EP0493197B1 - Process for molding a liquefiable material, especially soaps, and transparent or translucent soaps - Google Patents

Process for molding a liquefiable material, especially soaps, and transparent or translucent soaps Download PDF

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Publication number
EP0493197B1
EP0493197B1 EP91403438A EP91403438A EP0493197B1 EP 0493197 B1 EP0493197 B1 EP 0493197B1 EP 91403438 A EP91403438 A EP 91403438A EP 91403438 A EP91403438 A EP 91403438A EP 0493197 B1 EP0493197 B1 EP 0493197B1
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EP
European Patent Office
Prior art keywords
chamber
mould
wall
product
mold
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Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP91403438A
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German (de)
French (fr)
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EP0493197A1 (en
Inventor
Jean Gautier
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LOreal SA
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LOreal SA
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    • BPERFORMING OPERATIONS; TRANSPORTING
    • B65CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65BMACHINES, APPARATUS OR DEVICES FOR, OR METHODS OF, PACKAGING ARTICLES OR MATERIALS; UNPACKING
    • B65B3/00Packaging plastic material, semiliquids, liquids or mixed solids and liquids, in individual containers or receptacles, e.g. bags, sacks, boxes, cartons, cans, or jars
    • B65B3/04Methods of, or means for, filling the material into the containers or receptacles
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D13/00Making of soap or soap solutions in general; Apparatus therefor
    • C11D13/14Shaping
    • C11D13/16Shaping in moulds
    • CCHEMISTRY; METALLURGY
    • C11ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11DDETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D17/00Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0095Solid transparent soaps or detergents

