The present invention relates to free-flowable compositions in a pouch which contain different free-flowable components fixed in different regions and to process for making these pouched compositions. The pouch and the compartment (s) thereof are preferably made from stretchable, elastic film which is water-soluble. The compositions are preferably cleaning compositions or fabric care compositions.

The present invention relates to compositions in a pouch having a compartment containing different components fixed in different regions and process for making these pouched compositions.
Cleaning compositions nowadays come in a number of product forms, such as granules, liquids and tablets, each form having its advantages and disadvantages.
Recently, tablets have gained renewed interest, mainly because they are easy to handle for the consumer and easy to dose (xe2x80x98unit dosexe2x80x99) and they have as additional benefit that they allow incompatible ingredients to be incorporated separated from one another, for example in different layers. This can reduce the area of contact of these incompatible materials and thus reduce the occurrence of any reaction between such materials.
However, to make tablets storage stable and to prevent breakage of the tablets during handling, the ingredients need to be compressed together and generally binding agents are needed to ensure the tablets do not break. This can reduce their solubility and dispersibility, which is undesirable for the consumers and also from a performance point of view.
Thus, alternative ways or better ways are required for providing easy to handle, unit dose products whereby different ingredients can be present separate from one another in an easy way (for example to reduce intimate contact and improve stability of incompatible ingredients) which do not dust or break.
The inventors have now found an improved way for providing improved products addressing the above problems, namely by incorporating a product in a pouch in a specific way, such that the above requirements are fulfilled.
Pouches for detergents as such are known in the art to be useful to provide unit dose compositions and to separate ingredients from one another. For example, U.S. Pat. No. 5,224,601 describes a packages made with different compartments for different materials. However, this type of structure and also other pouches known in the art have their problems and often requires a complicated manufacturing route and a relatively large amount of sheet material.
The inventors have now found improved pouched particulate compositions which are such that intimate contact with different components thereof is reduced, without the need to compact them to the extent of tablets and without the need of difficult structures, such as multiple separate compartments, to separate different ingredients from one another. In the products of the invention, the different components of the compositions are namely packed tightly in different regions of one and the same compartment or pouch, such that they are substantially immobilised or fixed and thus remain like that during handling and storage. However, because the components are still in powder or granular form and are not stuck together as in tablets, the dissolution or dispersion of the composition comprising these components into water is very fast. Thus, improved storage stability of for example incompatible ingredients like enzymes and bleach is achieved, with a minimum of pouch material and with very good product delivery and performance.
Furthermore, improved processes are provided to form the pouched composition, such that the components in the regions stay fixed or immobilised.
The present invention provides a composition in a pouch, the composition comprising two or more particulate components and the pouch comprising one or more water-disintegrating, water-soluble or water-dispersable compartments, whereby at least two of the components are present in one and the same compartment and each form a fixed region in said compartment.
In particular, the composition in a pouch of the invention is obtainable by a process comprising the steps of:
a) obtaining a open pouch comprising an open compartment;
b) introducing one particulate component prior to at least one other particulate component in the open compartment and/or introducing one particulate component in a different part of the open component than at least one other particulate component; and
c) subsequently closing the open compartment such that a pouch with a (water-soluble water or water-dispersible) compartment comprising fixed regions of said particulate components is obtained.
The components are so tightly packed that the regions are fixed, whilst the composition is still free-flowing (which can be noted when the pouch is removed). This provides the benefits as set out above.
Typically this can be done by overfilling the open compartment, using stretchable and preferably elastic material for the compartment, or using heat-shrinkable material for the compartment or filling and closing the open compartment under reduced pressure or even vacuum.
The composition in the pouch is preferably such that the bulk density of the composition after closing the compartment is 5% to 45% or even to 35%, preferably 5% to 30% or even 10% to 25% higher than the average of the bulk density of the components prior to introduction into the compartment.
Preferably, the pouch as a whole is water-soluble. Preferably the composition is a cleaning composition or fabric care composition or rinse additive composition.
The invention also provides processes for making the pouched compositions of the invention, for example by the process described above and preferred processes as claimed and described hereinafter. One preferred process is such that it results in a non-uniform thickness of the compartment material, which can provide very rapid release of product into water, or can help control the time of release of the different components to the wash water.
Compositions and Components Thereof
The composition of the invention is present in a pouch and is herein also referred to as pouched composition. The composition comprises at least two different particulate components. Generally, the particulate component is a powder or granules, extrudate or flakes.
When used herein, xe2x80x98differentxe2x80x99 component means that one component has at least one different chemical property, for example at least one different ingredient, than the other component or components, or one component has at least one different physical property than another component or component. Typically, one component comprises one or more oxidising ingredients and another component comprises one or more reducing ingredients or oxidisable ingredients. Examples are described herein after.
The particulate components are present in the compartment such that they form fixed or immobilized regions within this compartment.
The fixation of the regions limits the direct contact of the components of the composition with one another, preferably only to the area were the regions touch, without the need of separate compartment structures for the components.
Typically, regions are formed by introducing one particulate components into an open compartment prior to another particulate component, so that for example layers of components are obtained. Alternatively, or in addition, this can be formed by introducing one component in a different part of the open compartment.
Typically, the regions are fixed or immobilized by tightly packing the components together and ensuring that there is substantially no free head-space within the compartment which would allow the powders to move. Typically, the tight packing is such that the bulk density of the components after closing the compartment and thus the bulk density of the compositions in the pouch is from 5% to 45% preferably to 35%, preferably 5% or even 10% to 30% or even to 25% or it may be preferred that this is from 8% to 20% or even 15% higher than the average bulk density of the components prior to incorporation in the pouch.
The bulk density of a component prior to incorporation in the pouched composition can be determined by the Repour Cup method, as described in ISO 3424-1975-E. The average bulk density of the components prior to incorporation in the compartment is worked out by first measuring the bulk density of each component using ISO 3424. Then, a weighted average is calculated based on the weight percentage of the component in the final composition. For example, a pouch consist of one compartment with a composition consisting of two components A and B. Component A is present at 40% by weight of the final composition. Component B is present at 60% by weight of the final composition. Component A has a Repour Cup bulk density (as measured by ISO 3424) of 500 g/l. Component B has a bulk density of 800 g/l (as measured by ISO 3424). The average bulk density of the composition prior to being incorporated into the pouch is therefore ((500xc3x970.4)+(800xc3x970.6))=680 g/l.
The average bulk density of the pouched composition, after closing of the compartment, can be determined by a method of volume displacement. A vessel with a wide neck and an off-take arm is filled with a solvent of known density, which must not affect the compartment material or pouch material, up to the level of the collecting arm. The pouched composition to be tested is accurately weighed and then immersed in the liquid, for example by using a piece of thin metal wire. The amount of liquid that is displaced by the pouched composition in the liquid leaves the vessel through the arm and is collected and carefully weighed. The volume of this displaced liquid is easily calculated from the weight and the known density of the liquid. The density and the volume replacement due to the pouch material (rather than the composition therein) can be measured or calculated. This is deducted from the volume replacement of the liquid as measured in the above test. The density of the composition can then be calculated. (Errors associated with the thin wire used to immerse the pouch are minor and are not taken into account.) Depending on the material of the pouch or compartment, a suitable liquid can be selected. For example, for water-soluble material such as PVA, preferred liquid is glycerol. This is because the pouches may contain microscopic pinholes in the film as a result of the stretching. Using a viscous solvent such as glycerol will minimize any errors due to liquid seeping into the pouch. Also useful are nonionic surfactant such as Neodol 235.
The formation of fixed regions and the tight packing can be done by increasing the packing efficiency and reducing space between the particles of the components, for example by vibration of the components in the open compartment shape, allowing the components to settle for a period of time, modestly increasing pressure, for example by applying a pressure of up to 20 Mpa, preferably up to 10 Mpa or more preferably up to 5 Mpa or even up to 2 MPa, if any pressure is used, provided that the components and the composition remain free-flowing,
The bulk density of the component can be achieved by a compaction step. Typically, the particulate component is first placed in the open compartment, and then a pressure is exerted on said component causing the bulk density of said component to increase from 5% to 50%, preferably from 10% or from 15% or from 20%, and preferably to 45%, or to 40%, or to 35%, or to 30% of the original bulk density of the component prior to the compaction step.
The pressure may be exerted in the form of a solid body, which is typically of a size and shape that is capable of fitting into the opening of the open compartment. The solid body is capable of applying pressure to said component. Preferably, the solid body applies a pressure of up to 20 Mpa, preferably up to 10 Mpa or more preferably up to 5 Mpa or even up to 2 MPa, to the particulate component.
To ensure tight packing of the components in the compartments, the particulate components are for example introduced in the open compartment (preferred processes herefor being described below) such that the open compartment is preferably almost completely filled, typically such that at least 95% of the volume of that open compartment shape, preferably at least 98% or even at least 100% of the open compartment shape is filled, prior to closing said open compartment shape, or it may even be preferred that the shape is overfilled with the components, i.e. that the volume of the components is more than 100% of the volume of the shape, preferably more than 105% or more preferably more than 110% or even more than 115%. Hereby, closing the open compartment which is filled for 95% by volume or more ensures that there is only very limited head-space in the compartment after closing and thus very limited movement of the components in that compartments, i.e. that the regions formed by the components are fixed.
