WO2010145677A1

WO2010145677A1 - Container for storing and metering delivery of a bulk material

Info

Publication number: WO2010145677A1
Application number: PCT/EP2009/004444
Authority: WO
Inventors: Peter Kertels
Original assignee: Noatec Gmbh
Priority date: 2009-06-19
Filing date: 2009-06-19
Publication date: 2010-12-23

Abstract

The invention relates to a dispensing container (10) for a bulk material stored under pressure in a filling space (22) of the container, comprising an elastically stretchable pressure body (20) bounding the filling space for generating a pressure acting on the bulk material and usable for discharging the bulk material. According to the invention, the pressure body comprises a material layer made of a polyurethane elastomer.

Description

Container for storage and metered delivery of a product

The invention relates to a container for storage and metered delivery of a product, which is received in a pressure chamber of the container.

The container considered in the context of the invention is intended to serve for the controlled dispensing, in particular, of liquid, creamy, pasty or gelatinous substances. Periodically, the container will be provided with suitable valve means which may be selectively opened by the user, for example by pressing or otherwise actuating a valve actuator (e.g., knob, lever). In the container, the substance (contents) received therein is under pressure. This pressure causes when opening the valve, that parts of the product flow out of the container. An additional force effect from the outside is not required. Depending on the configuration of the valve means, the outflowing substance can maintain its state of aggregation as within the container or, for example, foam on leaving the container or disperse into a spray mist.

As a pressure generating means for generating the pressure acting on the filling pressure gas (propellant gas) are known, which of course usually require a pressure-resistant design of the container and at least in former times often had harmful effects on the climate. As an alternative, the use of an elastically stretchable, tubular or condom-like filling bubble has been proposed in the printed prior art, in which the filling material is filled and which expands massively during filling. The stretching work is stored in the form of potential energy in the filling bubble. This energy is used to generate the force required to dispense the product. Because the application force is applied by the (expanded) bubble itself, it can also be called a (fillable) force or pressure body.

Examples of containers with elastically stretchable filling bubbles whose expansion stress is used to generate the required application force can be found in DE 43 33 627 C2, DE 201 20 143 Ul and DE 201 20 142 Ul. The invention relates to containers of the type shown in these documents, ie containers (of whatever shape), which have an elastically extensible pressure body, wherein said Pressure body limited at least one filling space for the contents and used to produce a force acting on the filling pressure.

In a container of this type, it is an object of the invention to enable mass production on an industrial scale and over a wide Füllgradbereich to achieve acceptable application forces for the contents, which should also not change significantly over the intended storage period of the contents.

This object is achieved in that a container for storage and metered delivery of a product is provided which has an elastically stretchable arranged pressure body for receiving the contents and for exerting pressure on the contents received therein, wherein the pressure body at least one layer of material from a polyurethane Has elastomer.

It has been shown that the polyurethane elastomers considered here (PUR elastomers) can offer a force-elongation characteristic which can produce the intended or desired application force even at very low elongation (low filling) and then over a comparatively large amount Füllbandbreite show no excessive increase in the Ausbringkraft generated by them. This is advantageous for two reasons: firstly, the user of a serving as a dispenser container regularly wishes that the contents flow with as constant a speed as possible from the container, no matter how large the current degree of filling. Second, it is desirable from the user's point of view to get as much of the contents out of the container as possible. In embodiments of the container with a rigid outer housing, where a possible filling residue can not be herausbekommen by manual compression of the container, therefore, the pressure body should still be able to muster a sufficient pressure on the remaining remainder of the contents even at almost complete emptying.