Definitions

  • the present invention relates to a process for molding a liquefiable material, in particular soap.
  • EP-A-321 179 proposes a process for molding, and optionally packaging simultaneously, a material such as soap. According to this method, at least partially a flexible material packaging is filled with the liquid or semi-liquid state, the packaging is closed in an airtight manner, the material is allowed to set mass and the material is stored in the packaging in which it was poured.
  • the compression operations essentially aim to ensure good contact of the material to be molded with the wall of the package, and to give the latter a shape other than that of a cushion which it would naturally take.
  • the product when a hot liquefied product is poured into a mold, or in its packaging, the product may, when it cools, have a significant shrinkage.
  • the adhesion to the walls of the mold, or of the packaging, of the layer of material immediately in contact prevents this layer from following the shrinking of the mass of material. This results in significant shrinkage and appearance defects, such as hollows, which can be unacceptable.
  • the shrinking is often accompanied by the formation of bubbles or cloudy areas in the product, which is unacceptable for transparent soaps.
  • EP-A-0 299 113 describes a process in which products are molded in an elastic mold having the shape of an open bag.
  • the object of the present invention is to provide a process for molding a liquefiable product which avoids the formation of a necking and which remains economical while giving the finished product a beautiful appearance.
  • the present invention therefore relates to a process for molding a liquefiable product, in particular soap, characterized in that there is produced, inside a rigid mold, a chamber limited by at least one wall of material elastic resistant to the temperature of the liquefied product; that the interior volume of the chamber, at rest, is less than that of the mold in a proportion such that the wall of the chamber, to reach the volume of the mold by swelling, must undergo an elongation at least equal, in absolute value, to shrinkage of the molding product; that the air is expelled from the chamber with a wall of elastic material; that the chamber is filled with the liquefied product until, thanks to the elasticity of its wall, the chamber fills the entire interior volume of the mold; that the product contained in the chamber is cooled in the mold, and that the product is removed from the mold.
  • the interior volume of the chamber at rest is such that the elongation of the wall of the chamber is at least 50% when it is filled against the walls of the mold.
  • the shape of the resting chamber can be substantially homothetic to that of the mold so that the elongation in the different directions of the space is relatively constant.
  • the elastic wall of the chamber will, at the end of filling, uniformly line the mold, then during cooling the elastic wall exerts a practically uniform pressure on the product which it contains which shrinks during cooling .
  • the product contained in the chamber with elastic wall will therefore peel off uniformly from the wall of the mold. This prevents the formation of shrinkage and bubbles. After assembly, a bread is obtained, having the shape of the mold.
  • the interior of the mold can be placed under partial vacuum; thanks to its elasticity, the wall of elastic material of the chamber expands while filling and will occupy the entire interior volume of the mold. It is also possible to exert pressure on the liquefied product so that the chamber fills and occupies the entire interior volume of the mold.
  • the product is then cooled.
  • the mold can be allowed to cool in the ambient atmosphere.
  • the cooling process is preferably accelerated either by circulating air around the mold, or by using a double jacket mold and by circulating cold water in this double jacket. It is understood that the cooling temperature is higher than the temperature where the elastic material of the wall of the chamber is likely to freeze.
  • the chamber may consist of a pocket made of elastic material, in particular latex.
  • the wall of the chamber is confused with that of the pocket.
  • the method with a latex bag can be applied to any product having a melting or liquefaction temperature at most equal to 85 ° C. It can be used for example for molding candles or a lipstick grape.
  • the elastic wall of the chamber comprises at least one sheet or plate of elastic material, in particular elastomeric material, placed in the imprint of at least one half-shell of the mold.
  • a sheet or plate of elastic material can be provided in each imprint of the half-shells.
  • the material of the elastomer sheet is chosen from silicones.
  • the elastomer wall preferably has a thickness of about 0.6 mm to 0.7 mm.
  • the rigid mold is provided with at least one opening, or a recess, in its side wall allowing the elastic sheet to expand during filling, in particular when hot under pressure.
  • the method of the invention is particularly advantageously applicable to the molding of soaps, preferably transparent or translucent soaps.
  • the mold used according to the invention can have any shape, ovoid, pebble, sphere, cube, or, more particularly, a shape of rectangular parallelepiped with rounded corners.
  • the interior volume of the mold can have different values. It is for example in the case of molding soaps, advantageously between 1 ml and 100 ml.
  • the mold in the case where the chamber is constituted by a pocket made of elastic material, the mold is constituted by a rigid box which serves as packaging for the bread of product contained in the pocket. In this case, it is not necessary to unmold the product contained in the flexible pouch and then put it in a package. This avoids a product recovery operation.
  • the pocket used according to the invention can be made of natural or synthetic rubber.
  • the rubber used must have an elongation at least equal to the constriction, that is to say, in the case of the molding of soap, at least equal to 5%.
  • the invention also relates to a soap, transparent or translucent, in particular obtained by the method of the invention, and characterized in that it is wrapped in a pocket of elastic material, having undergone elongation.
  • Pockets having various colors can be used, but preferably a pocket made of transparent or translucent material is used.
  • the pocket advantageously includes a cutting primer to allow the envelope to be easily torn before the use of the solidified product roll.