The composition in the pouch herein can for example be obtained by a process involving
a) obtaining an open pouch comprising an open compartment;
b) introducing one particulate component prior to at least one other particulate component in the open compartment and/or introducing one particulate component in a different part of the open component than at least one other particulate component; and
c) subsequently closing the open compartment such that a pouch with a compartment comprising fixed regions of said particulate components is obtained.
In one preferred process, step c) of the process above may be performed under reduced pressure, lower than atmospheric pressure, preferably by applying a vacuum, so that after filling and closing under reduced pressure or vacuum, a tightly packed compartment is obtained.
The compartment is preferably formed from a stretchable material, preferably a film, preferably an elastic film, as described hereinafter. This is in particular useful if the open compartment is filled completely or even overfilled, and is closed by stretchable film, so that by stretching the part of the film used for closing the compartment and/ or by stretching the film of the open compartment, a tight packing and fixed regions are obtained. The use of an elastic material is then preferred, to ensure the tight packing remains over time.
Alternatively, the open compartment is rigid and in step b) the components are introduced in the open compartment such at least 100%, preferably at least 105% of the open compartment is occupied by the components, and the open compartment is then preferably closed with a stretchable material.
The formation of fixed regions and the tight packing may also be achieved by using for the compartment a shrinkable material, whereof the surface area is reduced during or subsequent to closing the open compartment by shrinking the material. A suitable material is for example heat-shrinkable material.
The formation of the open compartment or open shape can be done my any known method. Preferred open shapes are made by introducing the material to form the compartment on to a mold, then applying a vacuum to the mold, so that the material adopts the shape of the mold, also referred to as vacuum-forming. Another preferred method is thermoforming to get the material to adopt the shape of the mold.
The introduction of the components can be done by any method suitable for introducing free-flowing materials into molds.
Whilst the compartment comprises at least two particulate component, a liquid component may be added. It may be preferred to first introduce a first particulate component into the open compartment, then spraying on a small amount of liquid, typically 0.5-10% or even 1% to 5% by weight of the first component, preferably water and subsequently adding the second particulate component. Hereby, the regions can be even more fixed or immobilized.
The component comprises at least an amount of at least one particulate compound, but typically the component comprises at least two particulate compounds, preferably thoroughly mixed to form the component. Because the components in the compartment of the pouch are fixed in fixed regions, the interaction between the different components is reduced. This allows the incorporation in a composition of incompatible ingredients, by separating these per fixed region.
The composition herein can be any particulate composition, in particular any free-flowable granular or powder composition to be delivered to, and active in water.
Preferred compositions are beverages, edible compositions, pharmaceutical compositions, personal care compositions, cleaning compositions, fabric care or conditioning compositions; most preferably, the compositions herein are cleaning compositions or fabric care compositions, preferably hard surface cleaners, more preferably laundry or dish washing compositions, including detergents, pretreatment or soaking compositions or fabric conditioners, and other rinse additives.
When used in cleaning compositions the component can contain any active cleaning ingredients. In particular preferred are active ingredients such as surfactant, chelating agents, builders, enzymes, perfumes, bleaches, bleach activators, fabric softeners, fabric conditioners, antibacterial agents, effervescence sources, brighteners, photo-bleaches. Fabric care compositions preferably comprise at least one or more softening agents, such as quaternary ammonium compounds and/ or softening clays, and preferably additional agent such as anti-wrinkling aids, perfumes, chelants, fabric integrity polymers.
Generally, water is present at a level of 0% to 10%, more preferably from 0.2% to 5% or even 0.2% to 3% or even form 0.5% to 2% by weight of the compartment, preferably of the pouch.
Typically, the composition comprises such an amount of a cleaning composition, that one or a multitude of the pouched compositions is or are sufficient for one wash.
Although the nature of the pouched composition is such that it readily dissolves or disperses into the water, it may be preferred that disintegrating agents such as effervescence sources, water-swellable polymers or clays are present in the pouch or compartment material it self, and/ or in the composition therein; in particular effervescence sources based on an organic acid and a carbonate source are useful. Suitable acids include citric acid, malic acid, maleic acid, fumaric acid; suitable carbonate sources include sodium salts of carbonate, bicarbonate, percarbonate. Preferred levels for the disintegrating aids or effervescence sources or both are from 0.05% to 15% or even from 0.2% to 10% or even form 0.3 to 5% by weight pouched composition.
In particular, for cleaning compositions, it is beneficial that one component comprises at least one or more enzymes and another component comprises a peroxygen bleach such as a salt of percarbonate. The component containing the peroxygen bleach is then free of enzymes, whilst the component comprising the enzyme may comprise a bleach activator, but no peroxygen bleach.
It is also beneficial to include the bleaching agents, but in particular the peroxygen bleach in a different component than any hygroscopic materials or anhydrous or hydratable materials including overdried materials, such as aluminosilicates, anhydrous salts or acids.
When the pouched compositions is such that it has a visually distinguishable top and bottom side, and then, when the regions are in the form of layers, it can also be beneficial to include in the bottom layer non-gelling detergent ingredients, such as water-soluble salts and acids, including for example effervescing salts and acids such as carbonate salts and organic carboxylic acids such as citric acid, and in a higher or top layer potential gelling ingredients such as anionic and nonionic surfactants. Then, it is beneficial to include any peroxygen bleach in the bottom layer and any enzymes in the top layer, if required. It has been found that when such a pouched composition is introduced into the wash via a dispensing device, in particular a dispensing drawer, faster and more complete delivery to the wash is achieved.
It can be beneficial to include any surfactant and bleach into the compartment such that it is delivered before any softening agents in the compartment or pouch.
It may even be possible that part or all of the components are not pre-granulated, such as agglomerated, spray-dried, extruded, prior to incorporation into the compartment, and that the component is a mixture of dry-mixed powder ingredients or even raw materials. Preferred may be that for example less than 60% or even less than 40% or even less than 20% of the component is a free-flowable pre-granulated granules.
Also, it has been found that it is beneficial for the cleaning performance, when the cleaning compositions herein or the material of the compartment or pouch, preferably both the composition and said material, comprise one or more chelating agents, in particular phosphonate- and/or carboxylate-containing chelating agents, in particular EDDS or EDTA or HEDP.
It has also been found that the presence in the wash water of high levels of certain dissolved compartment or pouch material having free hydroxy groups can have a negative effect on the removal of clay stains, under certain wash conditions. Therefore, it is not only beneficial to use as little compartment material as possible and thus to use preferably a pouch with only one compartment, but it has also been found that it is beneficial to incorporate in the composition or the pouch material a polyalkoxylated compound, preferably a polyalkoxylated alcohol, preferably having an average alcohol carbon chain length of 11 to 24, preferably 12 to 20 or even 14 to 18, and an average alkoxylation degree of at least 20 or even at least 40 or even at least 70. Highly preferred are from 0.1% to 8%, or even from 0.5 to 5% or even from 0.8% to 3% by weight of the pouched composition of such a compound; highly preferred is TAE80.
The composition may also comprise liquid compounds or gels or solutions of compounds, for example liquid or gel nonionic surfactants, liquid fabric softeners, preferably then comprised in a separate compartment of the pouch.
Another preferred ingredient is a perhydrate bleach, such as salts of percarbonates, particularly the sodium salts, and/ or organic peroxyacid bleach precursor or activator compound. When the pouch or compartment is formed from a material with free hydroxy groups, such as PVA, the preferred bleaching agent comprises a percarbonate salt and is preferably free form any perborate salts or borate salts. It has been found that borates and perborates interact with these hydroxy-containing materials and can reduce the dissolution of the materials and also that this may result in reduced performance.
Preferred activators or precursors are alkyl percarboxylic precursor compounds of the imide type include the N-,N,N1N1 tetra acetylated alkylene diamines wherein the alkylene group contains from 1 to 6 carbon atoms, particularly those compounds in which the alkylene group contains 1, 2 and 6 carbon atoms such as tetraacetyl ethylene diamine (TAED), sodium 3,5,5-tri-methyl hexanoyloxybenzene sulfonate (iso-NOBS), sodium nonanoyloxybenzene sulfonate (NOBS), sodium acetoxybenzene sulfonate (ABS) and pentaacetyl glucose, but also amide substituted alkyl peroxyacid precursor compounds.
