaning agent to emit a more intense fragrance for the toilet area than in a living area, where intense fragrances often tend to be considered troublesome. It has thus hitherto been necessary to use a plurality of special cleaning products having the corresponding fragrances, despite the preparations with a cleaning action being in each case identical or at least very similar.
Specifically in the case of very aggressive cleaning preparations the problem furthermore arises that the aggressive cleaning components also break down the fragrances present in the preparations, resulting in only short storage stability.
In addition to the preparation of individually perfumed products, there is a further requirement for a product package to be designed such that the fragrance of the product contained in the package may be olfactometrically perceptible.
Finally, packages are also increasingly being additionally functionalized by providing fragrance-emitting agents on the package which release a specific fragrance into the surroundings of the package and so additionally assume the function of a room fragrancing product.
Blister packs are conventionally used, for example in relation to providing pharmaceutical preparations, for ensuring that products are individually portioned as required. In such cases, individual doses of pharmaceutical preparations, for example in the form of tablets, are in each case packaged in one compartment of a blister pack.
Such a blister pack conventionally consists of a first flat element, in which a plurality of individual, conventionally well-shaped, separate cavities are formed for accommodating product doses and a second flat element which is joined to the first flat element over the surface thereof and closes the cavities.
The first flat element, in which the cavities are made, conventionally consists of a piece of plastics film in which the cavities are shaped, for example by thermoforming.
The second flat element which closes the cavities consists of a material which is sufficiently strong to avoid unintentional opening, but which can be opened by the application of appropriate pressure, for example by pressing with the thumb or tearing the film/foil with a fingernail.
Exerting pressure on a compartment of the blister pack results in pressure being exerted on the product located in the compartment, the product then ultimately puncturing the lower film/foil.
A blister pack may also be embodied such that the second flat element which closes the cavities is made stronger such that the well-shaped cavities of the first flat element are opened by the applied pressure and the second flat element which closes the cavities remains undamaged
DE4239082 discloses the use of such a blister pack for fragrance-emitting substances. The blister pack here consists of a plurality of compartments filled with fragrance, the reverse side of the blister pack being provided with an adhesive layer which can be stuck onto a garment or human skin.
A disadvantageous feature of this solution is that the blister pack cannot be non-detachably fastened to a carrier object. The blister pack may accordingly always be completely detached from the carrier object, such as for example human skin. However, in particular for sales packages this is not desirable and is disadvantageous in that a blister pack can fall off unintentionally, for example due to adhesive failure, from the sales package or, with criminal intent, be removed from the sales container.
Moreover, the product in the well-shaped indentations of the blister pack cannot be released by the destruction of the lower film/foil, since, according to the teaching of DE4239082, this lower film/foil is adhesively bonded over its entire surface to the carrier object. Thus, when a well-shaped cavity is destroyed to release a product portion, it is not possible to avoid this product coming into contact with the user's hands. However, for many applications, such as for example when apportioning cleaning substances or highly concentrated fragrance oils, this is unwanted.
WO2004/084660 discloses arranging fragrance-emitting substances in a closure flap of a container. Fragrance-emitting substances are here arranged in a chamber of the container closure, said chamber being sealed with a film/foil which may be removed in order to use the cap of the room fragrancer, such that fragrance may be released from the closure flap into the surroundings. A disadvantageous feature of this solution is the comparatively large size of the closure which is thus inconvenient for the consumer to handle. Because the internal volume of the closure is virtually completely filled with a fragrance, there is virtually no further dispensing volume available, such that the closure cannot in general be used as a dispensing unit, as is the case for example for rinse conditioner or floor cleaner closures. Due to its necessarily enlarged size in comparison with conventional closures, the storage space requirements for containers equipped in this way are also increased, which inevitably also results in increased logistics costs.
CA983437 discloses a container for medical applications, in which it is necessary to take a prescribed dose of a tablet or capsule in conjunction with a liquid. To this end, a container according to CA983437 comprises means for accommodating the individual doses on the outer wall of the container. These are indentations in the outer wall, into which the individual doses may be inserted or placed. The doses located in the indentations may then be fastened in the indentations with an adhesive tape. A dose can then be removed by lifting and peeling away the adhesive tape, such that a dose is released and may be removed from the indentation in the outer wall of the container.
This solution has the disadvantage that producing such a container is costly and technically complex. Furthermore, large areas are required, which considerably limits space for promotional and/or descriptive labels. Moreover, the overall esthetic impression of the container is appreciably impaired thereby. Another disadvantage of this solution is that preparations in paste or gel form cannot be dispensed and removed.