This requirement profile I means that in the unfilled state of the container the smallest possible void volume should be present in the interior of the pressure body (this defines not, at least not self-contraction of the pressure body, ausbringbaren Füllgutrest), but at the same time that the pressure body comparison should be strong enough to provide an acceptably large fill volume. It has been found that with a pressure bubble made of a polyurethane elastomer for practical use acceptable levels of emptying can be achieved. The pressure body is suitably sized and designed so that when filling a container according to the invention with a specified for the container nominal capacity stored in the pressure body expansion energy ensures a Ausbringrate of at least 87%, preferably at least 90% and more preferably at least 93% of the nominal filling, anyway within a planned or predetermined life or maximum storage duration of the filled container. Under certain circumstances, the invention can even ensure discharge rates of more than 95% up to more than 98%, ie 95% or 98% of the filled product quantity can be applied. Containers according to the invention preferably have a nominal filling volume of at least several tens of milliliters, for example at least 50 ml or at least 80 ml, and are readily usable up to nominal filling volumes of several liters. For example, containers according to the invention with nominal filling volumes in the high single-digit or even in the double-digit liter range are conceivable.

In addition, polyurethane elastomers are easy to process and cost-effective. This makes them particularly suitable for mass production. In addition, polyurethane polymers have no harmful properties and are chemically very stable.

The polyurethane elastomers considered within the scope of the present invention include all elastically deformable polyurethane plastics which are suitable for the production of the pressure hull of the container according to the invention. These include polyurethane elastomers which crosslink rubber-elastically during processing (crosslinked polyurethanes) and those with thermoplastic properties (thermoplastic polyurethanes (TPU)).

Polyurethane elastomers are formed by polyaddition reaction of polyisocyanates with polyols. As polyisocyanate diisocyanates according to the present invention may be used, individually or in any desired mixture. Examples of these include diphenylmethane diisocyanate (MDI, methylene bis (4-phenyl diisocyanate), polymeric diphenylmethane diisocyanate (PMDI), toluene diisocyanate (TDI), naphtha lene diisocyanate (NDI), hexamethylene diisocyanate (HDI), isophorone diisocyanate (IPDI) and 4,4'-diisocyanatodicyclohexylmethane (H12MDI). Particularly suitable for the preparation of a polyurethane elastomer used in the present invention is diphenylmethane diisocyanate.

Polyols which may be used in the present invention are long-chain polyether polyols and polyester-polyols, in particular polyether and polyester diols, or mixtures thereof. Preference is given to polyether polyols, in particular polyether diols. Polyols having more than two hydroxyl groups can be used for the preparation of crosslinked polyurethane, wherein the hardness of the polyurethane can be adjusted via the proportions of these polyols having more than two hydroxyl groups to form diols. Alternatively, crosslinked polyurethanes can also be prepared by the reaction of, for example, triisocyanates or by the addition of so-called "crosslinkers", for example 1,4-butanediol.

Suitable polyether polyols can be obtained by base-catalyzed reaction of di- and polyhydric StarT alcohols with epoxides (propylene and / or ethylene oxide). Examples of starting alcohols are glycols, trimethylolpropane, pentaerythritol and glycerol. Thus, long and short chain polyether polyols having two (polyether diols) to eight hydroxyl groups can be obtained. Polyethers with a particularly low mono-ol content, which are obtainable with the aid of special catalysts such as zinc hexacyano-cobaltate, are also usable. Also, amino-polyether polyols obtainable by reacting diamines (e.g., ethylenediamine) or alkanolamines with epoxides can be used.

Suitable polyester polyols may be prepared, for example, by polycondensation of one or more organic dicarboxylic acids of 2 to 12 carbon atoms, such as succinic, glutaric, adipic, suberic, azelaic, sebacic, decanedicarboxylic, maleic, fumaric, phthalic, isophthalic and terephthalic acids with one or more diols such as 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, ethylene glycol, 1,2- and 1,3-propylene glycol, 1,8-octanediol, neopentyl glycol, 1,4-bis-hydroxymethylcyclohexane , 2-methyl-l, 3-propanediol, 3-methyl-l, 5-pentanediol, diethylene glycol, dipropylene glycol, dibutylene glycol, glycerol, trimethylo- lethane, trimethylolpropane and trimethylolbutane. It is also possible to use carbonate ester polyols which are obtained by transesterification of diphenylcarboxylic bonat with diols, such as hexanediol, are accessible. It is also possible to use the poly-ε-caprolactone polyols obtainable by Ti-catalyzed ring-opening polymerization of ε-caprolactone with diols or triols.