  • FIGS. 1 a to 7 a of these drawings illustrate a first embodiment of the method of the invention.
  • Figures 1b to 7b illustrate a second embodiment.
  • FIGS. 1 c to 4 c illustrate another embodiment.
  • Figure 1 d illustrates an alternative embodiment.
  • Figure 8 finally, illustrates a soap obtained with the mold of Figure 1 d .
  • FIGS. 1 a to 7 a in a first stage illustrated by FIGS. 1 a and 2 a , we take a mold 1 composed of two rigid half-shells 2, 3 mounted on a hinge (not shown).
  • the half-shell 2 is provided with a tube 6 passing through the thickness of the mold.
  • recesses are provided in the opposite faces of the half-shells so as to form a sort of passage or tubing t (FIG. 2 a ) when the half-shells are applied. one against the other.
  • volume at rest, or in the free state, of the bag 4 is meant the volume of liquid, or gas that can contain this bag without undergoing expansion or elongation.
  • the pocket 4 is provided with a sort of neck g , forming a mouth, which passes through the passage t and which allows the pocket to be held.
  • the pocket 4 determines, by its internal volume, a chamber R.
  • the mold 1 is closed so as to fix the pocket using a seal (not shown) by its mouth (see FIG. 2 a ).
  • a partial vacuum is then made in the interior volume V of the mold by putting it in communication with a vacuum pump via the tube 6.
  • the bag 4 fills and expands until it occupies the entire interior volume of the mold 1 (FIG. 6 a ).
  • the liquefied product is then allowed to cool and harden. It is possible to exert a slight overpressure between the interior wall of the mold and the bag 4 by introducing a pressurized gas through the tube 6 so as to detach the bag 4 from the mold and to accompany the product during its shrinking.
  • the mold 1 When the molded product is cooled and solidified, the mold 1 is opened and the loaf P of formed product is removed which is wrapped in the bag 4. Finally, the excess product is cut at the orifice t remaining and the neck g of the pocket.
  • the bread P of product wrapped in the bag 4 is sold as is, the bag serving as packaging, or is placed in an additional packaging such as box or paper.
  • a pocket 14 is introduced into a mold 10 provided with a vent 16 and the mold 10 is closed (FIGS. 1 b , 2 b ). Vacuum is then made in the pocket 14 by putting its mouthpiece g into communication with a vacuum pump (FIG. 3 b ). When the pocket is flattened, its mouth is placed in communication with a source of liquefied product 15 (FIG. 4 b ). Pressure is exerted on the liquefied product so as to fill the bag 14 by expanding it until it completely fills the interior volume of the mold 10. As the bag 14 expands and elongates in in all directions, the air contained in the interior volume V of the mold is expelled by the vent 16 (FIG. 5 b ).
  • the wall of the pocket because of its elasticity, will follow the product, in particular the soap, keeping any imprints of the mold while remaining stuck to the product.
  • the pouch filling orifice determined by the passage t , has a reduced section so that the loss of product corresponding to the part of product solidified in this passage is reduced.
  • the area of the finished product not covered by the pocket, corresponding to the removal of said neck portion g is also reduced.
  • This zone is however advantageous since it constitutes a cutting initiation facilitating the withdrawal of the envelope when the product is going to be used.
  • the walls 24 a , 24 b of the chamber R are constituted by two sheets, or plates, or membranes of elastic material, in particular elastomer material. These sheets (or plates) are placed in the respective imprint of the two half-shells 22, 23 of the mold.
  • the mold 20 is closed, the edges of the elastic walls 24 a , 24 b are joined and the chamber R communicates with the outside only through the passage t formed by recesses provided in the opposite faces of the half-shells 22, 23.
  • Each half-shell is provided with a tube 26 passing through the thickness of its wall in a central zone.
  • the mold is closed so as to expel the air from the interior of the mold by putting it in communication with a vacuum pump via the tube t (FIG. 1 c ).
  • the tube t When the vacuum is reached, the tube t is placed in communication with a source of liquefied product 25 (FIG. 2 c ). Pressure is exerted on the liquefied product so as to fill the mold until the two elastic walls 24 a , 24 b , adhere perfectly to the walls of the mold.
  • the tubes 26 can be connected to the suction of a vacuum pump to facilitate the application of the elastic walls 24 a , 24 b against the walls of the mold.
  • the interior volume of the chamber R delimited by the elastic walls 24 a , 24 b , unexpanded, is approximately 5% to 7% less than the total volume of the mold cavities 20.
  • the tubing 26 is constituted by a recess (or an opening) of relatively large dimensions (for example with a diameter of the order of 2 cm or 3 cm), communicating with the outside through the side wall of the mold; the elastic wall is thus in direct communication with the atmosphere.
  • This recess allows the elastic sheet to expand during hot filling under pressure.
  • the bar of soap obtained can then be engraved by striking.
  • the two elastic walls 24 a , 24 b remain attached to the half-shells 22, 23 of the open mold.
  • the chamber R is limited on one side of the joint plane of the half-shells 32, 33 of the mold 30 by an elastic wall 34 constituted by a sheet, or the like, of elastic material, in particular elastomeric material placed in the cavity of the half-shell 33.
  • the rigid wall w of the cavity the other half-shell 32 comes directly into contact with the molded product.
  • This wall w advantageously comprises patterns, letters, etc., in relief or in hollow, suitable for directly etching the product P1 during molding, without requiring a subsequent striking.
  • Tubing 36 is provided in the wall of the single half-shell 33, the imprint of which is equipped with the elastic wall 34.
  • the pressure for following the constriction is located only on the face of the bread P1 in contact with the elastic wall 34.
  • the internal volume enclosed by the elastic wall 34, not expanded, and the wall w , when the mold 30 is closed, is approximately 5 to 7% less than the total volume of the mold cavities 30.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Mechanical Engineering (AREA)
  • Detergent Compositions (AREA)
  • Cosmetics (AREA)
  • Moulds For Moulding Plastics Or The Like (AREA)