OBJECT OF THE INVENTION

The object of the present invention is accordingly to provide a package which may be produced inexpensively and which makes it possible to provide individually packaged, portionable additive units on a container in a simple and easily usable manner.
The object is achieved according to the invention by a packaging unit comprising a container for accommodating a product, a closure and an opening closable by the closure for discharging the product from the container, wherein the packaging unit comprises at least one receiving means for a plurality of additive portions of in each case less than 50 ml, the additive comprising at least one substance from the group of fragrances, dyes or surfactants and the receiving means for the additive portions being detachably fastenable to the packaging unit.
For the purposes of the present application, a packaging unit is taken to mean the entire assembly of container, container opening and closure.
The receiving means for a plurality of product portions may, for example, take the form of a tearable package, cushion package, shrink package, see-through package, blister package, bubble package, contour package, push-through package, skin package, stretch package, strip package, vacuum package, combination package, multicomponent package, multipart package, portion package, consolidated package or multipackage.
In particular, the receiving means may also take the form of a substantially dimensionally stable body to which individual additive portions may be fastened.
The additive portions are in each case enclosed at least in part by a flexible or dimensionally stable container in such a way that the additive disposed in the portion is not released unintentionally. The additive portions may be joined detachably or fixedly to the receiving means.
The additive portions may be formed, for example, by a substantially flexible blister pack, bubble pack or contour pack, which are then joined in suitable manner to the receiving means for fastening to the container.
It is also feasible to shape the additive portions as a dimensionally stable container such as for example a closable cup or vial, which may then preferably be fastened detachably in the packaging unit.
The receiving means for the additive portions may be fastened to the container using detachable connections deemed suitable by a person skilled in the art. In particular, fastening to the container may be effected frictionally, interlockingly and/or by material bonding for example by one or more of the connection types from the group comprising snap-in connections, hook-and-loop connections, press connections, melt connections, adhesive connections, welded connections, brazed connections, screw connections, keyed connections, clamped connections or rebound connections.
The contents of the additive portions may consist for example of one or more identical or different products such as for example fragrances, cleaning substances, dyes, surfactants, fungicides, enzymes, hygroscopic substances and the like.
According to one particular embodiment of the invention, it is possible for the container for the additive portions to consist at least in part of a material which allows release of a product enclosed in the additive portions into the surroundings by diffusion. In addition, in this case the additive portion may be covered by an additional protective film which initially prevents the product from being released into the surroundings. The protective film may be removed from an additive portion for example by tearing or rubbing, such that additive product may then be released into the surroundings.
The invention is particularly suitable for dimensionally stable containers such as cups, cans, buckets, barrels, bottles, jerricans, pots, cartons, drums or tubes, but may also be used for flexible containers such as pouches or bags.
Cans may in particular include ironed cans, ring-pull cans, friction top cans, necked-in cans, open-top cans, open-top vent-hole cans, interlocked sideseam cans, drawn cans, piston cans, convolute cans, tear-strip cans, beaded cans, lidded tins or stepped-rim cans.
Barrels may be selected from the group comprising belly barrels, staved barrels, tight barrels, oil drums, semi-tight barrels, dry casks, trundle rolling hoop drums, heavy casks, channel drums or rolling channel drums.
A bottle may for example take the form of an aerosol bottle, see-through bottle, drinks bottle, in particular a beer bottle, bocksbeutel, codd-neck bottle, German-type bottle, steinie bottle, stubby bottle, Vichy bottle, wide-necked bottle, as well as a meplat bottle, squeezy bottle, dropper bottle, packaging bottle such as for instance a perfume bottle.
For the purposes of the present application cartons are in particular taken to mean folding cartons such as for example erectable cartons, pull-through cartons, folding bottom cartons, folder cartons, folding cartons with internal liner, two-piece staple-joined cartons, folding tube and slide cartons, interlocking bottom cartons, folding telescope cartons and tray lid cartons, window cartons, hinge-cover cartons such as for example coated hinge-cover cartons or knurled hinge-cover cartons, and flap-lid cartons, double cover cartons, tube and slide cartons, chip boxes, telescope cartons, carrying cartons or shipping cartons.
The container opening may in particular comprise a push-in flap, collar, in particular external collar, as well as a mouthpiece or orifice or valve carrier, cork mouthpiece, crown cork mouthpiece, hole mouthpiece, threaded mouthpiece, sprayer mouthpiece, plughole or bunghole.
The closure may comprise a closing means from the group of lids, tear-off lids, roll-off lids, ring-pull lids, hooded lids, friction tops, tuck-in tops, open-top lids, film/foil lids, flap lids, cam lids, bayonet closure lids, grooved lids, hinged lids, sliding lids, insertion lids, snap lids, clamp lids, screw lids, snap-fit lids, overlap lids, tuck-in tongues, flaps, external flaps, internal flaps, closing flaps, keystones, plugs, bungs, screw bungs, stoppers, capped stoppers, ground glass stoppers, closing caps, tube caps, crown corks, screw caps, valve protection caps, closing capsules, bottle capsules, tear-off capsules, crimped capsules and spigots.
The closure and/or the opening of the container may optionally comprise dispensing and discharge aids such as for instance an aerosol valve, pourer, spray cap, spray head, atomizer, dispensing device, dispensing cap, dispensing mouthpiece or a dropper.
For the purposes of the present application, an additive is taken to mean a substance or mixture of substances which, by mixing with the product present in the container, is suitable for bringing about or influencing, in particular improving, producing, emphasizing or attenuating, a property of the product, for accelerating or retarding a process which proceeds over time, or for initiating, inhibiting or catalyzing a reaction. An additive should furthermore also be taken to mean a substance or mixture of substances which is suitable for bringing about or influencing a property of the container, in particular fragrance and/or active ingredient release, adsorption or absorption on or in the container.
The additive may for example comprise one or more substances from the group of fragrances, bleaching agents, cleaning substances, solvents, surfactants, dyes, enzymes, hygroscopic substances, flame retardants, curing agents, levelling agents, wetting agents, dispersants, foaming agents, defoamers, deaerating agents, corrosion protection agents, biocides, water softeners, preservatives, emulsifiers, stabilizers, vitamins, minerals and the like.
Thanks to the spatial separation achievable with the invention between certain added active substances (fragrance, enzymes, bleach etc.) and the actual product and the portionable additive units arranged immediately on the container, the product present in the container may be formulated in a straightforward manner.
The additive portions of the receiving means may contain identical or different products. It would accordingly be conceivable, for example, to arrange substances having different fragrances in the additive portions in order to permit the container contents or the container itself to be differently perfumed. For example, when using a cleaning liquid with a neutral fragrance which is first mixed with water to obtain a wipe-down preparation, it is possible to apportion a different fragrance from the receiving means for the additive portions each time a wipe-down solution is prepared. On the one hand, this prevents olfactometric adaptation to one specific fragrance, while on the other hand a fragrance can be selected depending on the requirements of a specific room in which the product is used (toilet, living room, kitchen). It is then no longer necessary to use several specially perfumed cleaning substances for this purpose, an outcome which is also desirable from an environmental and resource conservation aspect.
Another substantial advantage of the invention is the simple and thus inexpensive manner in which it may be produced. It is accordingly possible to have the receiving means for the additive portions manufactured completely independently from a container. A receiving means for the additive portions is subsequently fastened to the container in accordance with the disclosed teaching of the invention.
The receiving means for the additive portions is detachable by the consumer at any time, whereby according to a preferred embodiment of the invention the receiving means for the additive portions may also be fastened to articles outside the product container.
It is accordingly, for example, also possible, once the additive portions have been completely consumed, to remove them from the container and to arrange a new unconsumed receiving means for additive portions on the container.
Polymeric Support Material
According to a preferred embodiment of the invention, the active additive substances are bound to or in a polymeric support material. Fragrances are particularly preferably bound in or to a polymeric support material.
Polymers or polymer blends which are suitable for the fragrance-containing particles are in general any such which meet the above-stated criteria with regard to melting or softening temperature. Fragrance-releasing systems which are preferred for the purposes of the present application are characterized in that the polymeric support material contains at least one substance from the group comprising ethylene/vinyl acetate copolymers, low or high density polyethylene (LDPE, HDPE) or mixtures thereof, polypropylene, polyethylene/polypropylene copolymers, polyether/polyamide block copolymers, styrene/butadiene (block) copolymers, styrene/isoprene (block) copolymers, styrene/ethylene/butylene copolymers acrylonitrile/butadiene/styrene copolymers, acrylonitrile/butadiene copolymers, polyether esters, polyisobutene, polyisoprene, ethylene/ethyl acrylate copolymers, polyamides, polycarbonate, polyesters, polyacrylonitrile, polymethyl methacrylate, polyurethanes, polyvinyl alcohols.
Polyethylene (PE) is a collective term for polyolefin polymers comprising groupings of the type
CH₂—CH₂
as a characteristic base unit of the polymer chain. Polyethylenes are generally produced by polymerizing ethylene by two fundamentally different methods, the high pressure process and the low pressure process. Accordingly, the resultant products are frequently respectively referred to as high pressure polyethylenes or low pressure polyethylenes; they differ mainly with regard to their degree of branching and consequently in terms of their degree of crystallinity and density. Both processes can be performed as solution polymerization, emulsion polymerization or gas phase polymerization.
The high pressure process yields branched polyethylenes of low density (approx. 0.915-0.935 g/cm³) and degrees of crystallinity of approx. 40-50%, which are known as LDPE (low density polyethylene) grades. Products of a higher molar mass and consequently improved strength and stretchability are known by the abbreviation HMW-LDPE (HMW=high molecular weight). By copolymerizing ethylene with longer-chain olefins, in particular with butene and octene, it is possible to reduce the pronounced degree of branching of the polyethylenes produced by the high pressure process; the copolymers are designated LLD-PE (linear low density polyethylenes).
The macromolecules of polyethylenes produced by the low pressure process are largely linear and unbranched. These polyethylenes, abbreviated HDPE (high density polyethylene), have a degree of crystallinity of 60-80% and a density of approx. 0.94-0.965 g/cm³. They are offered for sale as products with high or ultrahigh molar mass (approx. 200,000-5,000,000 g/mol or 3,000,000-6,000,000 g/mol) under the abbreviations HD-HMW-PE or UHMW-HD-PE respectively. Medium density products (MDPE) prepared from mixtures of low and high polyethylenes are also commercially obtainable. Linear polyethylenes with densities of <0.918 g/cm³(VLD-PE=very low density polyethylenes) are only slowly gaining commercial significance.