For the preparation of the polyurethane elastomers used in the present invention, so-called "chain extenders" may also be used, which are usually low molecular weight dihydroxy or diamino compounds, polyurethane elastomers which are formed with diamino compounds as chain extenders As a rule, however, short-chain diols are used as chain extenders in the context of the present invention, for example ethylene glycol, glycerol, 1,4-butanediol, 2,3-butanediol, 2,5-hexanediol, 1,6-hexanediol , 2,5-dimethyl-2,5-hexanediol, 1,2-propanediol, 1,3-propanediol, 1,5-pentanediol, trimethylolpropane and hydroxyquinone bis (2-hydroxyethyl) ether.

Polyaddition allows the polyols and the short chain diols used as chain extenders to react with the diisocyanate to form the polyurethane. By reaction of polyol with diisocyanate, a soft fraction (soft segments) can thereby form. From the compound of diisocyanate with short-chain diol, a hard portion (hard segments) arise. The resulting polyurethane polymer may therefore have a segmental structure and consist of "crystalline" and "amorphous" blocks ("hard segments" and "soft segments") in a particular sequence. While the hard segments function as network fixed points due to their "crystalline" properties, the soft segments dissolve under the influence of heat without the polyurethane polymers decomposing.

Besides the above main components, the polyurethane elastomer used in the present invention may also contain auxiliaries for production and processing and other additives. To accelerate the reaction between see the polyols, polyisocyanates and optionally chain extenders the reaction mixtures usually conventional catalysts, such as tertiary amines and / or metal compounds added. Other auxiliaries and additives include reaction retardants, stabilizers, anti-aging agents, anti-hydrolysis agents, dyes, pigments, fillers, surfactants, flame retardants and antimicrobial substances. The polyurethane elastomers used in the present invention for producing the at least one polyurethane elastomer material layer of the pressure body generally have a density of 1.0 to 1.25 g / cm ³ (measured according to DIN EN ISO 1183), in particular one Density of 1.1 to 1.2 g / cm ³ , on. The hardness (measured according to DIN 53505) of the polyurethane elastomers is preferably in the range of 40 to 90 Shore A, more preferably in the range of 50 to 80 Shore A and particularly preferably in the range of 60 to 70 Shore A. The tensile strength (measured according to DIN 53504) is preferably 5.0 to 60 N / mm ² , more preferably 10.0 to 35 N / mm ^2, and particularly preferably 15.0 to 30 N / mm ² . The elongation at break of the polyurethane elastomer (measured according to DIN 53504) is at least 100%, but may also be significantly higher. For example, the elongation at break is often in the range of 300% to 600% and in some cases exceeds 600%, 700% or even 800%. The tear propagation resistance (measured according to DIN 53515) is usually at least 10 kN / m and is preferably above 25, 50 or 100 kN / m. The rebound resilience (measured according to DIN 53 512) is preferably in the range of 40 to 80%, in particular in the range of 50 to 70%.

The properties of the material layers of the pressure hull of the container according to the invention produced from the polyurethane elastomers described herein depend primarily on the type and proportions of the starting materials. The polyols used essentially influence certain properties of the polyurethane elastomers. The choice of the type and proportions of the starting materials depend on the desired properties of the polyurethane elastomer, which in turn result from the requirement profile of the pressure body of the container according to the invention. Such desirable properties include, for example, mechanical strength, hardness, elongation (high tensile strength at high elongation at break), elasticity (high modulus of elasticity), good recovery behavior, high flexibility, high tear propagation resistance, high resistance to oxidation and hydrolysis, high resistance to chemicals and good heat resistance. and / or cold resistance.