Abstract

Process for moulding a liquefiable product, especially soap, according to which a chamber, bounded by at least one wall (4) of elastic material which is resistant to the temperature of the liquefied product, is made inside a rigid mould (1); the internal volume of the chamber (R) is less than that of the mould; the air is expelled from the chamber and it is filled with the liquefied product until it fills all the internal volume of the mould (1). The product contained in the chamber (R) is cooled in the mould and the product is removed from the mould. <IMAGE>

Description

La présente invention concerne un procédé de moulage d'une matière liquéfiable, notamment de savons.The present invention relates to a process for molding a liquefiable material, in particular soap.

EP-A-321 179 propose un procédé pour mouler, et éventuellement emballer simultanément, une matière telle que du savon. Selon ce procédé, on remplit à l'aide de la matière à l'état liquide ou semi-liquide un emballage au moins partiellement en matériau flexible, on ferme de façon étanche à l'air l'emballage, on laisse la matière prendre en masse et on stocke la matière dans l'emballage dans lequel elle a été coulée.EP-A-321 179 proposes a process for molding, and optionally packaging simultaneously, a material such as soap. According to this method, at least partially a flexible material packaging is filled with the liquid or semi-liquid state, the packaging is closed in an airtight manner, the material is allowed to set mass and the material is stored in the packaging in which it was poured.

Il est possible de comprimer l'emballage au cours du refroidissement entre deux surfaces planes ou de l'introduire dans un moule de façon à le comprimer.It is possible to compress the packaging during cooling between two flat surfaces or to introduce it into a mold so as to compress it.

Les opérations de compression, ou opérations analogues, visent essentiellement à assurer un bon contact de la matière à mouler avec la paroi de l'emballage, et à donner à ce dernier une forme autre que celle de coussin qu'il prendrait naturellement.The compression operations, or similar operations, essentially aim to ensure good contact of the material to be molded with the wall of the package, and to give the latter a shape other than that of a cushion which it would naturally take.

Or, lorsque l'on coule dans un moule, ou dans son emballage, un produit chaud liquéfié, le produit peut, lors de son refroidissement, présenter un rétreint important. L'adhérence sur les parois du moule, ou de l'emballage, de la couche de matière immédiatement au contact empêche cette couche de suivre le rétreint de la masse de matière. Il en résulte des retassures importantes et des défauts d'aspect, tels que des creux, qui peuvent être rédhibitoires. Le rétreint s'accompagne souvent de la formation de bulles ou de zones troubles dans le produit, ce qui est inacceptable pour des savons transparents.However, when a hot liquefied product is poured into a mold, or in its packaging, the product may, when it cools, have a significant shrinkage. The adhesion to the walls of the mold, or of the packaging, of the layer of material immediately in contact prevents this layer from following the shrinking of the mass of material. This results in significant shrinkage and appearance defects, such as hollows, which can be unacceptable. The shrinking is often accompanied by the formation of bubbles or cloudy areas in the product, which is unacceptable for transparent soaps.

Ce problème n'a pas été véritablement traité dans EP-A-321 179 dont certains passages parlent seulement de provoquer une extension de l'enveloppe, par exemple une extension provoquée par la chaleur, pour mieux la mettre en contact avec le produit. Mais les difficultés créées par un rétreint du produit restent sous silence, en particulier lorsqu'il s'agit de savons transparents.This problem was not really addressed in EP-A-321 179, certain passages of which speak only of causing an extension of the envelope, for example an extension caused by heat, to better bring it into contact with the product. However, the difficulties created by shrinking the product remain silent, in particular when it comes to transparent soaps.

EP-A-0 299 113 décrit un procédé dans lequel on moule des produits dans un moule élastique ayant la forme d'un sac ouvert.EP-A-0 299 113 describes a process in which products are molded in an elastic mold having the shape of an open bag.

La présente invention a pour but de fournir un procédé de moulage de produit liquéfiable qui évite la formation d'un rétreint et qui reste économique tout en donnant au produit fini un bel aspect.The object of the present invention is to provide a process for molding a liquefiable product which avoids the formation of a necking and which remains economical while giving the finished product a beautiful appearance.