Polyethylenes have very low water vapor permeability, while the diffusion of gases and aroma substances and essential substances through polyethylenes is relatively high. Mechanical characteristics are highly dependent on the molecular size and structure of the polyethylenes. In general, the degree of crystallinity and density of polyethylenes increase as the degree of branching falls and the side chains shorten. Shear modulus, hardness, yield point and melting range rise with density, while shock resistance, transparency, swellability and solubility fall. At constant density of the polyethylenes, tensile strength, elongation, shock resistance, impact strength and creep strength increase with a rising molar mass. Depending on process control during polymerization, it is possible to obtain products having characteristics similar to paraffin wax (M_rof around 2000) and products having extreme toughness (M_rgreater than 1 million).
The various grades of polyethylene may be processed by any methods conventional for thermoplastics.
Polypropylene (PP) is the name for thermoplastic polymers of propylene of the general formula:
—(CH₂—CH[CH₃])_n.
The basis for producing polypropylene was Natta's development of the stereospecific polymerization process for propylene in the gas phase or in suspension. This is initiated not only with Ziegler-Natta catalysts but, increasingly, also by metallocene catalysts and gives rise either to highly crystalline isotactic or to less crystalline syndiotactic or amorphous atactic polypropylenes.
Polypropylene is distinguished by elevated hardness, resilience, rigidity and heat resistance. Articles made from polypropylene may even briefly be heated to 140° C. At temperatures of below 0° C., a certain degree of embrittlement of the polypropylene occurs, but this may be shifted to substantially lower temperature ranges by copolymerizing propylene with ethylene (EPM, EPDM). In general, the impact strength of polypropylene may be improved by elastomer modification. In common with all polyolefins, chemical resistance is good. The mechanical properties of polypropylenes may be improved by reinforcement with talcum, chalk, wood flour or glass fibers. Polypropylenes are even more susceptible to oxidation and sensitive to light than PE, for which reason it is necessary to add stabilizers (antioxidants, light stabilizers, UV absorbers).
Polyether is a term used in macromolecular chemistry to describe polymers whose organic repeat units are joined together by ether functions (C—O—C). According to this definition, numerous structurally very different polymers belong among polyethers, for example polyalkylene glycols (polyethylene glycols, polypropylene glycols and polyepichlorohydrins) as polymers of 1,2-epoxides, epoxy resins, polytetrahydrofurans (polytetramethylene glycols), polyoxetanes, polyphenylene ethers (c.f. polyaryl ethers) or polyetherether ketones (c.f. polyether ketones). Polymers with lateral ether groups, such as inter alia cellulose ethers, starch ethers and vinyl ether polymers, are not classed among polyethers.
The group of polyethers furthermore also includes functionalized polyethers, i.e. compounds with a polyether skeleton which bear still further functional groups, such as for example carboxy, epoxy, allyl or amino groups etc., attached laterally to their main chains. Block copolymers of polyethers and polyamides (polyether amides or polyether block amides, PEBA) have many uses.
Polyamides (PA) is the name given to polymers whose building blocks are joined together by amide bonds (—NH—CO—). Naturally occurring polyamides are peptides, polypeptides and proteins (e.g. protein, wool, silk). With only a few exceptions, synthetic polyamides are thermoplastic, chain-like polymers, some of which have gained considerable industrial significance as synthetic fibers and materials. Depending on their chemical structure, “homopolyamides” may be divided into two groups, the aminocarboxylic acid types (AC) and the diaminodicarboxylic acid types (AA-CC; A here denoting amino groups and C carboxy groups). The former are produced from only one monomer, for example by polycondensation of an w-aminocarboxylic acid (1) (polyamino acids) or by ring-opening polymerization of cyclic amides (lactams) (2).
In addition to homopolyamides, some co-polyamides have gained significance. It is conventional to state the composition in qualitative and quantitative terms, e.g. PA 66/6 (80:20) for polyamides produced from 1,6-hexanediamine, adipic acid and ε-caprolactam in a molar ratio of 80:80:20. Due to their particular characteristics, polyamides which exclusively contain aromatic residues (for example those from p-phenylenediamine and terephthalic acid) are known generically as aramids or polyaramids (for example Nomex®).
The most frequently used types of polyamides (primarily PA 6 and PA 66) consist of unbranched chains with average molar masses of 15,000 to 50,000 g/mol. In a solid state they are partially crystalline and have degrees of crystallization of 30-60%. Polyamides prepared from building blocks with side chains or co-polyamides prepared from very different components, which are largely amorphous, are an exception. In contrast with the generally milky-opaque, partially crystalline polyamides, these are almost crystal clear. The softening temperatures of the commonest homopolyamides are between 200 and 260° C. (PA 6: 215-220° C., PA 66: 255-260° C.).
Polyester is the collective term for polymers whose building blocks are joined together by ester bonds (—CO—O—). Depending on their chemical structure, “homopolyesters” may be divided into two groups, hydroxycarboxylic acid types (AB polyesters) and dihydroxydicarboxylic acid types (AA-BB polyesters). The former are produced from only one monomer by for example polycondensation of an w-hydroxycarboxylic acid 1 or by ring-opening polymerization of cyclic esters (lactones) 2.
Branched and crosslinked polyesters are obtained from the polycondensation of tri- or polyhydric alcohols with polyfunctional carboxylic acids. Polycarbonates (polyesters of carbonic acid) are generally also included among polyesters. AB type polyesters (I) are inter alia polyglycolic acid, polylactic acid, polyhydroxybutyric acid [poly(3-hydroxybutyric acid), poly(ε-caprolactone)s and polyhydroxybenzoic acids.
Purely aliphatic AA-BB type polyesters (II) are polycondensation products prepared from aliphatic diols and dicarboxylic acids, which are used inter alia as products with terminal hydroxy groups (as polydiols) for producing polyesterpolyurethanes [for example polytetramethyleneadipate]. In quantity terms, AA-BB type polyesters prepared from aliphatic diols and aromatic dicarboxylic acids are of the greatest industrial significance, in particular polyalkylene terephthalates, with polyethylene terephthalate (PET), polybutylene terephthalate (PBT) and poly(1,4-cyclohexanedimethylene terephthalate)s (PCDT) being the most important representatives. The properties of these types of polyesters may be widely varied and adapted to different areas of application by joint use of other aromatic dicarboxylic acids (for example isophthalic acid) or by using diol mixtures during polycondensation.
Purely aromatic polyesters are polyarylates which inter alia include poly(4-hydroxybenzoic acid). In addition to the previously stated saturated polyesters, it is also possible to produce unsaturated polyesters from unsaturated dicarboxylic acids, which have gained industrial significance as polyester resins, in particular as unsaturated polyester resins (UP resins).
Polyesters are generally thermoplastics. Products based on aromatic dicarboxylic acids have pronounced material properties. Purely aromatic polyarylates are distinguished by elevated thermal stability.
Polyurethanes (PU) is the name given to polymers having macromolecules with repeat units linked together by urethane groups —NH—CO—O—. Polyurethanes are generally obtained by polyaddition from dihydric or more highly hydric alcohols and isocyanates.
Depending on the starting materials selected and their stoichiometric ratio, polyurethanes with very different mechanical characteristics are obtained which are used as constituents of adhesives and coating materials (polyurethane resins), as ionomers, as thermoplastic material for bearing parts, rollers, tires, rolls and as elastomers of greater or lesser hardness in fiber form (elastomeric fibers, abbreviated to PUE for these elastane or spandex fibers) or as polyether urethane or polyester urethane rubber (EU or AU).
Polyurethane foams are obtained on polyaddition if water and/or carboxylic acids are present since these react with the isocyanates and liberate carbon dioxide which has a blowing and foam-forming action. Flexible polyurethane foams are obtained when using polyalkylene glycol ethers as the diols and water as a reaction component, while rigid polyurethane foams and structural or integral foams are obtained with polyols and CFC blowing gases (especially R11). Auxiliary materials which are additionally required are here for example catalysts, emulsifiers, foam stabilizers (especially polysiloxane/polyether copolymers), pigments, antioxidants and flame retardants. RIM (reaction injection molding) was developed in the 1970s to allow the production even of complicated shaped articles from polyurethane foam. The RIM process is based on rapid apportioning and mixing of the components, injection of the reactive mixture into the mold and rapid curing; the cycle time amounts to only a few minutes. RIM is used to produce, among other things, automotive body parts, shoe soles, window profiles and television casings.
Polyvinyl alcohols (PVAL, occasionally also PVOH) is the name given to polymers of the general structure
which also contain small proportions (approx. 2%) of structural units of the type
Conventional commercial polyvinyl alcohols are offered for sale as white-yellowish powders or granules with degrees of polymerization in the range from approx. 100 to 2500 (molar masses of approx. 4000 to 100,000 g/mol). Manufacturers differentiate polyvinyl alcohols by stating the degree of polymerization of the starting polymer, the degree of hydrolysis, the saponification value or the solution viscosity.
Depending on their degree of hydrolysis, polyvinyl alcohols are soluble in water and less strongly polar organic solvents (formamide, dimethylformamide, dimethyl sulfoxide); they are not attacked by (chlorinated) hydrocarbons, esters, fats and oils. Polyvinyl alcohols are classed as toxicologically safe and are at least partially biodegradable. Water solubility can be reduced by post-treatment with aldehydes (acetalization), by complexation with Ni or Cu salts or by treatment with dichromates, boric acid or borax. Coatings of polyvinyl alcohol are largely impenetrable by gases such as oxygen, nitrogen, helium, hydrogen, carbon dioxide, but allow water vapor to pass through.
Polyvinyl alcohols of a specific molecular weight range are preferably used as materials for the containers, wherein it is preferred according to the invention for the water-soluble or water-dispersible container to comprise a polyvinyl alcohol having a molecular weight in the range from 10,000 to 100,000 gmol⁻¹, preferably from 11,000 to 90,000 gmol⁻¹, particularly preferably from 12,000 to 80,000 gmol⁻¹and in particular from 13,000 to 70,000 gmol⁻¹.
In one particularly preferred embodiment of the present invention, the polymeric support material of the particles consists at least in part of ethylene/vinyl acetate copolymer. The present application accordingly preferably also provides a fragrance release system, wherein the polymeric support material contains at least 10 wt. %, preferably at least 30 wt. %, particularly preferably at least 70 wt. % of ethylene/vinyl acetate copolymer, preferably is completely produced from ethylene/vinyl acetate copolymer.
Ethylene/vinyl acetate copolymer is the name given to copolymers of ethylene and vinyl acetate. This polymer is in principle produced in a process comparable to that for the production of low density polyethylene (LDPE). As the proportion of vinyl acetate increases, the crystallinity of the polyethylene is broken down and in this manner the melting and softening points or the hardness of the resultant products are reduced. The vinyl acetate additionally makes the copolymer more polar and so improves its adhesion to polar substrates.
The above-described ethylene/vinyl acetate copolymers are commercially widely available, for example under the trademark Elvax® (Dupont). Polyvinyl alcohols which are particularly suitable for the purposes of the present invention are for example Elvax® 265, Elvax® 240, Elvax® 205 W, Elvax® 200 W and Elvax® 360.
Some particularly suitable copolymers and their physical characteristics may be found in the table below:


	Wt. % vinyl acetate
Product name	(relative to total weight)	Melting point

Elvax ® 40 W	40	47° C.
Elvax ® 150	33	63° C.
Elvax ® 265	28	75° C.
Elvax ® 240	28	74° C.
Elvax ® 205 W	28	72° C.
Elvax ® 200 W	28	71° C.
Elvax ® 360	25	78° C.
Elvax ® 460	18	88° C.
Elvax ® 660	12	96° C.
Elvax ® 760	9	100° C.