Highly preferred ingredient for use herein are one or more enzymes. Preferred enzymes include the commercially available lipases, cutinases, amylases, neutral and alkaline proteases, cellulases, endolases, esterases, pectinases, lactases and peroxidases conventionally incorporated into detergent compositions. Suitable enzymes are discussed in U.S. Pat. Nos. 3,519,570 and 3,533,139. Preferred commercially available protease enzymes include those sold under the tradenames Alcalase, Savinase, Primase, Durazym, and Esperase by Novo Industries A/S (Denmark), those sold under the tradename Maxatase, Maxacal and Maxapem by Gist-Brocades, those sold by Genencor International, and those sold under the tradename Opticlean and Optimase by Solvay Enzymes. Preferred amylases include, for example, xcex1-amylases obtained from a special strain of B lichenifornis, described in more detail in GB-1,269,839 (Novo). Preferred commercially available amylases include for example, those sold under the tradename Rapidase by Gist-Brocades, and those sold under the tradename Termamyl, Duramyl and BAN by Novo Industries A/S. Highly preferred amylase enzymes maybe those described in PCT/ US 9703635, and in WO95/26397 and WO96/23873. The lipase may be fungal or bacterial in origin being obtained, for example, from a lipase producing strain of Humicola sp., Thermomyces sp. or Pseudomonas sp. including Pseudomonas pseudoalcaligenes or Pseudomas fluorescens. Lipase from chemically or genetically modified mutants of these strains are also useful herein. A preferred lipase is derived from Pseudomonas pseudoalcaligenes, which is described in Granted European Patent, EP-B-0218272.
Another preferred lipase herein is obtained by cloning the gene from Humicola lanuginosa and expressing the gene in Aspergillus oryza, as host, as described in European Patent Application, EP-A-0258 068, which is commercially available from Novo Industri A/S, Bagsvaerd, Denmark, under the trade name Lipolase. This lipase is also described in U.S. Pat. No. 4,810,414, Huge-Jensen et al, issued Mar. 7, 1989.
Preferred are also anionic surfactants, which include salts (including, for example, sodium, potassium, ammonium, and substituted ammonium salts such as mono-, di- and triethanolamine salts) of the anionic sulfate, sulfonate, carboxylate and sarcosinate surfactant, preferably linear or branched alkyl benzene sulfonate, alkyl sulphates and alkyl ethoxylsulfates, isethionates, N-acyl taurates, fatty acid amides of methyl tauride, alkyl succinates and sulfosuccinates, monoesters of sulfosuccinate (especially saturated and unsaturated C12-C18 monoesters) diesters of sulfosuccinate (especially saturated and unsaturated C6-C14 diesters), N-acyl sarcosinates. Highly preferred is that when anionic surfactants are present, at least one alkyl sulphate surfactant is present, preferably a branched alkyl sulphate surfactant, preferably at a level of 1% to 20% or even to 15% by weight of the composition.
Also preferred are also nonionic surfactants such as nonionic surfactant selected from the classes of the nonionic condensates of alkyl phenols, nonionic ethoxylated alcohols, nonionic ethoxylated/propoxylated fatty alcohols, nonionic ethoxylate/propoxylate condensates with propylene glycol, and the nonionic ethoxylate condensation products with propylene oxide/ethylene diamine adducts.
Cationic surfactants and softening agents may also be present herein, for example quaternary ammonium surfactants and softening agents, and choline ester surfactants.
Colouring agent such as iron oxides and hydroxydes, azo-dyes, natural dyes, may also be present in the composition or preferably in the compartment or pouch material, preferably present at levels of 0.001% and 10% or even 0.01 to 5% or even 0.05 to 1% by weight of the pouched composition
In one preferred embodiment of the present invention, the composition in the pouch comprises a first particulate component which forms a first fixed region in the compartment of the pouch and comprises perfume, and a second particulate component which forms a second fixed region in the compartment of the pouch comprises a member selected from the group consisting of bleach, nonionic surfactant, polyethylene glycol having a molecular weight of 4000 or more, enzyme, and combinations thereof. Typically, the second component is free from perfume. In this preferred embodiment of the present invention, the perfume in the composition is more stable since is contained in a separate fixed layer to the above ingredients which cause instability of the perfume. This allows the perfume to remain stable in the composition comprising perfume destabilizing ingredient.
Pouch and Compartment(s) Thereof
The pouch herein has a closed structure, made of materials described herein, enclosing a volume space which comprises the composition. Thus, the pouch can be of any form, shape and material which is suitable to hold the composition prior to use, e.g. without allowing the release of the composition from the pouch prior to contact of the pouched composition to water. The exact execution will depend on for example the type and amount of the composition in the pouch, the number of compartments in the pouch, the characteristics required from the pouch to hold, protect and deliver or release the compositions.
The pouch may be of such a size that it conveniently contains either a unit dose amount of the composition herein, suitable for the required operation, for example when the composition is a detergent composition, this may be a sufficient amount for one wash, or only a partial dose, to allow the consumer greater flexibility to vary the amount used, for example depending on the size and/ or degree of soiling of the wash load.
Preferably, the pouched composition is formed in a mold with a round or flat bottom and round walls. Thus, preferred is also that the pouched composition is a spheroid or more preferably cylinder-shaped.
The pouch has one or more compartments, whereof at least one holds at least two different particulate components. In a preferred execution, all particulate components are present in one and the same compartment of the pouch; it may be preferred that the pouch only has one compartment. This reduces the material needed to form the compartment and pouch. However, it may be preferred that one or more additional compartments for liquid component are present in addition to the compartment comprising the two or more particulate components.
The compartment of the pouch has a closed structure, made of materials described herein, enclosing a volume space which comprises the components. Thus, the compartment is suitable to hold the particulate components prior to use, e.g. without allowing the release of the components from the compartment prior to contact of the pouched composition to water. The compartment can have any form or shape, depending on the nature of the material of the compartment, the nature of the components or composition, the intended use, amount of the components etc. If more than one compartment is present, the compartments are linked or connected to one another by any means, for example sealed by heat sealing or by wetting sealing, glued by any known glue material, examples of which are described hereinafter.
Preferably, the compartment or preferably the pouch as a whole is made of a material which is stretchable, as set out herein. This for example facilitates the closure of the open compartment shape which is filled for more than 95% by volume or even 100% or even over filled as described above. Moreover, the material is preferably elastic, to ensure the tight packing and fixation of the regions remains during handling, e.g. to ensure no (additional) head space can be form after closure of the compartment.
Preferred stretchable materials have a maximum stretching degree of at least 150%, preferably at least 200%, more preferably of at least 400% as determined by comparison of the original length of a piece of material with the length of this piece of material just prior to rupture due to stretching, when a force of at least 1 Newton is applied. Preferably, the material is such that it has a stretching degree as before, when a force of at least 2Newton, or even at least 3 Newton is used. Preferably, it has this stretching degree when a force of the above lower limits is used, but not more than 20 Newton, or even 12 Newton, or even 8 Newton. For example, a piece of film with a length of 10 cm and a width of 1 cm and a thickness of 40 microns is stretched lengthwise with a 2.8 Newton force and thus an increasing stress, up to the point that it ruptures. The extent of elongation just before rupture can be determined by continuously measuring the length and the degree of stretching can be calculated. For example, this piece of film with an original length of 10 cm can be stretched with a force of 2.8 Newton to 52 cm just before breaking, and then is has a maximum stretching degree of 520%.
The force to stretch such a piece of film (10 cmxc3x971 cmxc3x9740 microns) to a degree of 200% should preferably be at least I Newton, preferably at least 2 Newton, more preferably at least 2.5 or even 3 Newton, and preferably no more than 20 Newton, preferably less than 12 Newton, most preferably less than 8 Newton. This in particular ensures that the elastic force remaining in the film after forming is high enough to immobilize the powders within the pouch, but not so high that the film cannot be drawn into a vacuum mold of reasonable depth.
As is clear form the definition herein, the stretchable material is defined by a degree of stretching measured when it is not present in the closed compartment. However, as said above, the material is preferably stretched when forming the compartment. This can for example been seen by printing a grid onto the material, e.g. film, prior to stretching, then forming a compartment with the component from this material with grid. It can be seen that squares of the grid are elongated and thus stretched.
The elasticity of the stretchable material of the compartment, and preferably the pouch as a whole can be defined as the xe2x80x98elasticity recoveryxe2x80x99. This can be determined by stretching the material for example to an elongation of 200%, as set out above, and measuring the length of the material after release of the stretching force. For example a piece of film of a length of 10 cm and width 1 cm and thickness of 40 microns is stretched lengthwise to 20 cm (200% elongation) with a force of 2.8 Newtons (as above), and then the force is removed. The film snaps back to a length of 12 cm, which means 80% elastic recovery.
The elasticity of the pouch material referred to herein, is the elasticity at the time of making the pouch. Prolonged stretching, for example that typically occurs during storage of the pouch, will decrease the elasticity of the pouch material due to plastic creeping. It is preferred that at the time of making the pouch or compartment thereof, the compartment material has an elasticity such that the elastic recovery is from 20% to 100%, more preferably from 50% or from 60% or more preferably from 75% or even 80% to 100%.