The polyurethane elastomers which can be used in the context of the present invention can be prepared according to processes known in polyurethane chemistry. For example, a one-step process may be used in which a polyol and optionally a chain extender are reacted directly with a polyisocyanate. It is also possible to use a "prepolymer process." In a first step, an isocyanate group-containing prepolymer is prepared by reacting a polyol with an excess of polyisocyanate, which is then converted in a second step by reaction with polyols and / or chain extenders A modification of this is the "semi-polymer process" in which, unlike the prepolymer process in the first step, the polyisocyanate is reacted with only part of the polyol and the other part of the polyol together with the polyols and / or the chain extenders is added in the second step. Based on the above-mentioned principles, continuous mixing processes can also be carried out.

Particularly suitable for the purposes of the present invention, the pre-polymer method has been found. Especially two-component polyurethane systems have proven to be useful for this purpose. In such two-component polyurethane systems, a component A comprising polyols and optionally chain extenders and a component B comprising the preformed prepolymer are mixed in a particular ratio and used to make the polyurethane elastomers. In the pre-formulated A and / or B

Component are usually all required auxiliaries or additives, in particular catalysts, included.

Polyurethane elastomers which are particularly suitable for the purposes of the present invention are cast elastomers, in particular two-component polyurethane systems. Component A usually comprises a mixture of polyols and catalysts. Component B comprises the prepolymer, for example based on diphenylmethane diisocyanate. The two components are mixed together in a suitable ratio, for example 2: 1 to 1: 1, and then processed to polyurethane elastomer. The mold temperature here is typically in the range of 70 to 110 ⁰ C. The polyurethane elastomer may further to a thermal aftertreatment, for example at 100 ⁰ C for 5 to 24 hours, are subjected. Chain extenders can also be added to component A, as a result of which the properties of the polyurethane elastomer can be matched to the respective area of use. The chain extenders are usually in an amount of up to 15 Parts by weight, usually in an amount of 1 to 10 parts by weight, based on 100 parts by weight of component A used.

According to the present invention, for example, the two-component polyurethane cast elastomers available under the product designation Elasturan® (Elastogran GmbH, Germany) can be used. Particularly suitable are Elasturan® polyether systems. As an example, Elasturan® 6065/104 / A60 can be mentioned. By adding chain extenders, the properties of the Elasturan® base material, in particular the Shore A hardness, the tensile strength and the tear propagation resistance, can be adjusted according to the requirement profile.

The at least one polyurethane elastomer material layer of the pressure body of the container according to the invention can be produced by processing methods known per se. In the case of solid starting components, the processing can be carried out, for example, by injection molding, extrusion or pressing. In the case of liquid starting components, the processing is preferably carried out by means of casting.

The pressure body may be a monolayer or a multilayer structure. He may have a single polyurethane elastomer produced from polyurethane elastomer material layer. Alternatively, however, it may also have a plurality of superimposed material layers, of which at least two are made of polyurethane elastomer material layers. These several polyurethane elastomer material layers may at least partially lie directly on one another or be separated from one another by one or more layers of other material. In the case of a multi-layer structure of the pressure hull, all layers can be bonded together in a material-tight manner, either by direct cross-linking or by using an adhesive. However, at least some of the layers may lie on top of each other even without intimate adhesion and adhere to one another, for example, due to friction. In particular, it should not be ruled out, the double-layered (or generally: multi-layered) to perform the pressure body on the type of packaging shown in DE 43 33 627 C2 and to manufacture only a portion of the layers of the pressure hull of a polyurethane elastomer, the other part from another Elastomer material. In any case, at least one main material layer of the pressure body is preferably formed by a polyurethane elastomer material layer produced from a polyurethane elastomer.

5 Irrespective of whether provided individually or repeatedly, each polyurethane elastomeric material layer can be provided with a thin coating on the inside and / or outside as required, for example for a particularly aggressive product.