For the purposes of the present invention, in particular in the field of fragrancing interiors, particularly preferred fragrance release systems are those in which ethylene/vinyl acetate copolymer is used as the polymeric support material and this copolymer contains 5 to 50 wt. % of vinyl acetate, preferably 10 to 40 wt. % of vinyl acetate and in particular 20 to 30 wt. % of vinyl acetate, in each case relative to the total weight of the copolymer.
Fragrance release systems according to the invention contain the polymeric support materials in the form of particles. The three-dimensional shape of these particles is limited only by what is technically possible during their production. Three-dimensional shapes which may thus be considered include any developments which can sensibly be handled, thus for example cubes, cuboids and corresponding three-dimensional elements with planar side faces and in particular cylindrical developments with a circular or oval cross-section. This latter development encompasses shapes from tablet-shaped particles to compact cylindrical pieces with a ratio of height to diameter of greater than 1. Further possible three-dimensional shapes are spheres, hemispheres or “stretched spheres” in the form of ellipsoidal capsules as well as regular polyhedrons, for example tetrahedrons, hexahedrons, octahedrons, dodecahedrons, icosahedrons. Star-shaped configurations with three, four, five, six or more points are furthermore conceivable, as are completely irregular articles, which may for example take the form of a motif. Suitable motifs are selected depending on the area of application of the agents according to the invention, for example animal figures, such as dogs, horses or birds, floral motifs or representations of fruit. The motifs may, however, also relate to inanimate articles such as vehicles, tools, household items or clothing. Depending on the nature of the selected manufacturing process and/or of a selected coating, the surface of the solid particles may comprise irregularities. Due to the numerous possible developments of the particles, the agents according to the invention are not solely distinguished by advantages during the production thereof.
Due to the many and varied developments, the fragrance-containing particles are additionally visually distinguishable for the consumer and, thanks to the purposeful three-dimensional design of these particles, they permit a visual differentiation of the agents according to the invention which contain fragrances or further active substances optionally present in these agents which is particularly advantageous with regard to product acceptance. The visually perceptible multi-phase nature of these agents may accordingly, for example, emphasize the different modes of action of individual active substances (for example cleaning function plus additional functions such as glass protection, silver protection etc.).
For the purposes of the present application, particles are taken to mean particulate materials which, at room temperature, have a solid, i.e. dimensionally stable, non-free-flowing consistency. Preferred particles have an average diameter of 0.5 to 20 mm, preferably of 1 to 10 mm and in particular of 3 to 6 mm.
The polymeric support materials may be converted into the above-described particles using any process known to a person skilled in the art for processing these substances. For the purposes of the present invention, extrusion, injection molding and atomization to yield polymer pellets are preferred.
Fragrances
Perfume oils or fragrances which may be used for the purposes of the present invention are individual odoriferous compounds, for example synthetic products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type. Odoriferous 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. Ethers include, for example, benzyl ethyl ether, aldehydes include, for example, linear alkanals having 8-18 C atoms, citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal, ketones include, for example, ionones, α-isomethylionone and methyl cedryl ketone, alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, hydrocarbons mainly include terpenes such as limonene and pinene. Preferably, however, mixtures of various odoriferous substances which together produce an attractive fragrance note are used. Such perfume oils may also contain natural odoriferous mixtures, as are obtainable from plant sources, for example pine, citrus, jasmine, patchouli, rose or ylang-ylang oil. Muscatel oil, sage oil, camomile oil, clove oil, melissa oil, mint oil, cinnamon leaf oil, lime blossom oil, juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil and orange-blossom oil, neroli oil, orange peel oil and sandalwood oil are likewise suitable.
The general description of usable perfumes (see above) here generally represents the various different classes of odoriferous substances. If it is to be perceptible, an odoriferous substance must be volatile, wherein, in addition to the nature of the functional groups and the structure of the chemical compound, an important role is also played by molar mass. Most odoriferous substances accordingly have molar masses of up to approx. 200 Dalton, while molar masses of 300 Dalton and above tend to be an exception. Due to the differing volatility of odoriferous substances, the odor of a perfume or fragrance composed of two or more odoriferous substances varies over the course of vaporization, it being possible to subdivide odor impressions into “head or top note”, “heart or middle note” and “end note or dry-out”. Since odor perception largely also depends on odor intensity, the head note of a perfume or fragrance does not solely consist of highly volatile compounds, while the end note largely consists of less volatile, i.e. tenacious odoriferous substances. When formulating perfumes, more highly volatile odoriferous substances may, for example, be bound to certain fixatives, so preventing them from vaporizing rapidly. Accordingly, in the following classification of odoriferous substances into “more highly volatile” or “tenacious” odoriferous substances, no statement is made about odor impression nor about whether the corresponding odoriferous substance is perceived as a top or heart note.
Appropriate selection of the stated fragrances or perfume oils may in this manner have an influence on the agents according to the invention both in terms of product odor immediately on opening the brand new agent and in terms of the odor in service, for example during use in a dishwashing machine. These odor impressions may, of course, be identical, but may also differ. It is advantageous to use more tenacious odoriferous substances for the latter odor impression, while more highly volatile odoriferous substances may also be used for product fragrancing. Tenacious odoriferous substances which may be used for the purposes of the present invention are, for example, essential oils such as angelica root oil, anise oil, arnica blossom oil, basil oil, bay oil, bergamot oil, champak flower oil, silver fir oil, silver fir cone oil, elemi oil, eucalyptus oil, fennel oil, pine-needle oil, galbanum oil, geranium oil, ginger grass oil, guaiacwood oil, gurjun balsam oil, helichrysum oil, ho oil, ginger oil, iris oil, cajeput oil, calmus oil, camomile oil, camphor oil, canaga oil, cardamom oil, cassia oil, pine needle oil, copaiva balsam oil, coriander oil, spearmint oil, caraway oil, cumin oil, lavender oil, lemongrass oil, lime oil, mandarin oil, melissa oil, ambrette oil, myrrh oil, clove oil, neroli oil, niaouli oil, olibanum oil, orange oil, origanum oil, palmarosa oil, patchouli oil, Peru balsam oil, petitgrain oil, pepper oil, peppermint oil, pimento oil, pine oil, rose oil, rosemary oil, sandalwood oil, celery oil, spike oil, star anise oil, terpentine oil, thuja oil, thyme oil, verbena oil, vetiver oil, juniper berry oil, wormwood oil, wintergreen oil, ylang-ylang oil, hyssop oil, cinnamon oil, cinnamon leaf oil, citronellol, lemon oil and cypress oil. Higher-boiling or solid odoriferous substances of natural or synthetic origin may, however, also be used for the purposes of the present invention as tenacious odoriferous substances or odoriferous substance mixtures, i.e. fragrances. These compounds include the compounds stated below and mixtures thereof, ambrettolide, α-amylcinnamaldehyde, anethole, anisaldehyde, anisyl alcohol, anisole, anthranilic acid methyl ester, acetophenone, benzyl acetone, benzaldehyde, benzoic acid ethyl ester, benzophenone, benzyl alcohol, benzyl acetate, benzyl benzoate, benzyl formate, benzyl valerate, borneol, bornyl acetate, α-bromostyrene, n-decylaldehyde, n-dodecylaldehyde, eugenol, eugenol methyl ether, eucalyptol, farnesol, fenchone, fenchyl acetate, geranyl acetate, geranyl formate, heliotropin, methyl heptine carbonate, heptaldehyde, hydroquinone dimethyl ether, hydroxycinnamaldehyde, hydroxycinnamyl alcohol, indole, irone, isoeugenol, isoeugenol methyl ether, isosafrole, jasmone, camphor, carvacrol, carvone, p-cresol methyl ether, coumarin, p-methoxyacetophenone, methyl N-amyl ketone, methylanthranilic acid methyl ester, p-methylacetophenone, methylchavicol, p-methylquinoline, methyl-naphthyl ketone, methyl n-nonylacetaldehyde, methyl n-nonyl ketone, muscone, β-naphthol ethyl ether, β-naphthol methyl ether, nerol, nitrobenzene, n-nonylaldehyde, nonyl alcohol, n-octylaldehyde, p-oxyacetophenone, pentadecanolide, β-phenylethyl alcohol, phenylacetaldehyde dimethyl acetal, phenylacetic acid, pulegone, safrole, isoamyl salicylate, methyl salicylate, hexyl salicylate, cyclohexyl salicylate, santalol, skatole, terpineol, thymene, thymol, γ-undecalactone, vanillin, veratrumaldehyde, cinnamaldehyde, cinnamyl alcohol, cinnamic acid, ethyl cinnamate, benzyl cinnamate. More highly volatile odoriferous substances include in particular lower-boiling odoriferous substances of natural or synthetic origin, which may be used alone or in mixtures. Examples of more highly volatile odoriferous substances are alkyl isothiocyanates (alkyl mustard oils), butanedione, limonene, linalool, linalyl acetate and propionate, menthol, menthone, methyl n-heptenone, phellandrene, phenylacetaldehyde, terpinyl acetate, citral, citronellal.
The plastics particles are preferably loaded with the selected fragrance at a temperature of 15 to 30° C., preferably of 20 to 25° C. To this end, the particles are combined with the appropriate quantity of fragrance and intermixed. In any event, however, 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 primarily taken up by the polymeric support material or by further perfume support materials contained in the particle by adhesion, diffusion and/or capillary forces, said support materials possibly swelling slightly over the course of this procedure.
Further Active Substances
As previously mentioned, agents according to the invention may contain further active substances apart from the constituents necessary for fragrancing and deodorization. Further product groups which contain further preferred substances in addition to the above-stated constituents according to the invention may accordingly be differentiated from agents which serve solely for fragrancing.
Dyes
Dyes are the first kind of these optionally usable preferred substances. Dyes which are suitable for this purpose are any dyes which are known to a person skilled in the art to be suitable for coloring plastics or are soluble in perfume oils. It is preferred to select the dye in accordance with the fragrance used; for example particles with a lemon odor will preferably have a yellow color, while a green color is preferred for particles with an apple or herbal fragrance. Preferred dyes have elevated storage stability and are insensitive to the other constituents of the agents and to light. If the agents according to the invention are used in connection with cleaning textiles or dishes, the dyes used should not have any pronounced substantivity towards textile fibers, glass, plastic dishes or ceramics so that they do not color such items.
Suitable dyes and dye mixtures are commercially obtainable under various trade names and are offered for sale inter alia by the companies BASF AG, Ludwigshafen, Bayer AG, Leverkusen, Clariant GmbH, DyStar Textilfarben GmbH & Co. Deutschland 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 (Fat Orange W-2201), Sandoplast Blue 2B, Fat Yellow 3G, Iragon® Red SRE 122, Iragon® Green SGR 3, Solvent Yellow 33 and Solvent Yellow 16, but other dyes may also be present.
In a preferred embodiment, the dye not only has an aesthetic effect but also serves an indicator function. In this manner, the consumer is informed of the current state of consumption of the deodorant, so that, in addition to the absence of odor, which may for example also be due to habituation on the part of the user, he/she receives an additional reliable indication of when a deodorant has to be replaced with a new one.
The indicator action may be achieved in various different ways: on the one hand, a dye may be used which escapes from the particles over the course of use. This may be brought about, for example, by constituents present in the dishwashing detergent. To this end, a dye must be used which adheres well to the particles or only slowly diffuses out therefrom, in order to ensure that decolorization is not completed too soon, namely before the fragrance has been consumed. On the other hand, however, a color change may be brought about by a chemical reaction or thermal decomposition.
Antimicrobial Active Ingredients, Germicides, Fungicides
Further preferred constituents of agents according to the invention are substances such as antimicrobial active ingredients, germicides, fungicides, antioxidants or corrosion inhibitors, with the assistance of which additional benefits, such as for example disinfection or corrosion protection, may be achieved.
The agents according to the invention may contain antimicrobial active ingredients in order to combat microorganisms. In this connection, a distinction is drawn, depending on the antimicrobial spectrum and mechanism of action, between bacteriostatics and bactericides, fungistatics and fungicides etc. Significant substances from these groups are, for example, benzalkonium chlorides, alkylarylsulfonates, halophenols and phenol mercuriacetate.
Antioxidants
The agents may contain antioxidants in order to prevent unwanted changes to the agents according to the invention or to the, for example, treated textiles brought about by the action of oxygen and other oxidative processes. This class of compounds includes, for example, substituted phenols, hydroquinones, pyrocatechols 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, said agents may contain corrosion inhibitors to protect the articles being washed or the machine, with silver protection agents being of particular significance in relation to machine dishwashing. Known prior art substances may be used. In general, silver protection agents which may be used are those primarily selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes. Benzotriazole and/or alkylaminotriazole are particularly preferably used. Detergent formulations furthermore frequently comprise agents containing active chlorine which are capable of distinctly reducing corrosion of silver surfaces. Organic redox-active compounds containing oxygen and nitrogen, such as di- and trihydric phenols, for example hydroquinone, pyrocatechol, hydroxyhydroquinone, gailic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds are in particular used in chlorine-free detergents. Saline and complexed inorganic compounds, such as salts of metals Mn, Ti, Zr, Hf, V, Co and Ce are also frequently used. Preferred compounds are here transition metal salts, which are selected from the group of manganese and/or cobalt salts and/or complexes, particularly preferably the cobalt (ammine) complexes, cobalt (acetate) complexes, cobalt (carbonyl) complexes, the chlorides of cobalt or manganese and of manganese sulfate. Zinc compounds may likewise by used to prevent corrosion of the articles being washed.
Instead of or in addition to the above-described silver protection agents, for example benzotriazoles, it is possible to use redox-active substances in the agents according to the invention. These substances are preferably inorganic redox-active substances from the group comprising manganese, titanium, zirconium, hafnium, vanadium, cobalt and cerium salts and/or complexes, the metals preferably being present in one of oxidation numbers II, III, IV, V, or VI.
The metal salts or metal complexes used should be at least partially soluble in water. Counterions suitable for salt formation include not only any conventional mono-, di- or trinegatively charged inorganic anions, for example oxide, sulfate, nitrate, fluoride, but also organic anions such as for example stearate.