Thus, the material of the compartment and preferably the pouch as a whole is stretched during formation and/ or closing of the compartment or pouch, such that the resulting pouched composition has a compartment or pouch which is at least partially stretched. Typically and preferably, the degree of stretching in non-uniform over the compartment or pouch, due to the formation and closing process. For example, when a film is positioned in a mold and an open compartment is formed by vacuum forming (and then filled with the components and then closed) the part of the film in the bottom of the mold, furthest removed form the points of closing, will be stretched more than in the top part. Preferably, the elastic material which is furthest away from the opening, e.g. the material in the bottom of the mold, will be stretched more and be thinner than the material closest by the opening, e.g. at the top part of the mold. Therefor, it may be preferred that the component to be delivered first to the water is comprised in a bottom layer of the compartment, and a component which is to be delivered to the water at a later stage is comprised in a subsequent layer, closer to the top of the compartment. Alternatively, or in addition, it may be preferred that the least moisture sensitive component is comprised in the bottom layer of the compartment and a more moisture sensitive component is comprised in a subsequent or top layer.
As said before, another advantage of using stretchable and preferably also elastic material, is that the stretching action, when forming the shape of the compartment and/ or when closing the compartment, stretches the material of the compartment non-uniformly, which results in a compartment and pouch which has a non-uniform thickness. This allows control of the dissolution of water-soluble pouches herein, and for example sequential release of the components of the composition in the pouch to the water.
Preferably, the material is stretched such that the thickness variation in the compartment or pouch formed of the stretched material is from 10 to 1000%, preferably 20% to 600%, or even 40% to 500% or even 60% to 400%. This can be measured by any method, for example by use of an appropriate micrometer.
Material of Pouch and Compartment
Preferably, the composition is a composition to be delivered to water and thus the pouch and the compartment (s) thereof are designed such that at least one or more of the components is released at, or very shortly after, the time of addition to the water. Thus it is preferred that the compartment and preferably the pouch as a whole comprises material which is water-dispersible or more preferably water-soluble.
It is especially preferred that at least one component is delivered to the water within 3 minute, preferably even within 2 minutes or even within I minute after contacting the pouched composition to water.
Preferred water-dispersible material herein has a dispersibility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out hereinafter using a glass-filter with a maximum pore size of 50 microns. More preferably the material is water-soluble and has a solubility of at least 50%, preferably at least 75% or even at least 95%, as measured by the method set out hereinafter using a glass-filter with a maximum pore size of 20 microns, namely:
Gravimetric method for determining water-solubility or water-dispensability of the material of the compartment and/or pouch:
10 gramsxc2x10.1 gram of material is added in a 400 ml beaker, whereof the weight has been determined, and 245mlxc2x11 ml of distilled water is added. This is stirred vigorously on magnetic stirrer set at 600 rpm, for 30 minutes. Then, the mixture is filtered through a folded qualitative sintered-glass filter with the pore sizes as defined above (max. 20 or 50 micron). The water is dried off from the collected filtrate by any conventional method, and the weight of the remaining polymer is determined (which is the dissolved or dispersed fraction). Then, the % solubility or dispensability can be calculated.
Preferred materials are polymeric materials, preferably polymers which are formed into a film or sheet. The material in the form of a film can for example be obtained by casting, blow-molding, extrusion or blow extrusion of the polymer material, as known in the art.
Preferred polymer copolymers or derivatives thereof are selected from polyvinyl alcohols, polyvinyl pyrrolidone, polyalkylene oxides, (modified) cellulose, (modified)cellulose-ethers or -esters or -amides, polycarboxylic acids and salts including polyacrylates, copolymers of maleic/acrylic acids, polyaminoacids or peptides, polyamides including polyacrylamide, polysaccharides including starch and gelatine, natural gums such as xanthum and carragum. Preferably, the polymer is selected from polyacrylates and acrylate copolymers, including polymethacrylates, methylcellulose, sodium carboxymethylcellulose, dextrin, maltodextrin, ethylcellulose, hydroxyethyl cellulose, hydroxypropyl methylcellulose,; most preferably polyvinyl alcohols, polyvinyl alcohol copolymers and/ or hydroxypropyl methyl cellulose(HPMC).
The polymer may have any weight average molecular weight, preferably from about 1000 to 1,000,000, or even form 10,000 to 300,000 or even form 15,000 to 200,000 or even form 20,000 to 150,000.
Mixtures of polymers can also be used. This may in particular be beneficial to control the mechanical and/or dissolution properties of the compartment or pouch, depending on the application thereof and the required needs. For example, it may be preferred that a mixture of polymers is present in the material of the compartment, whereby one polymer material has a higher water-solubility than another polymer material, and/ or one polymer material has a higher mechanical strength than another polymer material. It may be preferred that a mixture of polymers is used, having different weight average molecular weights, for example a mixture of PVA (or a copolymer thereof) and/ or HPMC of a weight average molecular weight of 10,000-40,000, preferably around 20,000, and of PVA (or copolymer thereof) and/ or HPMC with a weight average molecular weight of about 100,000 to 300,000, preferably around 150,000.
Also useful are polymer blend compositions, for example comprising hydrolytically degradable and water-soluble polymer blend such as polylactide and polyvinyl alcohol, achieved by the mixing of polylactide and polyvinyl alcohol, typically comprising 1-35% by weight polylactide and approximately 65-99 by weight polyvinyl alcohol, if the material is to be water-dispersible, or water-soluble.
It may be preferred that the polymer present in the material of the compartment is from 60-98% hydrolyzed, preferably 80% to 90%, to improve the dissolution of the material.
Most preferred are materials which are water-soluble stretchable and elastic material comprising PVA polymer having properties such as the PVA films sold under the trade reference M8630, as sold by Chris-Craft Industrial Products of Gary, Ind. US.
Preferably, the level of a type polymer (e.g. commercial mixture) in the film material, for example PVA polymer, is at least 60% by weight of the material or film, preferably at least 60% or even at least 70% or even at least 80 or 90%. The upper level is up to 100%, but typically 99% or even 98% by weight.
The material herein may comprise other additive ingredients then the polymer or polymer material. For example, it may be beneficial to add plasticisers, for example glycerol, ethylene glycol, diethyleneglycol, propylene glycol, sorbitol and mixtures thereof, additional water, disintegrating aids. It may be useful when the pouched composition is a detergent composition, that the pouch or compartment material itself comprises a detergent additive to be delivered to the wash water, for example organic polymeric soil release agents, dispersants, dye transfer inhibitors.
The material in the form of a film may be coated, preferably only one-sided, with any coating method and with any coating agent, depending on the required properties; for example, it may be beneficial to coat the film such that the compartment or pouch or composition therein, is more storage stable and/or less sensitive to moisture and/ or acts as a improved moisture barrier.
A very useful form is to coat the material or film on one side with a coating that slows the dissolution of the film, prior to forming of the compartment and thus prior to stretching the material or film. Then, by stretching the material or film, the coating is stretched as well, resulting in cracks in the coating and/ or uneven distribution of the coating over the material and thus over the compartment. This then ensures still stability against moisture during storage, whilst the presence of cracks or the uneven distribution still ensures the required dissolution in use. Hence it is possible to make a pouched composition that is resistant to being handled with wet fingers when it is picked up at the sides but will still release product rapidly when it is immersed in water due to film rupture at the thinnest points.
Any coating material can be used, particular useful are hydrophobic coatings, or polymers with a low water-solubility, lower then defined herein before.
The compartment material may be shrinkable material, so that the surface area can be reduced during or subsequent to closing the open compartment by shrinking the material.
Preferably, the open compartment is closed with a piece of the same material as the material of the open compartment. The closing material, and thus preferably also the open compartment material or shape material, is preferably thermoplastic so that it can be closed by heat-sealing. Alternatively, a thermoplastic coating may be provided, either over the whole material or just in the areas where seals are to be formed. The sealing can also be made by solvent welding or wetting sealing. Suitable heat-sealable materials include polyvinyl alcohol, polyvinyl acetate, polyvinyl pyrrolidone, polyethylene oxide, acrylic resins and mixtures thereof, in particular polyvinyl alcohols.


A method includes receiving a communication from a party at a voice response system and capturing speech spoken by the party during the communication. Then a processor creates a voice model of the party, the voice model being created by processing the speech, without notifying the party. The voice model is then stored to provide voice verification during a subsequent communication.

1. Field of the Disclosure
The present disclosure relates to voice verification in service centers. More particularly, the present disclosure relates to a transparent method and system that registers a voice of a party in order to provide voice verification for communications with a service center.
2. Background Information
Many companies use service centers to provide information and services to callers and customers. Often, a company service center will use voice verification techniques to verify the identity of the caller. Voice verification technology uses human voice characteristics to verify whether a caller is the person that the caller claims to be.
During an enrollment phase, a statistical model of a caller's voice is computed and stored in a database. In the enrollment phase, the caller is requested to train the system by repeating random digits and/or phrases, under the supervision by a representative of the service center. The system then applies statistical learning methods to extract voice patterns of the caller, which will be used in subsequent calls to verify the identity of the caller. Then, during a subsequent call by the caller, the voice characteristics of the caller are compared with the stored voice model. If a match occurs, the system will permit the caller to continue. If no match occurs, the system can either reject the caller or direct the call to an operator. The accuracy of the system is dependent upon the quality of data collected from the caller during the enrollment phase.