La présente invention a donc pour objet un procédé de moulage d'un produit liquéfiable, notamment de savon, caractérisé par le fait qu'on réalise, à l'intérieur d'un moule rigide, une chamble limitée par au moins une paroi en matériau élastique résistant à la température du produit liquéfié ; que le volume intérieur de la chambre, au repos, est inférieur à celui du moule dans une proportion telle que la paroi de la chambre, pour atteindre le volume du moule par gonflement, doit subir un allongement au moins égal, en valeur absolue, au rétreint du produit à mouler ; qu'on chasse l'air de la chambre à paroi en matériau élastique ; qu'on remplit la chambre avec le produit liquéfié jusqu'à ce que, grâce à l'élasticité de sa paroi, la chambre remplisse tout le volume intérieur du moule ; qu'on refroidit dans le moule le produit contenu dans la chambre, et qu'on démoule le produit.The present invention therefore relates to a process for molding a liquefiable product, in particular soap, characterized in that there is produced, inside a rigid mold, a chamber limited by at least one wall of material elastic resistant to the temperature of the liquefied product; that the interior volume of the chamber, at rest, is less than that of the mold in a proportion such that the wall of the chamber, to reach the volume of the mold by swelling, must undergo an elongation at least equal, in absolute value, to shrinkage of the molding product; that the air is expelled from the chamber with a wall of elastic material; that the chamber is filled with the liquefied product until, thanks to the elasticity of its wall, the chamber fills the entire interior volume of the mold; that the product contained in the chamber is cooled in the mold, and that the product is removed from the mold.

De préférence, le volume intérieur de la chambre au repos est tel que l'allongement de la paroi de la chambre est d'au moins 50 % lors de son remplissage contre les parois du moule.Preferably, the interior volume of the chamber at rest is such that the elongation of the wall of the chamber is at least 50% when it is filled against the walls of the mold.

La forme de la chambre au repos peut être sensiblement homothétique de celle du moule de sorte que l'allongement dans les différentes directions de l'espace soit relativement constant.The shape of the resting chamber can be substantially homothetic to that of the mold so that the elongation in the different directions of the space is relatively constant.

Selon l'invention la paroi élastique de la chambre va, en fin de remplissage, tapisser de façon uniforme le moule, puis au cours du refroidissement la paroi élastique exerce une pression pratiquement uniforme sur le produit qu'elle contient qui rétrécit au cours du refroidissement. Le produit contenu dans la chambre à paroi élastique va donc se décoller de façon uniforme de la paroi du moule. On évite ainsi la formation de retassures et de bulles. Après assemblage, on obtient un pain, ayant la forme du moule.According to the invention the elastic wall of the chamber will, at the end of filling, uniformly line the mold, then during cooling the elastic wall exerts a practically uniform pressure on the product which it contains which shrinks during cooling . The product contained in the chamber with elastic wall will therefore peel off uniformly from the wall of the mold. This prevents the formation of shrinkage and bubbles. After assembly, a bread is obtained, having the shape of the mold.

Selon l'invention pour chasser l'air de la chambre à paroi élastique, on peut soit exercer une légère pression dans le moule, soit faire un vide partiel dans la chambre à paroi élastique.According to the invention, to expel air from the chamber with elastic wall, it is possible either to exert a slight pressure in the mold, or to make a partial vacuum in the chamber with elastic wall.

Pour remplir la chambre à partir d'une source de produit liquéfié, on peut mettre l'intérieur du moule sous vide partiel ; grâce à son élasticité, la paroi en matière élastique de la chambre se dilate tout en se remplissant et va occuper tout le volume intérieur du moule. On peut, également, exercer une pression sur le produit liquéfié de façon que la chambre se remplisse et occupe tout le volume intérieur du moule.To fill the chamber from a source of liquefied product, the interior of the mold can be placed under partial vacuum; thanks to its elasticity, the wall of elastic material of the chamber expands while filling and will occupy the entire interior volume of the mold. It is also possible to exert pressure on the liquefied product so that the chamber fills and occupies the entire interior volume of the mold.

Le produit est ensuite refroidi. On peut laisser le moule se refroidir dans l'atmosphère ambiante. On accèlère, de préférence, le processus de refroidissement soit en faisant circuler de l'air autour du moule, soit en utilisant un moule à double enveloppe et en faisant circuler de l'eau froide dans cette double enveloppe. Il est bien entendu que la température de refroidissement est supérieure à la température où le matériau élastique de la paroi de la chambre est susceptible de geler.The product is then cooled. The mold can be allowed to cool in the ambient atmosphere. The cooling process is preferably accelerated either by circulating air around the mold, or by using a double jacket mold and by circulating cold water in this double jacket. It is understood that the cooling temperature is higher than the temperature where the elastic material of the wall of the chamber is likely to freeze.

La chambre peut être constituée par une poche en matériau élastique, notamment en latex. Dans ce cas, la paroi de la chambre est confondue avec celle de la poche.The chamber may consist of a pocket made of elastic material, in particular latex. In this case, the wall of the chamber is confused with that of the pocket.