In the container according to the invention, the energy for pressurization lo of the filling material preferably originates solely from the elastic expansion of the pressure body. That is, the container according to the invention is preferably free of any propellant gases and also free of any other mechanical force generators, by means of which the filling material located in the pressure body could be pressurized, such as arranged outside the pressure body and acting on this Federan- i5 order.

The ability to make the dispensing container propellant-free, can be used to reduce the overall weight of the container by forming the outer shell of the container, the pressure body receiving housing

20 is made at least for the most part of a rigid plastic material. On the other hand, previous propellant-based dispensers often require a metallic outer housing, which can bring about a correspondingly high weight. This applies, for example, to numerous fire extinguishers which can be carried in the hand or which can be strapped onto the back. A weight

25 savings by not using a metallic, pressure-resistant outer housing can lead to enormous ease of use when using the fire extinguisher.

The accompanying single drawing shows in schematic form an embodiment of a dispenser in which the invention can be used. The container 3o nis - generally designated 10 - is designed here as a can or bottle-like container and has a stable, relatively rigid outer housing 12. In the exemplary case shown, the outer housing 12 is cylindrical (for example with a circular or rectangular cross-section), but in alternative embodiments it may also have a cross-section which varies over its height. The housing 12 has a housing bottom 14, an upper housing part 16 and a running between bottom 14 and upper part 16 jacket 18. Because the container 10 is free of propellant gas, the housing 12 can be made less resistant compared to pressure-resistant metal housings. It may therefore consist of a comparatively lightweight material and / or be designed comparatively thin-walled. For example, the housing 12 may be made of a plastic material or even at least partially of a cardboard material. It goes without saying, however, that the invention can equally be used with a metal housing, as is known, for example, from conventional spray cans with a sheet-metal housing.

10

In the case 12, a rubber-elastic pressure body (filling bladder) 20, which is made in one layer in a single layer, is accommodated in the housing 12, which is made of a polyurethane elastomer. The pressure body 20 is designed here as a single-chamber bladder, which limits a single filling space 22 for the contents to be stored in the dispensing container 10. In alternative embodiments, the pressure body 20 may also form, if necessary, at least two separate filling chambers. On the upper housing part 16, a dispensing unit 24 (valve assembly) is attached to a dispensing valve, not shown, which selectively by means of a trained here as niederdrückbarer actuator head actuator 26 by the user for the

2o delivery of contents from the container 10 can be opened. The substance to be dispensed exits at a dispensing opening 28, for example in strand form, as a foam or as a spray. The pressure body 20 is connected in a manner not shown close to the dispensing unit 24. Exemplary constructions for the tight coupling of a stretchable elastomer body serving for filling material intake

25 pers to a donation unit can be found in the above-mentioned documents DE 201 20 142 Ul and DE 201 20 143 Ul.

In the empty, i. not yet filled state, the pressure body 20 has, for example, the shape of a downwardly closed piece of tubing or tube, approximately in the form

30 of a rolled out condom with a small void volume. In this state, the pressure body touches neither the bottom 14 of the housing 12 nor the jacket 18. The small size of the void volume of the pressure hull 20 in the unfilled state ensures a correspondingly high discharge rate (emptying rate). When filling the pressure body 20, this expands both in length and in width

35 until it finally comes into contact with the jacket 18 and the bottom 14 of the housing 12. This situation is shown in FIG. It is understood that the in Fig. 1 shown state does not yet have to be the final filling state; Another filling beyond the state of FIG. 1 addition is quite possible. When filled, the pressure body 20, for example, the shape of a bubble (comparable to an inflated balloon). The pressure necessary for filling is absorbed by the elasticity of the pressure body 20 and is stored there in the form of potential energy. Upon actuation of the dispensing unit 24, the stretched pressure body 20 urges a portion of the contents contained therein out of the filling space 22; Here, the pressure body 20 pulls something together. The application force required for the application of the filling material is therefore applied solely by the pressure body 20.