For instance, ambient noise at the location of the caller during the enrollment phase may result in interference and a less than optimum voice model of the caller. Additionally, a customer's voice may change over time leading to a voice model that no longer matches the customer. Further, some callers who are cognizant of the enrollment phase may speak using a voice pattern, cadence, or tone not indicative of their ordinary conversational characteristics. All of these factors could lead to a potential future rejection of the caller, necessitating another enrollment phase.

Transparent voice registration and verification method and system


A process is provided for producing ethylene (co)polymer nanocomposites in a high pressure polymerization reactor. The process by which nanocomposites having organically modified clays incorporated and intimately dispersed therein involves polymerizing ethylene and one or more optional comonomers under high pressure polymerization conditions in the presence of an organic peroxide initiator and organically modified clay.

The invention relates to a method of producing nanocomposite materials by incorporating nanoclays during high pressure polymerizations. More specifically, the invention relates to a process wherein ethylene homopolymer or copolymer nanocomposites are produced by polymerizing the monomer(s) at high pressure in the presence of an organic peroxide initiator and an organically modified clay.
Ethylene polymers and copolymers are widely used because of their desirable physical properties; however, the applications for these polymers could be extended if certain properties, such as melt strength and stress crack resistance, could be improved. While conventional fillers can be employed to improve certain physical properties, it is often at the expense of other properties.
In recent years, nanoclays, i.e., organically modified clays, have been extensively used to enhance the performance of olefin polymers and overcome the problems heretofore observed when conventional fillers such as talc and calcium carbonate. The nanoclays have improved dispersibility in the polymer matrix due to their plate-like structure. As a result, the size of the filler particle, when dispersed, is on a nanoscale so that property enhancement is achieved at much lower filler levels compared to traditional fillers. Separation of the clay platelettes occurs in two steps. The first step is to separate the platelettes just enough to allow the polymer to locate between the plates and to maintain the spacing. This is known as intercalation. The second step is to delaminate or separate the platelettes further, which typically is achieved by melt mixing in an extruder or the like. This is called exfoliation. The extent of property improvement is typically related to the extent of exfoliation.
Various processes to produce in-reactor-filled polyolefin composite materials are known. U.S. Pat. Nos. 5,412,001; 5,412,025 and 5,422,386 describe processes for reactor-filling polyolefins by polymerizing xcex1-olefins in the presence of conventional fillers, such as Kaolin, mica or talc, which have been pretreated with catalytic amounts of organometallic compounds such as transition metal ester compounds.
U.S. Pat. Nos. 5,830,820; 5,906,955; 5,925,587; 6,034,187 and 6,110,858 disclose supported catalysts for the polymerization of olefins. Low levels of these supported catalysts are then used to catalyze the polymerization of olefins and provide polyolefins containing low levels of filler material.
U.S. Pat. No. 4,473,672 describes a process for making polyolefin compositions with a variety of fillers such as graphite, carbon black, aluminosilicate clay, mica, talc, vermiculite or glass fibers by pretreating the filler with an organic magnesium compound and then adding the resultant composition to a transition metal and subsequently initiating the polymerization with an organoaluminum compound.
U.S. Pat. No. 6,252,020 discloses clay-filled compositions produced by bulk and suspension polymerization of vinyl monomers, such as styrene, in the presence of clay and catalysts such as peroxides. The polymerization of olefins such as ethylene or propylene is not described or suggested.
There is a need for improved methods of dispersing clay fillers into ethylene homopolymers and copolymers utilizing in-reactor-filling procedures.
The present invention relates to a high pressure process for producing ethylene homopolymers and copolymers having organically modified clays incorporated and intimately dispersed therein. The process involves producing ethylene (co)polymer nanocomposites by (co)polymerizing ethylene under high pressure polymerization conditions in the presence of an organic peroxide initiator and organically modified smectite clay. Intercalation and exfoliation of the clay is effected in this manner. For the process the organically modified clay can be added to the high pressure polymerization reactor by one of several methods which can include the use of polar solvents, polar monomers or incorporation of the organic peroxide initiator on the clay. The latter procedure involves pretreating the organically modified clay with the organic peroxide. Polymerization can be accomplished utilizing autoclave or tubular reactors operated at pressures from about 10000 to 50000 psi and temperatures from about 250 to 650xc2x0 F.
Organically modified clays preferably used for the process are montmorillonite clays that have been ion exchanged and intercalated with a quaternary ammonium ion corresponding to the formula
(R)(R1)(R2)(R3)N+
where R represents a C18 alkyl substituent or mixture of alkyl substituents wherein the C18 alkyl moieties constitute 50% or more of the mixture and R1, R2 and R3 are independently selected from the group consisting of R, H and C1-22 hydrocarbon groups.
For the production of ethylene copolymers the comonomers are preferably olefinically unsaturated comonomers selected from the group consisting of C3-8 xcex1-olefins, vinyl C2-4 carboxylate and C1-4 alkyl (meth)acrylates.
Clays useful for the invention are smectite clays which are well described in the literature (see Izumi, Y., et al., Zeolite, Clay and Heteropoly Acid in Organic Reactions, VCH Publishers Inc. (1992)). They are layered materials with exchangeable cations between the layers to compensate for the negative charge of the layers. Clays are classified according to their layer charge. Smectite clay minerals have cation exchange capacity in the range of 50-100 meq/100 g-clay.
Smectite clays can be synthesized from magnesium silicates or, more commonly, they are obtained from naturally occurring bentonite ore. Two common types of smectite clay are montmorillonite and hectorite. Montmorillonite is classified as magnesium aluminum silicate and hectorite as magnesium silicate.
The cations on the clay surface affect the organophilicity of the clay. If the cation is a metallic cation such as sodium or calcium, the clay is not very organophilic. If the cation is an organic cation, such as an ammonium cation, then the clay becomes more organophilic. These latter types of organically modified clays are readily prepared by cation exchange of the sodium clay with an organic cation. Suitable organic cations include ammonium cations where the nitrogen has four non-hydrogen substituents, such as hexadecyloctadecyldimethyl ammonium, dimethyldioctadecyl ammonium, benzyl triethyl ammonium, methyltrioctylammonium and poly(oxypropylene)methyldiethyl ammonium. Organically modified clays of the above types, also referred to herein as organoclays or nanoclays, are employed for the process of the present invention.
For the process of the invention, smectite clays of the above types, and particularly montmorillonite clays, reacted with ammonium compounds having one or more C18 alkyl substituents are most advantageously employed. Montmorillonite clays that have been ion exchanged and intercalated with quaternary ammonium ions corresponding to the formula
(R)(R1)(R2)(R3)N+
where R represents a C18 alkyl substituent or mixture of alkyl substituents wherein the C18 alkyl moieties constitute 50% or more of the mixture and R1, R2 and R3 are independently selected from the group consisting of R, H or a C1-22 hydrocarbon group are particularly useful. Mixed alkyl substituents of the above types are typically obtained utilizing amines derived from natural sources such as beef tallow or mutton tallow. R moieties obtained from such natural products correspond to the constituent fatty acids and typically are mixtures of aliphatic radicals comprised of predominantly C14-18 carbon atoms. The carbon number range and distribution within the carbon number range, i.e., percentage of each component, can vary depending on factors such as the tallow source, treatment and age of the tallow. Typical constituent fatty acid values have, however, been generated and are as follows:
Source: CRC Handbook of Chemistry and Physics, 74th ed. (1993-94), pages 7-29. Thus, when hydrogenated and even allowing for the variations in tallow composition referred to above, it is expected that the C18 alkyl substituents will comprise at least 60% by weight and, more typically, at least 65% by weight of the R groups. More specifically, it is anticipated R would be comprised of approximately 5% C14, 30% C16, and 65% C18 alkyl groups.
Montmorillonite clays modified with dimethyl dihydrogenated tallow ammonium ion (abbreviated 2M2HT) and represented by the formula:
where HT represents the hydrogenated tallow group are highly effective. Montmorillonite clays modified with dimethyl dihydrogenated tallow ammonium ion at a modifier concentration of 50 to 150 meq/100 g are highly advantageous. Modified clays of this type are available from commercial sources. For example, Southern Clay Products, Inc., offers three montmorillonite clay products modified to different levels with dimethyl dihydrogenated tallow ammonium chloride, namely, Cloisite(copyright) 6A with a modifier concentration of 140 meq/100 g, Cloisite(copyright) 15A with a modifier concentration of 125 meq/100 g and Cloisite(copyright) 20A with a modifier concentration of 95 meq/100 g.