Le procédé avec une poche en latex peut s'appliquer à tout produit ayant une température de fusion ou liquéfaction au plus égale à 85°C. On peut l'utiliser par exemple pour le moulage de bougies ou d'un raisin de rouge à lèvres.The method with a latex bag can be applied to any product having a melting or liquefaction temperature at most equal to 85 ° C. It can be used for example for molding candles or a lipstick grape.

Selon un autre mode de réalisation, la paroi élastique de la chambre comprend au moins une feuille ou plaque de matière élastique, notamment matière élastomère, placée dans l'empreinte d'au moins une demi-coquille du moule. Une telle feuille ou plaque de matière élastique peut être prévue dans chaque empreinte des demi-coquilles.According to another embodiment, the elastic wall of the chamber comprises at least one sheet or plate of elastic material, in particular elastomeric material, placed in the imprint of at least one half-shell of the mold. Such a sheet or plate of elastic material can be provided in each imprint of the half-shells.

Selon une variante préférée, de ce mode de réalisation, la matière de la feuille en élastomère est choisie parmi les silicones. La paroi en élastomère présente, de préférence, une épaisseur d'environ 0,6 mm à 0,7 mm.According to a preferred variant, of this embodiment, the material of the elastomer sheet is chosen from silicones. The elastomer wall preferably has a thickness of about 0.6 mm to 0.7 mm.

Avantageusement, le moule rigide est muni d'au moins d'une ouverture , ou d'un évidement, dans sa paroi latérale permettant la dilatation de la feuille élastique lors du remplissage, en particulier à chaud sous pression.Advantageously, the rigid mold is provided with at least one opening, or a recess, in its side wall allowing the elastic sheet to expand during filling, in particular when hot under pressure.

Le procédé de l'invention s'applique de façon particulièrement avantageuse au moulage des savons, de préférence des savons transparents ou translucides.The method of the invention is particularly advantageously applicable to the molding of soaps, preferably transparent or translucent soaps.

Le moule utilisé selon l'invention peut avoir une forme quelconque, ovoïde, de galet, de sphère, de cube, ou, plus particulièrement une forme de parallélépipède rectangle à coins arrondis.The mold used according to the invention can have any shape, ovoid, pebble, sphere, cube, or, more particularly, a shape of rectangular parallelepiped with rounded corners.

Le volume intérieur du moule peut avoir des valeurs différentes. Il est par exemple dans le cas du moulage de savons, avantageusement compris entre 1 ml et 100 ml.The interior volume of the mold can have different values. It is for example in the case of molding soaps, advantageously between 1 ml and 100 ml.

Il est construit en matériau suffisamment rigide pour résister aux pressions exercées au cours du procédé de moulage.It is constructed of sufficient material rigid to withstand the pressures exerted during the molding process.

Selon un mode de réalisation particulier, dans le cas où la chambre est constituée par une poche en matériau élastique, le moule est constitué par une boîte rigide qui sert d'emballage au pain de produit contenu dans la poche. Dans ce cas, on n'est pas obligé de démouler le produit contenu dans la poche souple pour le mettre ensuite dans un emballage. On évite ainsi une opération de reprise du produit.According to a particular embodiment, in the case where the chamber is constituted by a pocket made of elastic material, the mold is constituted by a rigid box which serves as packaging for the bread of product contained in the pocket. In this case, it is not necessary to unmold the product contained in the flexible pouch and then put it in a package. This avoids a product recovery operation.

La poche utilisée selon l'invention peut être en caoutchouc naturel ou synthétique. Le caoutchouc utilisé doit avoir un allongement au moins égal au rétreint, c'est-à-dire, dans le cas du moulage de savon, au moins égal à 5 %.The pocket used according to the invention can be made of natural or synthetic rubber. The rubber used must have an elongation at least equal to the constriction, that is to say, in the case of the molding of soap, at least equal to 5%.

L'invention est également relative à un savon, transparent ou translucide, en particulier obtenu par le procédé de l'invention, et caractérisé par le fait qu'il est enveloppé dans une poche en matière élastique, ayant subi un allongement.The invention also relates to a soap, transparent or translucent, in particular obtained by the method of the invention, and characterized in that it is wrapped in a pocket of elastic material, having undergone elongation.