Metal complexes for the purposes 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. The central atom is one of the above-mentioned metals in one of the above-mentioned oxidation numbers. The ligands are neutral molecules or anions which are mono- or polydentate; the term “ligands” is explained in greater detail for the purposes of the invention for example in “Römpp Chemie Lexikon, Georg Thieme Verlag Stuttgart/New York, 9th edition, 1990, page 2507”. If the charge of the central atom and the charge of the ligand(s) does not add up to zero in a metal complex, either one or more of the above-mentioned anions or one or more cations, for example sodium, potassium or ammonium ions, ensures charge equalization depending on whether a cationic or an anionic charge surplus is present. Examples of suitable complexing agents are citrate, acetylacetonate or 1-hydroxyethane-1,1-diphosphonate.
The chemically familiar definition of “oxidation number” is given for example in “Römpp Chemie Lexikon, Georg Thieme Veriag Stuftgart/New York, 9th edition, 1991, page 3168”.
Particularly preferred metal salts and/or metal complexes are selected from the group comprising MnSO₄, Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, Mn(II) [1-hydroxyethane-1,1-diphosphonate], V₂O₅, V₂O₄, VO₂, TiOSO₄, K₂TiF₆, K₂ZrF₆, CoSO₄, Co(NO₃)₂, Ce(NO₃)₃and mixtures thereof such that preferred agents according to the invention are characterized in that the metal salts and/or metal complexes are selected from the group comprising MnSO₄, Mn(II) citrate, Mn(II) stearate, Mn(II) acetylacetonate, Mn(II) [1-hydroxyethane-1,1-diphosphonate], V₂O₅, V₂O₄, VO₂, TiOSO₄, K₂TiF₆, K₂ZrF₆, CoSO₄, CO(NO₃)₂, Ce(NO₃)₃.
These metal salts or metal complexes generally comprise conventional commercial substances, which may be used to protect silver against corrosion without prior cleaning in the agents according to the invention. Thus, the mixture known from SO₃production (contact method) of pentavalent and tetravalent vanadium (V₂O₅, VO₂, V₂O₄) is suitable, for example, as is the titanyl sulfate, TiOSO₄, arising through dilution of a Ti(SO₄) solution.
The stated metal salts and/or metal complexes are contained in the agents according to the invention preferably in a quantity of from 0.05 to 6 wt. %, preferably 0.2 to 2.5 wt. %, relative to the total agent without the container.
Agents for Preventing Glass Corrosion
In addition to the cleaning performance thereof, one important criterion for assessing a machine dishwashing detergent is the visual appearance of the dry dishes after cleaning has been performed. Any calcium carbonate deposits which may occur on dishes or inside the machine may have a disadvantageous effect on customer satisfaction, for example, and thus have a causal influence on the economic success of such a cleaning agent. A further long-standing problem of machine dishwashing is corrosion of glassware, which generally takes the form not only of cloudiness, streaks and scratches, but also of iridescence of the glass surface. The observed effects are the result substantially of two processes, on the one hand the discharge of alkali and alkaline earth ions from the glass in conjunction with hydrolysis of the silicate network and on the other hand the deposition of silicate compounds on the glass surface.
The stated problems may be solved with the agents according to the invention if, in addition to the above-stated compulsory and optional constituents, specific glass corrosion inhibitors are incorporated into the agents. Preferred agents according to the invention therefore additionally contain one or more magnesium and/or zinc salts and/or magnesium and/or zinc complexes.
A preferred class of compounds, which may be added to the agents according to the invention to prevent glass corrosion, are insoluble zinc salts. These may attach themselves to the surface of the glass during the dishwashing process and there prevent the dissolution of metal ions from the glass network and hydrolysis of the silicates. In addition, these insoluble zinc salts also prevent the deposition of silicate on the glass surface, such that the glass is protected from the above-described consequences.
For the purposes of this preferred embodiment, insoluble zinc salts are zinc salts which have a solubility of at most 10 grams of zinc salt per liter of water at 20° C. Examples of insoluble zinc salts particularly preferred according to the invention are zinc silicate, zinc carbonate, zinc oxide, basic zinc carbonate (Zn₂(OH)₂CO₃), zinc hydroxide, zinc oxalate, zinc monophosphate (Zn₃(PO₄)₂), and zinc pyrophosphate (Zn₂(P₂O₇)).
The stated zinc compounds are used in the agents according to the invention in quantities which bring about a zinc ion content in the agents of between 0.02 and 10 wt. %, preferably between 0.1 and 5.0 wt. % and in particular between 0.2 and 1.0 wt. %, in each case relative to the agent without the container. The exact zinc salt content of the agent is naturally dependent on the zinc salt type the lower the solubility of the zinc salt used, the higher should be the concentration thereof in the agents according to the invention.
A further preferred class of compounds comprises magnesium and/or zinc salt(s) of at least one monomeric and/or polymeric organic acid. These have the effect that, even with repeated use, the surfaces of glassware are not changed corrosively, in particular no clouding, streaks or scratching are caused, and also no iridescence of the glass surfaces.
Although, according to the invention, any magnesium and/or zinc salt(s) of monomeric and/or polymeric organic acids may be contained in the claimed agents, as described above preference is given to the magnesium and/or zinc salts of monomeric and/or polymeric organic acids from the groups comprising unbranched saturated or unsaturated monocarboxylic acids, branched saturated or unsaturated monocarboxylic acids, saturated and unsaturated dicarboxylic acids, aromatic mono-, di- and tricarboxylic acids, saccharic acids, hydroxy acids, oxo acids, amino acids and/or polymeric carboxylic acids. Within these groups, for the purposes of the present invention the acids stated below are in turn preferred:
The spectrum of zinc salts preferred according to the invention of organic acids, preferably organic carboxylic acids, extends from salts which are sparingly soluble or insoluble in water, i.e. exhibit a solubility of below 100 mg/L, preferably below 10 mg/L, in particular no solubility, up to those salts which display a solubility in water of above 100 mg/L, preferably above 500 mg/L, particularly preferably above 1 g/L and in particular above 5 g/L (all solubilities at 20° C. water temperature). The first group of zinc salts includes for example zinc citrate, zinc oleate and zinc stearate, the group of soluble zinc salts including for example zinc formate, zinc acetate, zinc lactate and zinc gluconate:
In a further preferred embodiment of the present invention, the agents according to the invention contain at least one zinc salt, but no magnesium salt, of an organic acid, the at least one zinc salt preferably being a zinc salt of an organic carboxylic acid, particularly preferably a zinc salt from the group comprising zinc stearate, zinc oleate, zinc gluconate, zinc acetate, zinc lactate and/or zinc citrate. Zinc ricinoleate, zinc abietate and zinc oxalate are also preferred.
An agent preferred for the purposes of the present invention contains zinc salt in quantities of from 0.1 to 5 wt. %, preferably of from 0.2 to 4 wt. % and in particular of from 0.4 to 3 wt. %, or zinc in oxidized form (calculated as Zn²⁺) in quantities of from 0.01 to 1 wt. %, preferably of from 0.02 to 0.5 wt. % and in particular of from 0.04 to 0.2 wt. %, in each case relative to the agent without the container.
The present application accordingly also preferably provides a fragrance release system, which contains further active substances, in particular active substances from the group comprising perfume carriers, dyes, antimicrobial active ingredients, germicides, fungicides, antioxidants or corrosion inhibitors.
Bleaching Agents
In addition to the above-stated active substances, the agents according to the invention, in particular agents for use in dishwashing machines, textile washing machines or dryers, may of course comprise all active substances conventionally contained in agents for cleaning textiles or dishes or for textile or dish care, particular preference being given to substances from the group comprising bleaching agents, bleaching activators, polymers, builders, surfactants, enzymes, electrolytes, pH adjusting agents, fragrances, perfume carriers, dyes, hydrotropes, foam inhibitors, antiredeposition agents, optical brighteners, graying inhibitors, shrinkage prevention agents, anti-crease agents, dye transfer inhibitors, antimicrobial active ingredients, germicides, fungicides, antioxidants, corrosion inhibitors, antistatic agents, waterproofing and impregnation agents, anti-swelling and anti-slip agents, nonaqueous solvents, rinse conditioners, protein hydrolysates, and UV absorbers. Such combination products are then, in addition to repeated fragrancing, also suitable for single or repeated care or cleaning of textiles or dishes.
Bleaching agents and bleaching activators may be present in the agents according to the invention as important constituents of detergents or cleaning agents in addition to other constituents Among those compounds acting as bleaching agents which release H₂O₂in water, sodium perborate tetrahydrate and sodium perborate monohydrate are of particular significance. Further usable bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H₂O₂-releasing per-acidic salts or per-acids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloimino per-acid or diperdodecanedioic acid. Detergent moldings for machine dishwashing may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaching agents are diacyl peroxides, such as for example dibenzoyl peroxide. Further typical organic bleaching agents are peroxy acids, with examples which may in particular be mentioned being alkylperoxy acids and arylperoxy acids. Preferred representatives which may be used are (a) peroxybenzoic acid and the ring-substituted derivatives thereof, such as alkylperoxybenzoic acids, as well as peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) aliphatic or substitutedly aliphatic peroxy acids, such as peroxylauric acid, peroxystearic acid, E-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassylic acid, diperoxyphthalic acids, 2-decyldiperoxybutane-1,4-dioic acid, N,N-terephthaloyldi(6-aminopercaproic acid).
If the agents according to the invention are used in combination with machine dishwashing detergents, the latter may contain bleaching activators in order to achieve an enhanced bleaching action when cleaning at temperatures of 60° C. and below. Bleaching activators which may be used are compounds which, under perhydrolysis conditions, yield aliphatic peroxycarboxylic acids with preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and/or optionally substituted perbenzoic acid. Suitable substances are those which bear O- and/or N-acyl groups having the stated number of C atoms and/or optionally substituted benzoyl groups. Preferred compounds are repeatedly acylated 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-nonanoylsuccinimide (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.
Further bleaching activators which are preferably used for the purposes of the present application are compounds from the group of cationic nitriles, in particular cationic nitrites of the formula
in which R¹denotes —H, —CH₃, a C_2-24alkyl or alkenyl residue, a substituted C_2-24alkyl or alkenyl residue with at least one substituent from the group —Cl, —Br, —OH, —NH₂, —CN, an alkyl or alkenylaryl residue with a C_1-24alkyl group, or denotes a substituted alkyl or alkenylaryl residue with a C_1-24alkyl group and at least one further substituent on the aromatic ring, R²and R³are mutually independently selected from —CH₂—CN, —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, —CH₂—OH, —CH₂—CH₂—OH, —CH(OH)—CH₃, —CH₂—CH₂—CH₂—OH, —CH₂—CH(OH)—CH₃, —CH(OH)—CH₂—CH₃, —(CH₂CH₂—O)_nH with n=1, 2, 3, 4, 5 or 6 and X is an anion.
Particularly preferred agents according to the invention contain a cationic nitrite of the formula
in which R⁴, R⁵and R⁶are mutually independently selected from —CH₃, —CH₂—CH₃, —CH₂—CH₂—CH₃, —CH(CH₃)—CH₃, wherein R⁴may additionally also be —H and X is an anion, wherein preferably R⁵=R⁶=—CH₃and in particular R⁴═R⁵=R⁶=—CH₃and compounds of the formulae (CH₃)₃N⁽⁺⁾CH₂—CNX⁻, (CH₃CH₂)₃N⁽⁺⁾CH₂—CNX⁻, (CH₃CH₂CH₂)₃N⁽⁺⁾CH₂—CNX⁻, (CH₃CH(CH₃))₃N⁽⁺⁾CH₂—CNX⁻, or (HO—CH₂—CH₂)₃N⁽⁺⁾CH₂—CNX⁻ are particularly preferred, wherein in turn from the group of these substances the cationic nitrile of the formula (CH₃)₃N⁽⁺⁾CH₂—CNX⁻, in which X⁻ denotes an anion which is selected from the group chloride, bromide, iodide, hydrogensulfate, methosulfate, p-toluenesulfonate (tosylate) or xylenesulfonate, is particularly preferred.
In addition to conventional bleaching activators or instead of them, it is also possible to incorporate “bleach catalysts” into the agents. These substances comprise bleach-boosting transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salen complexes or carbonyl complexes. Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with nitrogenous tripod ligands and Co, Fe, Cu and Ru ammine complexes may also be used as bleach catalysts.
Surfactants
For the purposes of the present application, preferred agents contain one or more surfactant(s) from the groups of anionic, nonionic, cationic and/or amphoteric surfactants.
Preferably used anionic surfactants in acid form are one or more substances from the group comprising carboxylic acids, sulfuric acid semiesters and sulfonic acids, preferably from the group comprising fatty acids, fatty alkyl sulfuric acids and alkylarylsulfonic acids If they are to exhibit adequate surface-active properties, the stated compounds should here comprise relatively long-chain hydrocarbon residues, thus at least 6 C atoms in the alkyl or alkenyl residue. The C chain distributions of anionic surfactants are conventionally in the range from 6 to 40, preferably 8 to 30 and in particular 12 to 22 carbon atoms.
Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaning agents are largely obtained industrially from native fats and oils by hydrolysis. While alkaline saponification, which was carried out as long ago as last century, gave rise directly to alkali metal salts (soaps), today only water, which cleaves the fats into glycerol and free fatty acids, is used for cleavage on a large industrial scale. Processes which are used on a large industrial scale are for example autoclave cleavage or continuous high pressure cleavage. Carboxylic acids usable in acid form for the purposes of the present invention as anionic surfactants are for example hexanoic acid (caproic acid), heptanoic acid (oenanthic acid), octanoic acid (caprylic acid), nonanoic acid (pelargonic acid), decanoic acid (capric acid), undecanoic acid etc. It is preferred for the purposes of the present compound to use 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), tetracosanoic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacontanoic acid (melissic acid) and the 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-octadecadienoic acid (linoleic acid), 9t,12t-octadecadienoic acid (linolaidic acid) and 9c,12c,15c-octadecatrienoic acid (linolenic acid). It is preferred on cost grounds not to use the pure species, but instead technical mixtures of the individual acids, as are obtainable from fat cleavage. Such mixtures are for example coconut oil fatty acid (approx. 6 wt. % C₈, 6 wt. % C₁₀, 48 wt. % C₁₂, 18 wt. % C₁₁, 10 Wt. % C₁₆, 2 wt. % C₁₈, 8 wt. % C_18′, 1 wt. % C_18″), palm kernel oil fatty acid (approx. 4 wt. % C₈, 5 Wt. % C₁₀, 50 wt. % C₁₂, 15 Wt. % C₁₄, 7 wt. % C₁₆, 2 wt. % C₁₈, 15 wt. % C_18′, 1 wt. % C_18″), tallow fatty acid (approx. 3 wt. % C₁₄, 26 wt. % C₁₆, 2 wt. % CO₅₆, 2 wt. % C₁₇, 17 wt. % C₁₈, 44 wt. % C_18′, 3 wt. % C_18″, 1 wt. % C₁₈), hydrogenated tallow fatty acid (approx. 2 wt. % C₁₄, 28 wt. % C₁₆, 2 wt. % C₁₇, 63 wt. % C₁₈, 1 wt. % C₁₈″), technical oleic acid (approx. 1 wt. % C₁₂, 3 wt. % C₁₄, 5 wt. % C₁₆, 6 wt. % C_16′, 1 Wt. % C₁₇, 2 wt. % C₁₈, 70 wt. % C_18′, 10 wt. % C_18″, 0.5 wt. % C_18′″), technical palmitic/stearic acid (approx. 1 wt. % C₁₂, 2 wt. % C₁₄, 45 wt. % C₁₆, 2 wt. % C₁₇, 47 wt. % C₁₈, 1 wt. % C_18′) and soybean oil fatty acid (approx. 2 wt. % C₁₄, 15 wt. % C₁₆, 5 wt. % C₁₈, 25 wt. % C_18′, 45 wt. % C_18″, 7 wt. % C_18′″).
Sulfuric acid semiesters of relatively long-chain alcohols are likewise anionic surfactants in their acid form and are usable for the purposes of the present invention. Their alkali metal salts, in particular sodium salts, namely fatty alcohol sulfates, are obtainable on a large industrial scale from fatty alcohols which are reacted with sulfuric acid, chlorosulfonic acid, amidosulfonic acid or sulfur trioxide to yield the corresponding alkylsulfuric acid and are subsequently neutralized. The fatty alcohols are here obtained from the corresponding fatty acids or fatty acid mixtures by high pressure hydrogenation of the fatty acid methyl esters. The most significant industrial process in volume terms for producing fatty alkylsulfuric acids is sulfonation of the alcohols with SO₃/air mixtures in special cascade, failing-film or tube-bundle reactors.