High pressure processes for the polymerization of ethylene are known and any of these known processes can be utilized for the invention. One such process is the so-called autoclave processxe2x80x94details of which are provided in U.S. Pat. No. 3,756,996 and which is incorporated herein by reference. Autoclave processes generally utilize elongated vertically disposed reactors having cylindrical interior reaction chambers having a length-to-diameter ratio of at least 2.5:1 or higher. These reactors have multiple reaction zones with means provided in each zone for the addition of monomer and/or initiator. Means for maintaining each of the reaction zones at the same or, more typically, different temperatures is also provided. Agitation is employed within the reactor by providing an agitator shaft extending through the axis of the reactor for its entire length with suitably configured and numbered blades to move the reaction mixture upwardly through the annular portion of the reaction chamber near the agitator shaft and downwardly along a portion of the reaction chamber near the side walls. In this way the desired radial and/or end-to-end mixing can be achieved. The agitator can be driven by an internally or externally located motor. Peroxide initiator can be added either in the monomer feed line to the reactor and/or at any of the various reaction zones. The nanoclay can be injected at various reactor locations. The injection point may lead to process or product optimization.
Pressures within the autoclave reactor will typically be maintained from about 10000 to 50000 psi. Temperatures varying longitudinally within the reaction chamber zones can range from about 250xc2x0 F. to 650xc2x0 F.
To achieve in-reactor incorporation and intimate dispersion of the organically modified clay in accordance with the process of the invention, the organically modified clay is introduced to and present in the autoclave reactor during the polymerization. Introduction of the organically modified clay may be accomplished using any of several procedures or a combination of these techniques can be employed. The manner and mode of nanoclay addition is dependent on a variety of factors but primarily is a function of whether the organically modified clay is pretreated with peroxide initiator and/or combined with a polar solvent and/or polar comonomer.
For example, the organically modified clay may be combined with a polar solvent, such as toluene, capable of exfoliating the clay and this mixture fed to the reactor through the feed line or it can be introduced into the first, second or last reactor zones depending on the desired effect and molecular weight of the polymer produced. The nanoclay may be first blended with the polar solvent capable of exfoliation and then the exfoliated mixture further blended with a carrier solvent, such as mineral spirits, for introduction to one or multiple reactor locations. Peroxide initiator may also be added to the above-described nanoclay/solvent mixtures. Typically if an organic peroxide is included, the mixture is introduced during the early stages of the polymerization.
In those situations where ethylene is to be copolymerized with polar comonomers, such as vinyl acetate, the organically modified clay may be combined with the comonomer and this mixture fed to the autoclave reactor at one or multiple locations. The polar comonomer serves as a diluent and exfoliant for the clay and further disperse it as polymerization occurs with monomer present in the layers of the clay. Other diluents, such as mineral spirits or the like, may also be included with the organically modified clay/polar comonomer mixture to facilitate handling and introduction to the reactor.
In an especially useful embodiment of the invention which can be used for both homo- and copolymerizations, the organically modified clay may be impregnated with the organic peroxide initiator by a slurry or incipient wetness technique and fed to one or more reactor locations. All or only a portion of the organic peroxide initiator required to maintain polymerization may be added in this manner. In most instances, the peroxide impregnated nanoclay will be combined with mineral spirits, toluene or xylene to facilitate introduction to the autoclave.
An amount of organoclay having organic peroxide deposited thereon is introduced to the autoclave reactor. This serves to initiate the polymerization. The amount will be such that the resulting filled ethylene polymer will have from about 0.25 to 12 weight percent clay and, more preferably, 1 to 10 weight percent intimately dispersed therein. The peroxide pretreated nanoclay may be introduced at one or more zones in the reactor; however, most effective initiation and dispersion will be achieved when at least a substantial portion of the peroxide pretreated clay is present in the first reaction zone. Introducing the pretreated clay to the early stages of the reactor enables maximum diffusion of ethylene into the spacings between the clay platelettes which can optimize polymerization on the clay surface and thus provide highly effective intercalation and exfoliation as high levels of polymer are produced. Also, if additional initiator is required to maintain polymerization, either neat organic peroxide or organoclay which has been precontacted with the same or different organic peroxide can be introduced into one or more of the reactor zones.
Organic peroxides can be any of those known to be useful initiators for high pressure polymerization processes. Representative organic peroxides include, for example: 2,4-dichlorobenzoyl peroxide, caprylyl peroxide, lauroyl peroxide, tert-butylperoxyisobutyrate, benzoyl peroxide, para-chlorobenzoyl peroxide, di-tert-butyl diperphthalate, tert-butyl peroxyacetate, tert-butyl peroxybenzoate, dicumyl peroxide, tert-butyl hydroperoxide, methyl ethyl ketone peroxide, di-tert-butyl peroxide, tert-butyl peroxyacetate, tert-amyl peroxyacetate, tert-butyl peroxypivalate, tert-amyl peroxypionalate, tert-butyl peroxymeodecanoate, tert-butyl peroctoate, di-sec-butyl peroxydicarbonate, di-(3,5,5-trimethylhexanoyl)peroxide, paramenthane hydroperoxide, pinene hydroperoxide, cumene hydroperoxide, 2,5-dimethylhexane-2,5-dihydroperoxide, and mixtures thereof.
Pretreatment, i.e., impregnation, of the organoclay with the organic peroxide can be accomplished by slurrying wherein the peroxide and modified clay are contacted in a suitable hydrocarbon medium and the hydrocarbon then evaporated. evaporating the hydrocarbon. If the peroxide is a solid, the hydrocarbon is preferably one in which the peroxide is soluble or can be easily dispersed. Suitable hydrocarbons can include aliphatic solvents, such as hexane and heptane; aromatic solvents such as benzene; alkyl-substituted benzenes such as toluene and xylene; halogenated benzenes such as dichloro- or trichlorobenzene; and the like. Pretreatment may also be accomplished using an incipient wetness procedure wherein a controlled amount of the organic peroxide with a suitable hydrocarbon is added in a controlled manner to the organically modified clay and thereafter subjected to drying which is carried out at a controlled temperature at or below the boiling point of the hydrocarbon to a point of incipient wetness. Such procedures are well known to those skilled in the art.
The amount of organic peroxide deposited on the nanoclay can vary but will generally be from about 0.01 to about 10 weight percent. A more preferred range would be 0.1 to 5 weight percent. If desired or required for the process, additional organic peroxide which is not deposited on the organoclay, may also be introduced during the course of the polymerization process. This additional peroxide may be dispersed/dissolved in a hydrocarbon solvent such as isobutane, cyclohexane, mineral spirits or the like.
Conventional procedures can be employed to recover the nanocomposite at the conclusion of the polymerization. The nanocomposite material having the organically modified clay intimately dispersed therein is removed from the end of the reactor through a suitable conduit with a pressure control value. At these very high pressures, the temperature of ethylene rises as the pressure is reduced. Therefore, the presence of unpolymerized ethylene will cause a temperature rise as the gas-polymer mixture exits the reactor through the pressure control valve. Post-reactor cooling is therefore applied after the pressure control value. After separation and removal of unreacted ethylene and any other unreacted comonomers, the resin is sent to the finishing operation where it is extruded into pellets and stored. At the finishing operation, various additives can be added. Any clay not incorporated in the polymer can be removed from recycled gas streams by the use of suitable filters.
Another common high pressure process which can be used for the invention is the so-called tubular process. Tubular processes for the polymerization of ethylene homopolymers and copolymers are known. One such process is described in U.S. Pat. No. 3,282,911 which is incorporated herein by reference. Operation of tubular reactors is similar to that described for autoclave reactors. For example, tubular reactors typically have several zones where initiator and/or fresh or recycled ethylene are introduced. Each zone can be run at a different temperature thus enabling direct control of the mix of molecular species. High gas velocities are employed to minimize tube wall fouling. By utilizing an oscillating pressure control valve, periodic pressure pulse and gas velocity changes within the tube can be produced to sweep polymer from the reactor walls and reduce the fouling tendency.
The process of the invention can be utilized for the polymerization of ethylene, alone or in combination with one or more olefinically unsaturated comonomers, at high pressure utilizing an organic peroxide initiator. It is particularly useful for the preparation of low density polyethylene (LDPE) nanocomposites and ethylene copolymer, e.g., ethylene-vinyl acetate (EVA), nanocomposites. Copolymers will typically have ethylene as the major constituent.
Most ethylene homopolymer nanocomposites made by high pressure, peroxide initiated processes will fall in the density range 0.915 g/cm3 to 0.0.965 g/cm3 and, more generally, 0.915 to 0.955 g/cm3. Polyethylene homopolymers produced by high pressure processes generally have 0.1 to 5 branches per hundred carbon atoms and crystallinities varying from about 35 to 75 percent.
Olefinically unsaturated comonomers which can be copolymerized with the ethylene include xcex1-olefins, such as propylene, butene-1, hexene-1, and octene-1; vinyl carboxylates such as vinyl acetate and vinyl propionate; alkyl acrylates and methacrylates such as methyl acrylate, ethyl acrylate, methyl methacrylate, and n-butyl acrylate; vinyl silanes, such as vinyltrimethoxysilane and vinyltriethoxysilane; acrylic and methacrylic acids; and carbon monoxide. Vinyl carboxylates and alkyl (meth)acrylate comonomers are particularly useful polar comonomers for the process of the invention. Of these vinyl acetate, ethyl acrylate and n-butyl acrylate are especially useful polar comonomers.