On peut utiliser des poches ayant des colorations diverses, mais on utilise, de préférence une poche en matériau transparent ou translucide. La poche comporte, avantageusement, une amorce de découpe pour permettre de déchirer facilement l'enveloppe avant l'utilisation du pain de produit solidifié.Pockets having various colors can be used, but preferably a pocket made of transparent or translucent material is used. The pocket advantageously includes a cutting primer to allow the envelope to be easily torn before the use of the solidified product roll.

L'invention consiste, mises à part les dispositions exposées ci-dessus, en un certain nombre d'autres dispositions dont il sera plus explicitement question ci-après dans la description détaillée de modes de réalisation particuliers, description donnée à titre explicatif, et non limitatif, avec référence aux dessins annexés.The invention consists, apart from the arrangements set out above, of a certain number of other arrangements which will be more explicitly discussed below in the detailed description of particular embodiments, description given by way of explanation, and not limiting, with reference to the accompanying drawings.

Les figures 1a à 7a de ces dessins illustrent un premier mode de réalisation du procédé de l'invention.Figures 1 a to 7 a of these drawings illustrate a first embodiment of the method of the invention.

Les figures 1b à 7b, illustrent un second mode de réalisation.Figures 1b to 7b illustrate a second embodiment.

Les figures 1c à 4c illustrent un autre mode de réalisation.Figures 1 c to 4 c illustrate another embodiment.

La figure 1d illustre une variante de réalisation.Figure 1 d illustrates an alternative embodiment.

La figure 8, enfin, illustre un savon obtenu avec le moule de la figure 1d.Figure 8, finally, illustrates a soap obtained with the mold of Figure 1 d .

Dans le procédé des figures 1a à 7a, dans un premier stade illustré par les figures 1a et 2a, on prend un moule 1 composé de deux demi-coquilles rigides 2, 3 montées sur une charnière (non représentée). La demi-coquille 2 est munie d'une tubulure 6 traversant l'épaisseur du moule.In the process of FIGS. 1 a to 7 a , in a first stage illustrated by FIGS. 1 a and 2 a , we take a mold 1 composed of two rigid half-shells 2, 3 mounted on a hinge (not shown). The half-shell 2 is provided with a tube 6 passing through the thickness of the mold.

A l'opposé de la partie articulée des demi-coquilles, des évidements sont prévus dans les faces en regard des demi-coquilles de manière à former une sorte de passage ou tubulure t (figure 2a) lorsque les demi-coquilles sont appliquées l'une contre l'autre.Opposite the articulated part of the half-shells, recesses are provided in the opposite faces of the half-shells so as to form a sort of passage or tubing t (FIG. 2 a ) when the half-shells are applied. one against the other.

Une poche 4 en matériau élastique, notamment en latex naturel, dont le volume à l'état libre est très inférieur (par exemple au moins 10 fois inférieur) au volume de l'espace interne V du moule, est placée dans cet espace V. Par volume au repos, ou à l'état libre, de la poche 4, on désigne le volume de liquide, ou de gaz que peut contenir cette poche sans subir de dilatation ou allongement. La poche 4 est munie d'une sorte de goulot g, formant embouchure, qui traverse le passage t et qui permet le maintien de la poche. La poche 4 détermine, par son volume intérieur, une chambre R.A pocket 4 made of elastic material, in particular natural latex, the volume of which in the free state is much less (for example at least 10 times less) than the volume of the internal space V of the mold, is placed in this space V. By volume at rest, or in the free state, of the bag 4, is meant the volume of liquid, or gas that can contain this bag without undergoing expansion or elongation. The pocket 4 is provided with a sort of neck g , forming a mouth, which passes through the passage t and which allows the pocket to be held. The pocket 4 determines, by its internal volume, a chamber R.

On referme le moule 1 de façon à fixer la poche à l'aide d'un joint (non représenté) par son embouchure (voir figure 2a).The mold 1 is closed so as to fix the pocket using a seal (not shown) by its mouth (see FIG. 2 a ).

Pour chasser l'air de la poche 4, on envoie par l'intermédiaire de la tubulure 6 un gaz sous pression. Lorsque la poche 4 est complètement aplatie, on la met en communication avec une source 5 de produit liquéfié (figure 4a) (par exemple un entonnoir rempli de produit) et on ferme la tubulure 6.To expel the air from pocket 4, we send via the pipe 6 a gas under pressure. When the bag 4 is completely flattened, it is placed in communication with a source 5 of liquefied product (FIG. 4 a ) (for example a funnel filled with product) and the tube 6 is closed.