The pressure body 20 is preferably designed so that it is applied to the housing bottom 14 when filled up to a predetermined nominal filling quantity, but there is no upturning, ie. sometimes lifts off from the ground 14 and bulges toward the inside of the housing away from the ground. An attachment of the

Pressure body 20 on the housing bottom 14 ensures stabilization of the pressure hull within the housing 12. This stability is endangered when the pressure hull kinks and thus partially removed from the ground. In addition, reduced by such a collapse of the pressure hull 20 of the available filling space.

Containers according to the invention are suitable for the metered delivery of any liquid, pasty, creamy or gelatinous substances. They can also be used for example as a fire extinguisher and serve for the application of a suitable flowable extinguishing powder or extinguishing gel.

Exemplary substances which can be applied in a controlled manner with the container according to the invention are from the cosmetics sector creams and lotions for body care, shaving gels and shaving foams, hair sprays, hair foams, deodorant sprays, foot sprays and perfumes, from the pharmaceutical industry asthma sprays, nasal sprays, disinfectant sprays and wound sprays, from the household sector

Room sprays, polishing sprays, laundry starches, carpet foams, insecticides, leather sprays, impregnating sprays, ironing sprays, bathroom cleaners etc., from the technical field car care products and lubricants, and from the food industry spray cream, mayonnaise, ketchup, mustard and cheese. It is understood that this is only exemplary Products and applications are and that numerous other applications are possible.

Claims

claims

1. Container for storage and metered delivery of a filling material, wherein the container 5 has an elastically stretchable arranged pressure body (20) for receiving the contents and for exerting pressure on the contents received therein, characterized in that the pressure body at least one material layer of a polyurethane Has elastomer.

2. Container according to claim 1, characterized in that the polyurethane elastomer has a hardness in the range of 40 and 90 Shore A, preferably in the range of 50 to 80 Shore A and more preferably in the range of 60 to 70 Shore A.

3. Container according to one of the preceding claims, characterized in that the polyurethane elastomer has a density of 1.0 to 1.25 g / cm ³ , preferably between 1.10 and 1.20 g / cm ³ .

4. Container according to one of the preceding claims, characterized in net 20, that the polyurethane elastomer has a tensile strength in the range of 5.0 to 60

N / mm ² , preferably from 10.0 to 35 N / mm ² .

5. Container according to one of the preceding claims, characterized in that the breaking elongation of the polyurethane elastomer is at least 100%.

25

6. Container according to one of the preceding claims, characterized in that when filling the container with a specified for the container nominal filling quantity in the pressure body (20) stored strain energy at a discharge rate of at least 87%, preferably at least 90%, more preferably

30 guaranteed at least 93% of the nominal filling quantity.

7. Container according to one of the preceding claims, characterized in that the polyurethane elastomer is obtainable by polyaddition of a diisocyanate, a polyether or polyester polyol and optionally chain extenders having two hydroxyl groups.

5

8. Container according to one of the preceding claims, characterized in that the polyurethane elastomer material layer is a Hauptmateriallage the pressure hull (20).

9. A container according to any one of claims 1 to 8, characterized in that the pressure body (20) has a single polyurethane elastomer material layer made of a polyurethane elastomer.

10. Container according to one of claims 1 to 8, characterized in that i5 of the pressure body has a plurality of superimposed layers of material, of which at least two polyurethane elastomer material layers.

11. Container according to one of the preceding claims, characterized in that the polyurethane elastomer material layer inside or / and outside

20 is coated.

12. Container according to one of the preceding claims, characterized in that the polyurethane elastomer material layer is produced by injection molding, extrusion or casting.

25

13. Container according to one of the preceding claims, characterized in that the pressure body (20) is received in a stiffer compared to this housing executed.

14. The container according to claim 13, characterized in that at least a predominant part of the housing (12) is made of a plastic material, cardboard or sheet metal.

15. Container according to claim 13 or 14, characterized in that the pressure body (20) is designed so that it rests upon filling up to a predetermined nominal filling quantity without invagination on a bottom (14) of the housing (12).