Another class of anionic surfactant acids which may be used according to the invention are alkyl ether sulfuric acids, the salts thereof, alkyl ether sulfates, which, in comparison with alkyl sulfates, are distinguished by higher water solubility and lower sensitivity to water hardness (solubility of Ca salts). Alkyl ether sulfuric acids are synthesized in the same manner as alkylsulfuric acids from fatty alcohols which are reacted with ethylene oxide to yield the corresponding fatty alcohol ethoxylates. Propylene oxide may also be used instead of ethylene oxide. Subsequent sulfonation with gaseous sulfur trioxide in short retention time sulfonation reactors provides yields of above 98% of the corresponding alkyl ether sulfuric acids.
Alkanesulfonic acids and olefinsulfonic acids may also be used for the purposes of the present invention as anionic surfactants in acid form. Alkanesulfonic acids may contain the sulfonic acid group attached terminally (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only secondary alkanesulfonic acids being of commercial significance. These are produced by sulfochlorination or sulfoxidation of linear hydrocarbons. In Reed sulfochlorination, n-paraffins are reacted with sulfur dioxide and chlorine under UV light irradiation to yield the corresponding sulfochlorides which, when hydrolyzed with alkalis, directly give rise to alkane sulfonates and, on reaction with water, give rise to alkanesulfonic acids. Since di- and polysulfochlorides and chlorinated hydrocarbons may occur as secondary products of the free-radical reaction during sulfochlorination, the reaction is conventionally carried out only up to a degree of conversion of 30% and then terminated.
Another process for producing alkanesulfonic acids is sulfoxidation, in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation. This free-radical reaction yields successive alkylsulfonyl radicals which react further with oxygen to yield alkylpersulfonyl radicals. The reaction with an unreacted paraffin yields an alkyl radical and the alkylpersulfonic acid, which breaks down into an alkylperoxysulfonyl radical and a hydroxyl radical. The reaction of the two free radicals with an unreacted paraffin yields alkylsulfonic acids and water, which reacts with alkylpersulfonic acid and sulfur dioxide to yield sulfuric acid. In order to keep the yield of the two final products alkylsulfonic acid and sulfuric acid as high as possible and to suppress secondary reactions, this reaction is conventionally carried out only up to a degree of conversion of 1% and then terminated.
Olefin sulfonates are produced industrially by reaction of α-olefins with sulfur trioxide. This results in the intermediate formation of zwitterions which cyclize to yield “sultones”. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to yield hydroxylalkanesulfonic acids or alkenesulfonic acids, which may both likewise be used as anionic surfactant acids.
Alkylbenzenesulfonates have been known as high-performance anionic surfactants since the 1930s. At that time, alkylbenzenes were produced by monochlorination of Kogasin fractions and subsequent Friedel-Crafts alkylation, the alkylbenzenes then being sulfonated with oleum and neutralized with sodium hydroxide. In the early 1950s, alkylbenzenesulfonates were produced by tetramerizing propylene to yield branched α-dodecylene, and the product was converted via a Friedel-Crafts reaction, using aluminum trichloride or hydrogen fluoride, to tetrapropylene benzene, which was then sulfonated and neutralized. This economical capability for producing tetrapropylene benzenesulfonates (TPS) led to a breakthrough for this surfactant class, which subsequently displaced soaps as the main surfactant in detergents and cleaning agents.
Due to the inadequate biodegradability of TPS, the need arose to provide new alkylbenzenesulfonates which were characterized by better environmental behavior. These requirements have been met by linear alkylbenzenesulfonates, which today are almost the only alkylbenzenesulfonates produced, and are abbreviated ABS or LAS.
Linear alkylbenzenesulfonates are produced from linear alkylbenzenes, which are in turn obtainable from linear olefins. This is done on a large industrial scale by separating petroleum fractions with molecular sieves into n-paraffins of the desired purity, and dehydrogenating them to yield n-olefins, resulting in both α- and i-olefins. The resultant olefins are then reacted with benzene, in the presence of acid catalysts, to yield alkylbenzenes, the Friedel-Crafts catalyst selected having an influence on the isomer distribution of the resulting linear alkylbenzenes: if aluminum trichloride is used, the content of 2-phenyl isomers in the mixture with 3-, 4-, 5-, and other isomers is about 30 wt %, while if hydrogen fluoride is used as the catalyst, the 2-phenyl isomer content can be reduced to approx. 20 wt. %. Lastly, sulfonation of linear alkylbenzenes is performed today on a large industrial scale with oleum, sulfuric acid, or gaseous sulfur trioxide, the latter being by far the most significant, Sulfonation is carried out using special film or tube-bundle reactors which yield a 97 wt. % alkylbenzenesulfonic acid (ABSA) as product, which may be used for the purposes of the present invention as an anionic surfactant acid.
By selection of the neutralizing agent, it is possible to obtain a very wide variety of salts, i.e. alkylbenzenesulfonates, from ABSA. For reasons of economy, it is preferred in this context to produce and use the alkali metal salts, and among these preferably the sodium salts, of ABSA. These can be described by the general formula IX:
in which the sum of x and y is conventionally between 5 and 13. C_8-16, preferably C_9-13, alkylbenzenesulfonic acids are preferably used according to the invention as an anionic surfactant in acid form. It is further preferred for the purposes of the present invention to use C_8-16, preferably C_9-13alkylbenzenesulfonic acids which are derived from alkylbenzenes having a tetralin content of less than 5 wt. % relative to the alkylbenzene. It is further preferred to use alkylbenzenesulfonic acids whose alkylbenzenes have been produced by the HF process, such that the C_8-16, preferably C_9-13alkylbenzenesulfonic acids used have a 2-phenyl isomer content of below 22 wt. % relative to the alkylbenzenesulfonic acid.
The above-stated anionic surfactants may be used in their acid form alone or mixed with one another. It is, however, also possible and preferred for further, preferably acidic, constituents of detergents and cleaning agents to be incorporated in quantities of from 0.1 to 40 wt. %, preferably of from 1 to 15 wt. % and in particular of from 2 to 10 wt. %, in each case relative to the weight of the mixture to be reacted, into the anionic surfactant in acid form prior to addition onto the support material(s).
It is, of course, also possible to use the anionic surfactants in partially or completely neutralized form. These salts may then be present in the granulation liquid not only as a solution, suspension or emulsion, but also as a solid constituent of the solids bed. Cations for such anionic surfactants which may be considered, apart from alkali metals (here in particular salts as claimed and K salts), are ammonium as well as mono-, di-, or triethanolalkonium ions. Instead of mono-, di-, or triethanolamine, it is possible for the analogous representatives of mono-, di-, or trimethanolamine, or those of the alkanolamines of higher alcohols to be quaternized and present as a cation.
Cationic surfactants may also advantageously be used as the active substance. The cationic surfactant may here be added directly to the mixer in its form as delivered, or be sprayed onto the solid supports in the form of a liquid to pasty cationic surfactant preparation. Such cationic surfactant preparations may be produced, for example, by mixing conventional commercial cationic surfactants with auxiliary substances such as nonionic surfactants, polyethylene glycols or polyols. Lower alcohols such as ethanol and isopropanol may also be used, in which case the quantity of such lower alcohols in the liquid cationic surfactant preparation should be below 10 wt. % for the above-stated reasons.
Cationic surfactants which may be considered for the agents according to the invention are any conventional substances, with cationic surfactants having a textile-softening action being distinctly preferred.
The agents according to the invention may contain one or more cationic textile-softening agents of the formulae X, XI or XII as cationic active substances having a textile-softening action:
in which each group R¹is mutually independently selected from among C_1-6alkyl, alkenyl or hydroxyalkyl groups; each group R²is mutually independently selected from among C_8-28alkyl or alkenyl groups; R³=R¹or (CH₂)_n-T-R²; R⁴=R¹or R²or (CH₂)_n-T-R²; T=—CH₂—, —O—CO— or —CO—O— and n is an integer from 0 to 5.
In preferred embodiments of the present invention, the agents additionally contain nonionic surfactant(s) as an active substance.
Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and on average 1 to 12 mol of ethylene oxide (EO) per mol of alcohol, in which the alcohol residue may be linear or preferably methyl-branched in position 2 or may contain linear and methyl-branched residues in the mixture, as they are usually present in oxo alcohol residues, are preferably used as nonionic surfactants. In particular, however, alcohol ethoxylates with linear residues prepared from alcohols of natural origin with 12 to 18 C atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and on average 2 to 8 EO per mol of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C_12-14alcohols with 3 EO or 4 EO, C_9-11alcohols with 7 EO, C_13-15alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C_12-18alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C_12-14alcohol with 3 EO and C_12-18alcohol with 5 EO. The stated degrees of ethoxylation are statistical averages which, for a specific product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homologue distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
Alkylglycosides of the general formula RO(G)_x, in which R means a primary straight-chain or methyl-branched aliphatic residue, in particular methyl-branched in position 2, with 8 to 22, preferably 12 to 18 C atoms and G is the symbol which denotes a glycose unit with 5 or 6 C atoms, preferably glucose, may moreover be used as further nonionic surfactants. The degree of oligomerization x, which indicates the distribution of monoglycosides and oligoglycosides, is any desired number between 1 and 10; x is preferably 1.2 to 1.4.
A further class of preferably used nonionic surfactants, which may be 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters.
Nonionic surfactants of the amine oxide type, for example N-coconut alkyl-N,N-dimethylamine oxide and N-tallow alcohol-N,N-dihydroxyethylamine oxide, and the fatty acid alkanolamide type may also be suitable. The quantity of these nonionic surfactants preferably amounts to no more than that of the ethoxylated fatty alcohols, in particular no more than half the quantity thereof.
Further suitable surfactants are polyhydroxyfatty acid amides of the formula XIII,
in which RCO denotes an aliphatic acyl residue with 6 to 22 carbon atoms, R¹denotes hydrogen, an alkyl or hydroxyalkyl residue with 1 to 4 carbon atoms and [Z] denotes a linear or branched polyhydroxyalkyl residue with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxyfatty acid amides comprise known substances which may conventionally 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 polyhydroxyfatty acid amides also includes compounds of the formula XIV,
in which R denotes a linear or branched alkyl or alkenyl residue with 7 to 12 carbon atoms, R¹denotes a linear, branched or cyclic alkyl residue or an aryl residue with 2 to 8 carbon atoms and R²denotes a linear, branched or cyclic alkyl residue or an aryl residue or an oxyalkyl residue with 1 to 8 carbon atoms, wherein C_1-4alkyl or phenyl residues are preferred, and [Z] denotes a linear polyhydroxyalkyl residue, the alkyl chain of which is substituted with at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated derivatives of this residue.
[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds may then be converted into the desired polyhydroxyfatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
It is particularly preferred for many applications for the ratio of anionic surfactant(s) to nonionic surfactant(s) to amount to between 10:1 and 1:10, preferably between 7.5:1 and 1:5 and in particular between 5:1 and 1:2, Containers according to the invention are here preferred which contain surfactant(s), preferably anionic and/or nonionic surfactant(s), in quantities of from 5 to 80 wt. %, preferably of from 7.5 to 70 wt. %, particularly preferably of from 10 to 60 wt. % and in particular of from 12.5 to 50 wt. %, in each case relative to the weight of the enclosed solids.
As has already been mentioned, the use of surfactants in cleaning agents for machine dishwashing is preferably limited to the use of small quantities of nonionic surfactants. Agents according to the invention for machine dishwashing therefore preferably contain only specific nonionic surfactants which are described below. Only low-foaming nonionic surfactants are conventionally used as surfactants in machine dishwashing detergents. Representatives from the groups of anionic, cationic or amphoteric surfactants are, in contrast, of less significance. Alkoxylated, advantageously ethoxylated, in particular primary alcohols with preferably 8 to 18 C atoms and on average 1 to 12 mol of ethylene oxide (EO) per mol of alcohol, in which the alcohol residue may be linear or preferably methyl-branched in position 2 or may contain linear and methyl-branched residues in the mixture, as they are usually present in oxo alcohol residues, are preferably used as nonionic surfactants. In particular, however, alcohol ethoxylates with linear residues prepared from alcohols of natural origin with 12 to 18 C atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and on average 2 to 8 EO per mol of alcohol are preferred. Preferred ethoxylated alcohols include, for example, C_12-14alcohols with 3 EO or 4 EO, C_9-11alcohols with 7 EO, C_13-15alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C_12-18alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, such as mixtures of C_12-14alcohol with 3 EO and C_12-18alcohol with 5 EO. The stated degrees of ethoxylation are statistical averages which, for a specific product, may be an integer or a fractional number. Preferred alcohol ethoxylates have a narrow homologue distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, fatty alcohols with more than 12 EO may also be used. Examples of these are tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
In particular in the case of cleaning agents for machine dishwashing, it is preferred for these to contain a nonionic surfactant which has a melting point above room temperature, preferably a nonionic surfactant with a melting point of above 20° C. Nonionic surfactants which are preferably to be used have melting points of above 25° C., while nonionic surfactants which are particularly preferably to be used have melting points of between 25 and 60° C., in particular between 26.6 and 43.3° C.
Suitable nonionic surfactants which have melting or softening points in the stated temperature range are for example low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If nonionic surfactants which are highly viscous at room temperature are used, it is preferred for them to have a viscosity of above 20 Pa·s, preferably of above 35 Pa·s and in particular of above 40 Pa·s. Nonionic surfactants which have a waxy consistency at room temperature are also preferred.
Preferably used nonionic surfactants which are in solid form at room temperature originate from the groups of alkoxylated nonionic surfactants, in particular ethoxylated primary alcohols and mixtures of these surfactants with structurally more complex surfactants such as polyoxypropylene/polyoxyethylene/polyoxypropylene (PO/EO/PO) surfactants. Such (PO/EO/PO) nonionic surfactants are furthermore distinguished by good foam control.
In one preferred embodiment of the present invention, the nonionic surfactant with a melting point of above room temperature is an ethoxylated nonionic surfactant which has been obtained from the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 C atoms with preferably at least 12 mol, particularly preferably at least 15 mol, in particular at least 20 mol of ethylene oxide per mol of alcohol or alkylphenol.
One particularly preferred nonionic surfactant to be used, which is solid at room temperature, is obtained from a straight-chain fatty alcohol having 16 to 20 carbon atoms (C_16-20alcohol), preferably a C₁₈alcohol and at least 12 mol, preferably at least 15 mol and in particular at least 20 mol of ethylene oxide. Among these, the “narrow range ethoxylates” (see above) are particularly preferred.