Useful copolymers produced using high pressure processes are typically comprised of ethylene, as the major component, with C3-8 xcex1-olefin, vinyl C2-4 carboxylate or C1-4 alkyl (meth)acrylate comonomers present in minor amounts. Comonomer contents of ethylene-C3-8 xcex1-olefin copolymers will generally range from 0.1 to 25 weight percent and, more preferably, from 0.5 to 15 weight percent.
Ethylene-vinyl acetate (EVA) copolymers are preferred ethylene-vinyl carboxylate polymers which can be produced and ethylene-ethyl acrylate (EEA) and ethylene-n-butyl acrylate (ENBA) copolymers are preferred ethylene-alkyl acrylate copolymers. Vinyl acetate contents of EVA copolymers will typically range from 2 to 48 weight percent and, more preferably, from 4 to 45 weight percent. Acrylate monomer contents for the EEA and ENBA copolymers are typically from 1 to 48 weight percent and, more preferably, from 2.5 to 45 weight percent.

In-reactor process for making ethylene polymer nanocomposite materials


A smart card connector switch that detects full installation of a smart card, includes first and second switch contacts (42, 40), with the second switch contact including a sheet metal switch blade (41) that can be depressed against the first contact. The second switch contact includes a polymer depressable element (60) mounted on the switch blade and having a rounded top (62) lying higher than the switch blade so a card engages and depresses the depressable element as the card approaches its fully installed position.

Applicant claims priority from French patent application 0206473 filed May 28, 2002.
A smart card, which may have about the same dimensions as a credit card, has one or more embedded integrated circuits, and has an active face with a plurality of contact pads that connect to the integrated circuit. A common arrangement includes six pads arranged in three columns and two rows. An electrical connector for connecting read/write circuitry to the card may include an insulative base with a card-receiving upper face, and with the contacts having pad-engaging ends projecting above the upper face, to be depressed by the pads of the smart card.
A card may be installed on the base in a number of ways, as by sliding it along the upper face or mounting it on a cover that pivots down the card until it lies facewise adjacent to the base upper face. Many card connectors include an electrical switch for detecting the presence of a card as it approaches the fully inserted position. Such a switch can make or break a switching circuit.
A switching circuit for detecting a smart card approaching a fully inserted position, can include a sheet metal switch blade that is depressed by the card so the blade engages another contact. Some problems that can arise with such a switch are that the card may become scratched by the portion of a sheet metal blade that the card engages, since the card is usually of plastic at its outside surface except at its metal contact pads. Also, there is a risk that the switch blade will engage one of the card contact pads and possibly pass a damaging current to it. A switch with a pair of switch contacts, wherein one of the switch contacts engages a card to detect the card approaching a full insertion position, which avoided the above disadvantages, would be of value.
In accordance with one embodiment of the present invention, a smart card connector is provided, with an electrical switch that detects a smart card close to its fully inserted position, while avoiding scratching of the card or the inadvertent connection of unwanted currents to contact pads of the card. The connector is of the type that includes an insulative base with an upper card-receiving surface and contacts with pad-engaging portions projecting above the surface to engage pads of a smart card that lies facewise adjacent to the base card-engaging surface. A switch for detecting a card near its fully installed position includes first and second switch contacts mounted on the base. The second switch contact includes a sheet metal switch blade that can be depressed by a card so the switch blade moves against the first contact or moves out of engagement with the first contact. A depressable element of insulating material is mounted on the blade, the depressable element having a top lying above the blade. As a result, a card near the fully installed position engages only the top of the depressable element to depress the contacting part of the second switch contact.
The depressable element is preferably formed of a polymer and has a rounded top, the polymer having a hardness no more than one fifth that of the metal of the switch blade. As a result, the depressing element, which is the only part engaged by a card, is unlikely to scratch the card, and cannot conduct electricity to a contact pad that happens to engage the element.
The switch blade has a blade hole, and the depressable element is trapped to walls of the blade hole by lying closely above and below the walls of the blade hole. This can be accomplished by projecting a stub upward through the blade hole and deforming the top of the stub to trap it to the blade while forming a rounded top on the stub.
The novel features of the invention are set forth with particularity in the appended claims. The invention will be best understood from the following description when used in conjunction with the accompanying drawings.


Cylinder block (32) of an axial piston compressor (20), in particular for use in a vehicle air conditioner with CO2 as coolant, which comprises at least one, in particular several cylinder bores distributed about a periphery, each of which defines a cylinder face and accommodates a piston (8) consisting of piston shaft (8a) and piston neck (8b), wherein the piston neck (8b) outside the cylinder bore serves for coupling to a swash- and/or wobble-plate drive mechanism (29, 33) operatively connected to a rotatable drive shaft (1), by means of which the piston (8) is movable back and forth within the cylinder bore, between a top-dead-center point (OT) and a bottom-dead-center point (UT), and wherein the edge of the opening of the cylinder face on the drive-mechanism side comprises at least one recess (26d) that can be at least partially engaged by a transitional region (8c) disposed between the shaft (8a) and the neck (8b) of the piston, so that the cylinder face effective for the piston (8) is enlarged or elongated.

The present application claims priority from German Patent Application No. 100 51 420.0, filed Oct. 17, 2000.
The invention relates to a cylinder block of an axial piston compressor, in particular for use in a vehicle air conditioner employing CO2 as coolant.
The air conditioners installed in motor vehicles employ coolant compressors of various constructions. In recent years, however, so-called axial piston compressors have become predominant. FIG. 4 shows this kind of axial piston compressor according to the state of the art, in diagrammatic longitudinal section. This is a so-called swash-plate compressor to be used with R134a as the coolant. A compressor shaft 1 is driven by way of a pulley associated with a magnetic coupling 2. A swash plate 3 is coupled to the drive shaft 1. The swash plate 3 is fixedly attached to the drive shaft 1 and rotates therewith. Various forms of linkage are known for mounting and centering the swash plate 3 on the drive shaft 1 in such a way that although the plate cannot rotate with respect to the shaft, it is possible for the axis 3a of the swash plate 3 to be tilted relative to the axis 1a of the drive shaft 1. The tilt angle of the swash plate 3 as a rule is limited to a minimal (3b) and a maximal (3c) value by two stopping devices. Customarily one or two guide pins 4 are needed so that the tilting movement can be carried out in a specified manner, with no risk of the plate becoming jammed during the adjustment. The means of limiting the tilting movement, i.e. the limit stops, can also be integrated into the region of the guide pins 4. In the example shown in FIG. 4, the guide pin is fixedly attached to the swash plate 3 and incorporates a bearing 5a that is movable with respect to a stopping plate 5 and that is responsible for centering the guide pin (see reference numeral 4a in FIG. 4). The stopping plate 5, which is likewise attached to the shaft, is supported by way of an axial bearing 6.
The swash plate is not only adjustable regarding its angle with respect to the drive shaft 1, but can also be shifted axially along the drive shaft 1. This shifting is necessary so that the top-dead-center point of the associated piston 8 can be maintained despite differences in the plate angle. Ordinarily limit stops are provided that prevent the swash plate 3 from being displaced beyond an upper seating 3d and a lower seating 3e on the drive shaft 1. The displacement mechanism is pretensioned to a specified degree by a compression spring 7. The stroke of the piston is determined by the tilt angle of the swash plate 3. When this angle is as large as possible, the stroke is maximal; a minimal tilt angle results in a minimal piston stroke.
The pistons 8 in the embodiment illustrated here are connected to the swash plate 3 by way of hemispherical linkage elements 9, 10. To absorb the tensile-pressure load, above a piston one linkage element 10 is disposed on the lower bearing surface 3gof the swash plate 3 and another linkage element 9 is disposed on its upper bearing surface 3f. By way of their flat surfaces 9a, 10a, the linkage elements run over complementary bearing surfaces of the swash plate 3 at the full circumferential velocity with a radial movement superimposed, with the result that the path of the linkage elements on the swash plate is elliptical. The convex upper surfaces 9b, 10b of the linkage elements are seated in indentations in the piston 8 that have a complementary, hemispherical form; while the compressor is in operation, there is a comparatively small amount of relative movement here. The axial piston compressors described above comprise several pistons distributed about their periphery, customarily three to eight pistons.
FIG. 9 shows a side view of a piston 8 such as is employed in an axial piston compressor like that shown in FIG. 4. The piston 8 consists of two sections, namely a piston shaft 8a and a piston neck 8b. The term xe2x80x9cshaftxe2x80x9d is used here to designate the part or section of the piston that is disposed within an associated cylinder bore which guides its back-and-forth it movement. The piston neck 8b, which customarily comprises a U-shaped cavity 8c, encloses the above-mentioned swash plate 3 and, in combination with the linkage elements 9, 10, serves to transmit the forces from the swash plate 3 to the piston shaft 8a. The back surface of the piston neck 8b is in contact with the inner surface of the drive-mechanism housing, in such a way that as the piston 8 moves back and forth, it is prevented from rotating within the associated cylinder bore.