The nonionic surfactant which is solid at room temperature preferably additionally comprises propylene oxide units in its molecule. Such PO units preferably constitute up to 25 wt. %, particularly preferably up to 20 wt. % and in particular up to 15 wt. % of the entire molar mass of the nonionic surfactant. Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally comprise polyoxyethylene/polyoxypropylene block copolymer units. The alcohol or alkylphenol moiety of such nonionic surfactant molecules here preferably constitutes more than 30 wt. %, particularly preferably more than 50 wt. % and in particular more than 70 wt. % of the entire molar mass of such nonionic surfactants.
Further nonionic surfactants with a melting point above room temperature which are particularly preferably to be used contain 40 to 70% of a polyoxypropylene/polyoxyethylene/polyoxypropylene block polymer blend, which contains 75 wt. % of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 mol of ethylene oxide and 44 mol of propylene oxide and 25 wt. % of a block copolymer of polyoxyethylene and polyoxypropylene, initiated with trimethylolpropane and containing 24 mol of ethylene oxide and 99 mol of propylene oxide per mol of trimethylolpropane.
Nonionic surfactants which may particularly preferably be used are for example obtainable from Olin Chemicals under the name Poly Tergente SLF-18.
Another preferred surfactant may be described by the formula
R¹O[CH₂CH(CH₃)O]_x[CH₂CH₂0]_y[CH₂CH(OH)R²]
in which R¹denotes a linear or branched aliphatic hydrocarbon residue with 4 to 18 carbon atoms or mixtures thereof, R²denotes a linear or branched hydrocarbon residue with 2 to 26 carbon atoms or mixtures thereof and x denotes values between 0.5 and 1.5 and y denotes a value of at least 15.
Further preferably usable nonionic surfactants are the end group-terminated poly(oxyalkylated) nonionic surfactants of the formula
R¹O[CH₂CH(R³)O]_x[CH₂]_kCH(OH)[CH₂]_jOR²
in which R¹and R²denote linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 1 to 30 carbon atoms, R³denotes H or a methyl, ethyl, n-propyl, iso-propyl, n-butyl, 2-butyl or 2-methyl-2-butyl residue, x denotes values between 1 and 30, k and j denote values between 1 and 12, preferably between 1 and 5. If the value of x is >2 each R³in the above formula may be different. R¹and R²are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon residues with 6 to 22 carbon atoms, wherein residues with 8 to 18 C atoms are particularly preferred. H, —CH₃or —OH₂CH₃are particularly preferred for the residue R³. Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
As described above, each R³in the above formula may be different if x is ≧2. In this manner, it is possible to vary the alkylene oxide unit in the square brackets. For example, if x denotes 3, the residue R³may be selected in order to form ethylene oxide (R³=H) or propylene oxide (R³=CH₃) units, which may be attached to one another in any sequence, for example (EO)(PO)(EO), (EO)(EO)(PO), (EO)(EO)(EO), (PO)(EO)(PO), (PO)(PO)(EO) and (PO)(PO)(PO). The value 3 for x has been selected here by way of example and may perfectly well be larger, wherein the range of variation increases as the value of x rises and for example comprises a large number of (EO) groups combined with a small number of (PO) groups, or vice versa.
Particularly preferred end group-terminated poly(oxyalkylated) alcohols of the above-stated formula have values of k=1 and j=1, such that the above formula may be simplified to
R¹O[CH₂CH(R³)O]_xCH₂CH(OH)CH₂OR²
In the latter-stated formula, R¹, R²and R³are as defined above and x denotes numbers from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18. Particularly preferred surfactants are those in which the residues R¹and R²comprise 9 to 14 C atoms, R³denotes H and x assumes values from 6 to 15.
Enzymes
Agents according to the invention may contain enzymes to enhance their washing or cleaning performance, it being in principle possible to use any enzymes established in the prior art for these purposes. These include in particular proteases, amylases, lipases, hemicellulases, cellulases or oxidoreductases, and preferably mixtures thereof. These enzymes are in principle of natural origin; starting from the natural molecules, improved variants are available for use in detergents and cleaning agents, said variants accordingly preferably being used. Agents according to the invention preferably contain enzymes in total quantities of 1×10⁻⁶to 5 wt. % relative to active protein. Protein concentration may be determined with the assistance of known methods, for example the BCA method (bicinchonic acid; 2,2′-biquinolyl-4,4′-dicarboxylic acid) or the biuret method.
Among proteases, those of the subtilisin type are preferred. Examples of these are subtilisins BPN′ and Carlsberg, protease PB92, subtilisins 147 and 309, alkaline protease from Bacillus lentus, subtilisin DY and the enzymes thermitase, proteinase K and proteases TW3 and TW7, which are classed among subtilases but not among the subtilisins as more narrowly defined. Subtilisin Carlsberg is obtainable in a further developed form under the trade name Alcalase® from Novozymes A/S, Bagsvasrd, Denmark. Subtilisins 147 and 309 are distributed under the trade name Esperase®, or Savinasee® by Novozymes. The variants sold under the name BLAP® are derived from the protease from Bacillus lentus DSM 5483.
Further usable proteases are for example the enzymes obtainable under the trade names Durazym®, Relase®, Everlase®, Nafizym, Natalase®, Kannase® and Ovozymes® from Novozymes, those obtainable under the trade names Purafect®, Purafect® 0xP and Properase® from Genencor, that obtainable under the trade name Protosol® from Advanced Biochemicals Ltd., Thane, India, that obtainable under the trade name Wuxi® from Wuxi Snyder Bioproducts Ltd., China, those obtainable under the trade names Proleather® and Protease P® from Amano Pharmaceuticals Ltd., Nagoya, Japan, and that obtainable under the name Proteinase K-16 from Kao Corp., Tokyo, Japan.
Examples of amylases usable according to the invention are the α-amylases from Bacillus licheniformis, from B. amyloliquefaciens or from B. stearothermophilus and the further developments thereof enhanced for use in detergents and cleaning agents. The enzyme from B. licheniformis is obtainable from Novozymes under the name Termamyl® and from Genencor under the name Purastar®ST. Further developed products of this α-amylase are obtainable from Novozymes under the trade name Duramyl® and Termamyl® ultra, from Genencor under the name Purastar® OxAm and from Daiwa Seiko Inc., Tokyo, Japan, as Keistase®. The α-amylase from B. amyloliquefaciens is distributed by Novozymes under the name BAN®, and variants derived from the α-amylase from B. stearothermophilus are distributed under names BSG® and Novamyl®, likewise by Novozymes.
Note should moreover be taken for this purpose of the α-amylase from Bacillus sp. A 7-7 (DSM 12368) and the cyclodextrin glucanotransferase (CGTase) from B. agaradherens (DSM 9948); fusion products of the stated molecules may likewise be used.
Furthermore, the further developments of α-amylase from Aspergillus niger and A. oryzae obtainable under the trade name Fungamyl® from Novozymes are also suitable. Another commercial product is for example Amylase-LT®.
Agents according to the invention may contain lipases or cutinases in particular because of their triglyceride-cleaving activities, but also in order to produce peracids in situ from suitable precursors. These include, for example, lipases originally obtainable or further developed from Humicola lanuginosa (Thermomyces lanuginosus), in particular those with the D96L amino acid substitution. They are distributed, for example, by Novozymes under the trade name Lipolase®, Lipolase® Ultra, LipoPrime®, Lipozyme® and Lipex®. Furthermore, the cutinases which were originally isolated from Fusarium solanipisi and Humicola insolens are, for example, also usable. Lipases which are likewise usable are obtainable from Amano under the names Lipase CE®, Lipase P®, Lipase B®, or Lipase CES®, Lipase AKG®, Bacillus sp. Lipase®, Lipase AP®, Lipase M-AP® and Lipase AML®. Lipases or cutinases from Genencor which may, for example, be used are those whose initial enzymes were originally isolated from Pseudomonas mendocina and Fusarium solanii. Further important commercial products which may be mentioned are the preparations M1 Lipase® and Lipomax®, originally distributed by Gist-Brocades, and the enzymes distributed by Meito Sangyo KK, Japan, under the names Lipase MY-30S, Lipase OF® and Lipase PL®, as may the product Lumafast® from Genencor.
In particular if they are intended for treating textiles, agents according to the invention may contain cellulases, depending on the intended purpose as pure enzymes, as enzyme preparations or in the form of mixtures in which the individual components advantageously complement each other with regard to their various performance characteristics. These performance characteristics in particular include contributions to the primary or secondary washing performance of the agent (antiredeposition action or graying inhibition), to finishing (fabric action) and even to the provision of a “stone washed” effect.
One usable fungal cellulase preparation with an elevated endoglucanase (EG) content or further developments thereof are offered for sale by Novozymes under the trade name Celluzyme. The products Endolase® and Carezyme® likewise obtainable from Novozymes are based on the 50 KD-EG or the 43 kD-EG from H. insolens DSM 1800. Further possible commercial products from this company are Cellusoft® and Renozyme®. The 20 KD-EG cellulase from Melanocarpus, which is obtainable from AB Enzymes, Finland, under the trade names Ecostone® and Biotouch® may also be used. Further commercial products from AB Enzymes are Econase® and Ecopulp® Another suitable cellulase from Bacillus sp. CBS 670.93 is obtainable from: Genencor under the trade name Puradax®. Further commercial products from Genencor are “Genencor detergent cellulase L” and IndiAge® Neutra.
Agents according to the invention may contain further enzymes which fall within the class of hemicellulases. These include, for example, mannanases, xanthan lyases, pectinlyases (=pectinases), pectin esterases, pectate lyases, xyloglucanases (=xylanases), pullulanases and β-glucanases. Suitable mannanases are obtainable, for example, under the name Gamanase® and Pektinex AR® from Novozymes, under the name Rohapec® B1L from AB Enzymes and under the name Pyrolase® from Diversa Corp., San Diego, Calif., USA. The β-glucanase isolated from B. subtilis is obtainable under the name Cereflo® from Novozymes.
In order to increase their bleaching action, detergents or cleaning agents according to the invention may contain oxidoreductases, for example oxidases, oxygenases₁catalases, peroxidases, such as halo-, chloro-, bromo-, lignin, glucose or manganese peroxidases, dioxygenases or laccases (phenol oxidases, polyphenol oxidases). Suitable commercial products which may be mentioned are Denilite® 1 and 2 from Novozymes. Compounds, preferably organic compounds, particularly preferably aromatic compounds which interact with the enzymes, are advantageously also added in order to enhance the activity of the oxidoreductases in question (enhancers) or, in the event of a major difference in redox potential between the oxidizing enzymes and the soiling, to ensure electron flow (mediators).
The enzymes used in agents according to the invention either originally originate from microorganisms, for instance of the genera Bacillus, Streptomyces, Humicola, or Pseudomonas, and/or are produced by suitable microorganisms using per se known biotechnological methods, for instance by transgenic expression hosts from the genera Bacillus or filamentous fungi.
The enzymes in question are favorably purified by per se established methods, for example by precipitation, sedimentation, concentration, filtration of the liquid phases, microfiltration, ultrafiltration, chemical action, deodorization or suitable combinations of these steps.
The enzymes may be added to the agents according to the invention in any form established in the prior art. This includes, for example, solid preparations obtained by granulation, extrusion or freeze-drying or, in particular in the case of agents in liquid or gel form, solutions of the enzymes, advantageously as concentrated as possible, with a low water content and/or combined with stabilizers.
Alternatively, both for the solid and the liquid presentation, the enzymes may be encapsulated, for example by spray drying or extruding the enzyme solution together with a preferably natural polymer or in the form of capsules, for example those in which the enzymes are enclosed as a solidified gel or in those of the core-shell type, in which an enzyme-containing core is coated with a protective layer which is impermeable to water, air and/or chemicals. Further active ingredients, for example stabilizers, emulsifiers, pigments, bleaching agents or dyes may additionally be applied in superimposed layers. Such capsules are applied in accordance with per se known methods, for example by agitated or rolling granulation or in fluidized bed processes. Advantageously, such granules are low-dusting, for example due to the application of a polymeric film former, and stable in storage thanks to the coating.
It is furthermore possible to formulate two or more enzymes together such that a single granular product displays two or more enzyme activities.
A protein and/or enzyme present in an agent according to the invention may be protected, particularly during storage, from damage such as for example inactivation, denaturation or degradation for instance due to physical influences, oxidation or proteolytic cleavage. If the proteins and/or enzymes are isolated from microbes, inhibition of proteolysis is particularly preferred, in particular if the agents also contain proteases. Agents according to the invention may contain stabilizers for this purpose; the provision of such agents constitutes a preferred embodiment of the present invention.
One group of stabilizers comprises reversible protease inhibitors. Benzamidine hydrochloride, borax, boric acids, boronic acids or the salts or esters thereof are frequently used, in particular derivatives with aromatic groups, for instance ortho-, meta- or para-substituted phenylboronic acids or the salts or esters thereof. Peptide aldehydes, in other words oligopeptides with a reduced C terminus, are also suitable. Peptide protease inhibitors which may inter alia be mentioned are ovomucoid and leupeptin; an additional option is the formation of fusion proteins from proteases and peptide inhibitors.
Further enzyme stabilizers are aminoalcohols such as mono-, di-, triethanol- and -propanolamine and mixtures thereof, aliphatic carboxylic acids up to C₁₂, such as succinic acid, other dicarboxylic acids or salts of the stated acids. End group-terminated fatty acid amide alkoxylates may also be used as stabilizers.
Lower aliphatic alcohols, but especially polyols, such as for example glycerol, ethylene glycol, propylene glycol or sorbitol are further frequently used enzyme stabilizers. Diglycerol phosphate also provides protection from denaturation by physical influences. Calcium salts, such as for example calcium acetate or calcium formate, and magnesium salts are likewise used.
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 with regard to physical influences or fluctuations in pH. Polymers containing polyamine N-oxide act simultaneously as enzyme stabilizers and as dye transfer inhibitors. Linear C₈-C₁₈polyoxyalkylenes are other polymeric stabilizers. Alkyl polyglycosides are likewise capable of stabilizing the enzymatic components of the agents according to the invention and even of enhancing their performance. Crosslinked nitrogenous compounds perform a twin function as soil-release agents and as enzyme stabilizers.
Reducing agents and antioxidants such as sodium sulfite or reducing sugars increase the resistance of the enzymes to oxidative degradation.
Combinations of stabilizers are preferably used, for example prepared from polyols, boric acid and/or borax, the combination of boric acid or borate, reducing salts and succinic acid or other dicarboxylic acids or the combination of boric acid or borate with polyols or polyamino compounds and with reducing salts. The action of peptidelaldehyde stabilizers may be enhanced by combination with boric acid and/or boric acid derivatives and polyols and accordingly further strengthened by the additional use of divalent cations, such as for example calcium ions.
The use of liquid enzyme formulations is particularly preferred for the purposes of the present invention. Preferred agents according to the invention are those which additionally contain enzymes and/or enzyme preparations, preferably solid and/or liquid protease preparations and/or amylase preparations, in quantities of 1 to 5 Wt. %, preferably of 1.5 to 4.5 and in particular of 2 to 4 wt. %, in each case relative to the entire agent.
A wide range of the most varied salts may be used as electrolytes from the group of inorganic salts. Preferred cations are alkali metals and alkaline earth metals, preferred anions are halides and sulfates. From a manufacturing standpoint, it is preferred to use NaCl or MgCl₂in the granules according to the invention.

The exemplary embodiments presented in the following Figures illustrate the invention in greater detail. In the Figures

FIG. 1: shows a perspective view of a container with a blister pack arranged by the container opening

FIG. 2 a: shows a blister pack for arrangement by a container opening and comprising a plurality of small portions

FIG. 2 b: shows a blister pack for arrangement by a container opening and comprising larger portions

FIG. 2 c: shows a blister pack for arrangement by a container opening and comprising portions separable into segments

FIG. 2 d: shows a blister pack for arrangement by a container opening and having bending lines

FIG. 2 e: shows a blister pack for arrangement by a container opening in the bent state

FIG. 3 a: shows a blister pack in cross-section

FIG. 3 b: shows a blister pack in cross-section with a permeable membrane and a sealing membrane

FIG. 4 a: shows a blister pack with snap-in closure

FIG. 5 a: shows a plan view of a dimensionally stable receiving means for additive portions

FIG. 5 b: shows a cross-section of a dimensionally stable receiving means for additive portions

FIG. 1 shows a particular embodiment of the invention, in which a blister pack (3), placed over the closure and pouring cylinder of the container (1), is fastened to the container (1). A closure (2) comprising a peripheral shoulder (2 a) is arranged on the closure and pouring cylinder.
FIGS. 2 a-e show a detail view of an embodiment of the blister pack according to the invention.
The blister pack (3) comprises an opening (4) which may be placed over the pouring cylinder (2) of the container (1). In a further embodiment (not shown), it is also possible for the blister pack (3) to be placed fixably with the opening (4) over the closure (2) of the container (1).
The opening (4) of the blister pack (3) may be entirely or only partially closed, the opening (4) being designed such that it prevents at least simple detachment of the blister pack from the container.
One or more blister elements (5 a, 5 b) extend from the collar (7), each element comprising a plurality of cavities (6) which are conventionally arranged over the surface (5 a, 5 b) of the blister pack (3).
The collar (7) is designed such that the closure (2), when in its closed position, exerts a clamping force acting substantially perpendicularly to the blister plane on the collar (7). The opening (4) of the blister pack is here smaller than the shoulder (2 a) of the closure (2), such that, when the container is closed, the blister pack does not become detached from the container (1), but is instead held on the container (1) by the shoulder (2 a) of the closure (2). The shoulder (2 a) of the closure (2) should be selected such that it may act at least in part on the surface surrounding the opening (4) of the blister pack (1).
In one particularly preferred embodiment, the blister pack (1) has a circular opening (4) and two flat elements (5 a, 5 b) arranged radially relative to the opening. The blister pack (3) is designed such that the two limbs (5 a, 5 b) of the blister pack (3) may in each case be lifted at their distal ends.
The blister pack (1) may, for example, be fastened to the container by an adhesive bond. The adhesive bond here extends only over a subarea of the blister pack (1) such that the remaining area may be lifted from the container in order to press a product portion out of the blister pack (1)
FIG. 2 b shows a further particularly preferred embodiment of the invention, in which the cavities (6) of the blister pack (3) extend substantially over the entire area of the blister elements (5 a, 5 b) arranged over the collar (7). These cavities (6) are in particular suitable for accommodating larger product portions, as is for example necessary for long-lasting fragrancing of the surroundings of the blister pack (3).
FIG. 2 c shows a further embodiment of a blister pack (3) for fastening to an outlet cylinder of a container (1). The blister pack (3) has cavities (6), which, thanks to the perforations (8) surrounding the cavities (6), are designed to be individually separable from the blister pack (3).
Instead of perforations (8), it is also possible to provide other means considered suitable by a person skilled in the art for separating a portion from the blister pack (3).
It is also possible to provide the perforations (8) only on the film/foil which seals the cavities (6), such that segment-by-segment opening of the blister pack (3) is possible by peeling off the corresponding portion of film/foil.
FIG. 2 d shows a blister pack (3) having an opening (4) which is completely or partially surrounded by a collar (7). A web (13) is arranged on the collar (7), said web having at least one predetermined bending line (8).
According to a particularly preferred embodiment of the invention, the web (13) comprises two predetermined bending lines (9) spaced apart from one another. The distance (b) between the two predetermined bending lines (9) spaced apart from one another should be selected such that it substantially corresponds to the height of the pouring cylinder (14).
The predetermined bending line (8) is conventionally a substantially linear weakening in the material of the web (13), which may for example be formed by perforation, provision of recesses or compaction of the material.
A blister element is arranged at the end of the collar (7) remote from the web (13), which element comprises a cavity (11) filled with a product and completely surrounded by a rim (10).
FIG. 2 e shows the blister pack according to FIG. 2 d placed over the closure cylinder (14) of a container (1). The blister pack (3) is bent along its predetermined bending lines (9) in each case by 90° in such a manner that the filled cavity (11) is positioned directly over the opening of the closure cylinder.
The cavity (11) of the blister pack (3) is designed such that it may be substantially completely introduced into the opening of the closure cylinder (14).
According to a particularly preferred embodiment, the upper side of the rim (10) in the bent state of the blister pack lies directly on the wall of the closure cylinder (14).
In a further particularly preferred embodiment, the rim (10) additionally comprises means which interact with the closure cylinder in such a manner that the blister pack (3) is secured against lateral slippage on the closure cylinder. This may be achieved, for example, by an appropriately shaped circumferential groove or lug on the rim (10) of the blister pack (3).
In another embodiment of the invention, it is also possible, by appropriate selection of the spacing (b) of the predetermined bending lines (9) and bending of the web (13) along the predetermined bending lines (9), for the cavity (11) to be positionable in an appropriately shaped opening or surface of the closure (2) arranged on the closure cylinder (14).
FIG. 3 a shows a cross-section through a representative cavity (6, 11) of a blister pack (3) according to the invention. In the simplest embodiment, the cavity (6) filled with product (16) is formed by a lower film/foil (17) and closed by a sealing film/foil (15). The material of the sealing film/foil (15) should be selected such that specific substances in the product (16), in particular fragrances, are not released to the surroundings.
The lower film/foil (17) consists of a material which is sufficiently strong to avoid unintentional opening, but which can be opened by the application of appropriate pressure, for example by pressing with the thumb or tearing the film/foil with a fingernail. Exerting pressure on a cavity (6) of the blister pack (3) results in pressure being exerted on the product (16) located in the cavity (6), the product then ultimately puncturing the sealing film/foil (15).
The sealing film/foil may also be at least partially opened towards the cavity by tearing, piercing, rubbing, peeling, by contact with water, by heat, in particular by the heat of human skin, or other suitable measures.
According to a further embodiment of the invention, the blister pack (3) may also be configured such that the film/foil (17) forming the cavity (6) is so much stronger that the film/foil (17) forming the cavity (6) is opened by the applied pressure and the sealing film/foil (15) closing the cavity (6) remains undamaged.
FIG. 3 b shows a further developed embodiment of the blister pack (3) which, in addition to the sealing film/foil (15), comprises a permeable membrane (18). The permeable membrane (18) is arranged between the film/foil (17) forming the cavity (6) and the sealing film/foil (15), the sealing film/foil (15) preferably being arranged by a detachable adhesive bond over the surface of the permeable membrane (18).
The material and the properties of the permeable membrane (18) should be selected such that at least one substance in the product (16) may be released from the cavity (6) through the permeable membrane (18) to the surroundings. In the simplest case, the permeable membrane (18) comprises a mesh which is suitable for retaining appropriate solids in the cavity.
In particular, the properties of the permeable membrane (18) should be selected such that fragrances can be released from a liquid, gel-form or solid product out of a cavity (6) to the surroundings.
The permeable membrane (18) is preferably adhesively bonded with the film/foil (17) forming the cavity (6) such that the permeable membrane (18) closes the cavities (6). The adhesive forces between the permeable membrane (18) and the film/foil (17) forming the cavity (6) are preferably greater than the adhesive forces between the permeable membrane (18) and the sealing film/foil (15), such that, when the sealing film/foil (15) is peeled off, the permeable membrane (18) remains bonded to the blister pack (3) and closes the cavities (6).
FIG. 4 a shows another embodiment of the invention, in which a snap-in connector element (19) is arranged on the blister pack (3), which connector element may be interlockingly connected, preferably detachably, with a corresponding receptacle (20) on the packaging unit (1, 2, 14). It goes without saying that the blister pack (3) may also comprise a plurality of snap-in connectors (19, 20).
In one particularly preferred embodiment of the invention, the blister pack (3) may also be fastened by an appropriate snap-in connector to the closure (2) of the container (1).
According to a particularly preferred embodiment of the invention, the blister pack is at least in part provided with an adhesive layer which is covered with a detachable sealing film/foil, whereby the blister pack (3) or individual portions (6) of the blister pack (3) may be fastened to surfaces.
The products (16) disposed in the cavities (6) comprise in particular, but not exclusively, one or more substances selected from the group comprising fragrances, substances with a cleaning action, dyes, foaming agents etc.
FIG. 5 a shows a plan view of a dimensionally stable receiving means (3) for additive portions (21). The receiving means (3) comprises a plurality of receiving openings (22) for additive portions (21). A receiving opening (22) interacts with an additive portion (21) in such a manner that the additive portion (21) is detachably fastened in the receiving opening (22). This may be achieved, for example, by an interlocking, frictional or materially bonded connection between the additive portion (21) and the receiving opening (22). Fastening should in each case be provided such that the additive portion (21) cannot unintentionally fall out of the receiving opening (22), for example during transport or storage.
In a preferred embodiment of the invention, the additive portion (21) is fastened in a receiving opening (22) by a detachable press fit. In a further preferred variant embodiment, the additive portion (21) and receiving opening (22) are fastened together by a detachable snap-in connector.
The receiving openings (22) may for example take the form of a through-hole or a blind hole. Any other design of the opening deemed obviously equivalent by a person skilled in the art is feasible, such as for example openings with a rectangular, triangular or oval cross-section.
The additive portion (21) comprises a closure which impermeably closes the additive portion (21) relative to the surroundings. The closure is advantageously designed such that the additive portion (21) can be closed in fluid-tight manner relative to the surroundings. The closure is particularly preferably designed such that the additive portion (21) may be closed substantially impermeably with regard to the emission of fragrances.
The closure is arranged detachably on the additive portion (21) in interlocking, frictional or materially bonded manner. In particular, the additive portion (21) may be impermeably closable relative to the surroundings by the closure by means of a press fit, a screw closure, a snap-in connector or adhesive bonding.
In a further embodiment, the additive portion (21) is closed with a bung. The bung preferably consists of a resilient material and is designed such that it closes the additive portion (21) in at least fluid-tight manner.
It is furthermore conceivable to provide the additive portion (21) with sealed openings. The openings may take the form of holes through the lateral, bottom or top surface of the additive portion (21). Any other suitable form for the openings is, however, also feasible, such as for instance slots, meshes etc. The seal of the openings is designed such that the openings are closed in fluid-tight manner. In one particularly preferred embodiment, the seal is substantially impermeable with regard to the emission of fragrances from the portion volume into the surroundings. The seal may in particular comprise a plastics film which is at least in part, preferably detachably, adhesively bonded with the surface of the additive portion. It is also conceivable to seal the openings by means of a “sleeve”, a suitable plastics film being drawn tautly around the portion container.
In another embodiment, the additive portion (21) is filled with a non-free-flowing substance. In this case, the additive portion may be shaped like a cup which has an open end face. Alternatively, the additive portion (21) could also comprise openings on its lateral surface.
In this connection, non-free-flowing means that the substance disposed in an additive portion cannot escape into the surroundings through the openings. This may be achieved, for example, by using a solid or solid granules, the size of the solid granules being set, for example, such that they do not fit through the openings or the solid is fastened in the portion volume.
The additive portions may be arranged in two positions in the receiving means (3). In a first, closed position, the openings of the additive portion (21) are completely closed by the lateral or bottom surface of the receiving opening (22).
As is apparent from FIG. 5 b, it is possible, by taking an additive portion (21) out of the receiving opening (22), to arrange the additive portion (21) in a second position in a receiving opening (3) of the receiving means (3), in which the openings of the additive portion (21) correspond with the surroundings and constituents of the substance located in the additive portion (21) are released, preferably by diffusion, into the surroundings.
Additionally, in this case, the opening or openings of the additive portion (21) may be covered by a protective film which initially prevents release of the product into the surroundings by diffusion. The protective film may be removed for example by tearing or rubbing, such that product may then be released into the surroundings.
The receiving means (3) comprises an opening (4) which is detachably connected to the opening of the container in interlocking, frictional or materially bonded manner. In a preferred embodiment of the invention, the receiving means (3) comprises an opening (4) which may be placed over the pouring cylinder of the container. The opening (4) may here be entirely or only partially closed, the opening (4) being designed such that it prevents at least simple detachment of the receiving means from the container. Alternatively, it is also possible to connect the receiving means (3) detachably to the container closure in interlocking, frictional or materially bonded manner.

Claims

1-15. (canceled)

16. A packaging unit, comprising:

a container (1) for accommodating a product, said container having an opening (14) for discharging the product from the container,

a closure (2) for covering the opening (14), and

at least one receiving means (3) having at least one additive portion (6, 11, 21) for holding an additive prior to dispensing such additive into the product, wherein the receiving means (3) is detachably fastenable to the container (1) or the closure (2) or both.

17. The packaging unit as claimed in claim 16, wherein the receiving means (3) comprises a first means (4, 7, 19) for fastening the receiving means (3) to the container (1) or closure (2) or both, which first means interacts in such a manner with a second means (2, 14, 20) arranged on the packaging unit (1, 2, 14) so that the receiving means (3) is detachably fastenable, substantially in interlocking, frictional or materially bonded manner, to the container (1) or closure (2) or both.

18. The packaging unit as claimed in claim 17, wherein the receiving means (3) has an opening (4) that may be placed over a closure cylinder (14) of the container (1) so that the receiving means (3) is held in contact with the container (1) by the closure (2).

19. The packaging unit as claimed in claim 17, wherein the first and second means for fastening the receiving means (3) to the packaging unit form a snap-in connector.

20. The packaging unit as claimed in claim 16, wherein the additive portions take the form of a blister pack.

21. The packaging unit as claimed in claim 20, wherein the receiving means (3) defines a cavity (11) and includes a web (13), and wherein said web (13) comprises at least two predetermined bending lines (9), along which the receiving means (3) may be bent in such a manner that the cavity (11) may be positioned substantially in an opening defined by a closure cylinder (14) of the container (1).

22. The packaging unit as claimed in claim 20, wherein at least some of the additive portions (6) are surrounded by at least one perforation line (8) in such a manner that an individual additive portion or group of additive portions (6) is separable from the blister pack (3) along one or more perforation lines (8).

23. The packaging unit as claimed in claim 20, wherein the additive portion (6) is formed with a film/foil (17) and a removable sealing film/foil (15), and on removal of the sealing film/foil (15), a permeable membrane (18) adheres to the receiving means (3) and closes the additive portion (6).

24. The packaging unit as claimed in claim 20, wherein the receiving means (3) comprises an adhesive portion with an adhesive layer which is covered with a detachable sealing film/foil.

25. The packaging unit as claimed in claim 16, wherein the receiving means (3) is substantially dimensionally stable and comprises receiving openings (22) which are designed such that additive portions (21) are detachably fastenable in the receiving openings (22) in interlocking, frictional or materially bonded manner.

26. The packaging unit as claimed in claim 25, wherein the additive portions (21) comprise at least one opening which is closable with a closure means.

27. The packaging unit as claimed in claim 25, wherein the additive portions (21) comprise at least one opening which interacts with the receiving openings (22) in such a manner that the opening of an additive portion (21) fastened in the receiving opening (22) is closed.

28. The packaging unit as claimed in claim 25, wherein the at least one additive portion (21) contains a non-free-flowing substance (16).

29. The packaging unit as claimed in claim 16, wherein a first additive is held within at least one additive portion (6, 21) and a second additive that differs with regard to its fragrance, surfactant, and/or dye composition from the first additive is held within at least one other additive portion (6, 21).

30. The packaging unit as claimed in claim 16, wherein at least one part of the receiving means (3) is adhesively bonded to the container (1), or the closure (2) or both.

31. A holder for flowable product additives to be dispensed into a product, comprising:

a receiving means (3) having at least one receiving opening (22) for receiving an additive portion (21) that holds one or more additives prior to dispensing such additive(s) into the product, wherein the receiving means (3) is substantially dimensionally stable and is detachably fastenable to a product container, or a closure releaseably connectable to the product container (2), or both, and wherein the additive portions (21) are detachably fastenable in the receiving openings (22) in interlocking, frictional or materially bonded manner.

32. The holder as claimed in claim 31, wherein the receiving means (3) has a plurality of receiving openings (22) and associated additive portions (21), and the additive portions (21) comprise at least one opening which interacts with the receiving openings (22) in such a manner that the opening of one additive portion (21) fastened in its associated receiving opening (22) is closed.

33. The holder as claimed in claim 31, wherein the receiving means (3) has a plurality of receiving openings (22) and associated additive portions (21), and wherein a first additive is held within at least one additive portion (21) and a second additive that differs with regard to its fragrance, surfactant, and/or dye composition from the first additive is held within at least one other additive portion (21).