FIG. 7 shows a specific way in which this rotational stability is accomplished. Supplementary information is provided in the document EP 0 740 076 A2. In order to limit the rotation of the piston 8 about its long axis, on the side of the piston neck that faces the drive-mechanism housing a convex surface 72 is disposed. Opposite to and spaced somewhat away from this surface is a concave surface in the housing 71. The radius R1 of the convex surface 72 is larger than the radius Rp of the cylindrical outer surface of the piston shaft, but smaller than the radius R2 of the concave inner surface in the housing 71. The contact between the convex surface 72 and the concave surface of the housing 71 limits the extent to which the piston 8 can rotate about its long axis. The dashed line shows that if the piston 8 rotates, only one edge 74 of the convex surface 72 touches the concave inner surface of the housing 71. To reduce friction and avoid wear and tear, it is advisable to treat the surfaces appropriately.
In FIG. 8 an alternative means of guiding the piston longitudinally is illustrated. This alternative construction to prevent unintended rotation of the piston 8 comprises a ridge 82 disposed along the piston shaft, which engages with a corresponding groove 83 in the face of the cylinder bore 81.
The translational movement of the piston 8 in the associated cylinder bore requires the dimensions, shape, position and surface properties of the parts and/or surfaces that correspond to one another to be very close to specifications.
FIGS. 4, 7, 8 and 9 document the classical state of the art insofar as it pertains to the axial piston compressor for a vehicle air conditioner. When R134a is used as the coolant, the piston diameter is about 30 mm. Because CO2 is a distinctly higher-performance coolant, compressers employing CO2 can have a considerably smaller stroke volume. On the other hand, it is necessary to cope with comparatively large pressure differences. That is, when CO2 is used as the coolant, the pressures exerted on the piston 8 are considerably greater. To compensate for these higher pressures, CO2 compressors are provided with pistons of considerably smaller diameter, e.g. about 16 mm.
However, as is illustrated in FIG. 5, when the shaft of a piston has such a small diameter, its neck projects further outward; that is, it is displaced to the side with respect to the long axis of the piston. In the embodiment shown in FIG. 5 the pistons 8 are driven by a wobble plate 29. The wobble plate 29 rests against a swash plate 33 by way of antifriction bearings 30, 28 and 24. By means of an internally threaded fixation disk 31, the wobble plate is fixed so that its axis coincides with that of the swash plate. The pistons are coupled to the wobble plate by way of linkage bearings 27 and 25 and by a set screw 26. The piston 8 consists of a shaft 8a and a neck 8b. These are separated by a transitional region 8c, which connects the shaft to the neck. In the case of an R134a compressor this transitional region is not necessary, because (as shown in FIG. 9) the neck of the piston has a diameter no greater than that of the associated shaft. The pistons 8 shown in FIG. 5 are guided axially in their back-and-forth movement by bores within a cylinder block 32. If the pistons 8 are provided with piston rings, the bearing surface of the cylinder bores either is coated with a layer of particularly wear-resistant material, or there are set into it bushings 26 made of a correspondingly resistant material. As can be seen in FIG. 5, the bushings 26 at the drive-mechanism end of the cylinder are flush with the cylinder block. Accordingly, the transitional region 8c between the shaft and neck of the piston is always outside the bearing surface of the cylinder.
To put it simply, the forces acting on the piston 8 are a transverse force FQ (introduced by the drive mechanism) and transverse forces FA and FB, which are also applied to the cylinder bushing 26 (see FIG. 5). One of the factors determining the magnitude of the reactive forces FA and FB is the lever-arm ratio B/(B-A).
These transverse forces are plotted in FIG. 6 for one operating point. The lever-arm ratio is also plotted in this graph. The relationships between force and angle shown there must be regarded as qualitative, because they can be shifted or altered in magnitude to a considerable extent at different operating points.
When the drive shaft 1 for the axial piston compressor is at the angular position 0xc2x0, in the embodiment illustrated here, the piston 8 has reached its top dead center (OT), the position in which the coolant gas is being expelled from the compression space. As the angle increases, the piston moves towards its bottom dead center (UT), which it reaches when the drive shaft is in the 180xc2x0 position. At the bottom dead center the pressure in the compression space falls to the suction pressure, at which point traction forces operate. During the further rotation of the drive shaft 1, beyond 180xc2x0, the piston is returned to top dead center. In the process, the coolant gas is compressed and subsequently expelled from the compression space. In FIG. 5 the transverse forces are represented as vectors, as mentioned above. FIG. 5 shows the piston at top dead center, at which point the angular position of the drive shaft 1 is 0xc2x0. The transverse forces FQ are of relatively large amplitude in this position and are directed towards the central axis of the compressor. The transverse force FQ introduces the reactive forces FA and FB, also shown as vectors in this xe2x80x9csnapshotxe2x80x9d, as a result of a bending moment at the piston 8. During a complete piston movement (OT-UT-OT) the transverse forces make one complete circuit about the piston axis.
The critical region for the drive shaft 1 is in the range of angular positions from 250xc2x0 to 360xc2x0, because in this range the transverse forces are relatively large. This applies in particular to a drive-shaft position of 270xc2x0, in which the piston 8 is still pulled relatively far out of the cylinder liner 26. This signifies a particularly large reactive force FA. Accordingly, in this angular position (270xc2x0) the pistons 8 are especially exposed to wear. The diagram according to FIG. 6 also makes clear that the pistons, for instance in the angular position 180xc2x0 (UT), cannot be braced against the wall of the housing because then traction forces would act.
Finally, it is evident from FIG. 5 that if the introduced transverse force FQ encountered a support directly in the region where it is applied, a bending moment in the piston would be prevented. This would bring enormous advantages with respect to reducing wear and tear.
Accordingly, the objective of the present invention is to create a cylinder block for an axial piston compressor, the cylinder faces of which ensure considerably improved support of transverse forces, in order by this means to increase the working life of the axial piston compressor.
The central idea in the present invention is thus that the edge of the opening of the cylinder face on the drive-mechanism side comprises at least one recess with which a transitional region disposed between the shaft and the neck of the piston can engage, so that the cylinder face effective for the piston is enlarged or lengthened. As a result, the lateral support of the piston against the associated bearing surface in the cylinder bore is considerably improved, with the consequence that there is less wear and the working life of the axial piston compressor is prolonged.
Moreover, in the present invention the fundamental rule applies that the recess in accordance with the invention is in each case disposed at the site that is under the least load. To assist understanding of this basic idea, reference is made to FIGS. 10a to 10c. These drawings show the paths of the transverse forces around the piston and the length of its contact region in the course of a stroke; these two parameters determine the amount of wear and hence also the preferred position of the lengthened cylinder face. At top dead center OT the length of the contact region is maximal, whereas at bottom dead center UT it is minimal. Now if the revolving transverse force is projected onto the contact length, as shown in FIG. 10b, the sequence of priorities for a lengthened support surface for the piston, i.e. a correspondingly lengthened cylinder face, is as follows: D, A, B. C. That is, in position C the load is least, and hence this is the preferred position for construction of a recess in accordance with the invention. The position C is radially external to the longitudinal middle axis of the axial piston compressor and of the swash or wobble plate associated with the piston 8; that is, it is next to the inside of the drive-mechanism housing. At this juncture it should once again be mentioned that FIG. 10a leaves open the direction in which the swash or wobble plate rotates. Depending on the direction of rotation of the swash or wobble plate, of course, there will be a mirror-image reversal of the paths about the X (horizontal) axis shown in FIGS. 10b and 10c.
The first alternative is characterized by the fact that the surface of the cylinder bore is worked; i.e., there is no separate liner or similar component. Accordingly, in this embodiment the above-mentioned recess must be formed within the cylinder bore, at the edge of the opening on the drive-mechanism side.
The second alternative is characterized by the insertion into the at least one cylinder bore of a liner that projects from the cylinder bore on the drive-mechanism side and in this region is provided with the above-mentioned recess.
The third alternative is characterized in that, again, a liner is inserted into the at least one cylinder bore, but in this case its edge is flush with the opening of the cylinder bore on the drive-mechanism side. In this case the recess in accordance with the invention must be formed in both the cylinder bore and the associated liner, at the edge of the opening on the drive-mechanism side.
As can be discerned from the above explanations in combination with FIGS. 10a to 10c, the recess in accordance with the invention is situated in a region in which the transverse forces acting on the piston are weakest. This region is ordinarily in the position on the side of the piston opposite the coupling to the drive mechanism, i.e. the side next to the wall of the drive-mechanism housing.
Preferably the neck of the piston is also laterally supported against the drive-mechanism housing. The lateral support here is brought about by a guide pin, a feather key or a similar means of longitudinal guidance. Models for this are available in the state of the art.
Preferably the edge of the opening of the cylinder face on the drive-mechanism side is beveled or rounded, to facilitate installation of the piston and reduce wear on the piston as it moves past the edge.
The recess in accordance with the invention preferably extends over an angular region of about 80xc2x0 to about 160xc2x0, in particular about 120xc2x0.

Cylinder block of an axial piston compressor with elongated cylinder face