On fait ensuite un vide partiel dans le volume intérieur V du moule en le mettant en communication avec une pompe à vide par l'intermédiaire de la tubulure 6.A partial vacuum is then made in the interior volume V of the mold by putting it in communication with a vacuum pump via the tube 6.

La poche 4 se remplit et se dilate jusqu'à ce qu'elle occupe la totalité du volume intérieur du moule 1 (figure 6a). On laisse alors le produit liquéfié se refroidir et durcir. On peut exercer entre la paroi intérieure du moule et la poche 4 une légère surpression en introduisant un gaz sous pression à travers la tubulure 6 de façon à décoller la poche 4 du moule et à accompagner le produit pendant son rétreint.The bag 4 fills and expands until it occupies the entire interior volume of the mold 1 (FIG. 6 a ). The liquefied product is then allowed to cool and harden. It is possible to exert a slight overpressure between the interior wall of the mold and the bag 4 by introducing a pressurized gas through the tube 6 so as to detach the bag 4 from the mold and to accompany the product during its shrinking.

Lorsque le produit moulé est refroidi et solidifié, on ouvre le moule 1 et on retire le pain P de produit formé qui est enveloppé dans la poche 4. Pour finir, on coupe au niveau de l'orifice t de remplissage l'excès de produit restant et le goulot g de la poche. Le pain P de produit enveloppé dans la poche 4 est commercialisé tel quel, la poche servant d'emballage, ou est placé dans un emballage supplémentaire tel que boîte ou papier.When the molded product is cooled and solidified, the mold 1 is opened and the loaf P of formed product is removed which is wrapped in the bag 4. Finally, the excess product is cut at the orifice t remaining and the neck g of the pocket. The bread P of product wrapped in the bag 4 is sold as is, the bag serving as packaging, or is placed in an additional packaging such as box or paper.

Le procédé illustré schématiquement sur les figures 1b à 7b est analogue à celui illustré sur les figures 1a à 7a, sauf que le volume interne du moule 10 n'est pas pressurisé.The process illustrated schematically in Figures 1 b to 7 b is similar to that illustrated in Figures 1 a to 7 a , except that the internal volume of the mold 10 is not pressurized.

Les références numériques d'éléments identiques ou jouant des rôles analogues à des éléments des figures 1a à 7a, sont égales, sur les figures 1b à 7b, à la somme du nombre 10 et de la référence utilisée sur les figures 1a à 7a ; leur description n'est pas reprise.The numerical references of identical elements or playing roles analogous to elements of FIGS. 1 a to 7 a , are equal, in FIGS. 1 b to 7 b , to the sum of the number 10 and the reference used in FIGS. 1 a to 7 a ; their description is not repeated.

Au premier stade, on introduit dans un moule 10 muni d'un évent 16, une poche 14 et on ferme le moule 10 (figures 1b, 2b). On fait ensuite le vide dans la poche 14 en mettant en communication son embouchure g avec une pompe à vide (figure 3b). Lorsque la poche est aplatie, on met son embouchure en communication avec une source de produit liquéfié 15 (figure 4b). On exerce une pression sur le produit liquéfié de façon à remplir la poche 14 en la dilatant jusqu'à ce qu'elle remplisse entièrement le volume intérieur du moule 10. Au fur et à mesure que la poche 14 se dilate et s'allonge dans toutes les directions, l'air contenu dans le volume intérieur V du moule est chassé par l'évent 16 (figure 5b).At the first stage, a pocket 14 is introduced into a mold 10 provided with a vent 16 and the mold 10 is closed (FIGS. 1 b , 2 b ). Vacuum is then made in the pocket 14 by putting its mouthpiece g into communication with a vacuum pump (FIG. 3 b ). When the pocket is flattened, its mouth is placed in communication with a source of liquefied product 15 (FIG. 4 b ). Pressure is exerted on the liquefied product so as to fill the bag 14 by expanding it until it completely fills the interior volume of the mold 10. As the bag 14 expands and elongates in in all directions, the air contained in the interior volume V of the mold is expelled by the vent 16 (FIG. 5 b ).

On cesse ensuite l'alimentation en produit liquéfié de la poche 14 et on laisse le produit se refroidir et se solidifier (figure 6b). Lorsque le produit liquéfié est solidifié sous forme d'un pain P contenu dans l'enveloppe 14, on ouvre le moule et on sort l'enveloppe 14 contenant le pain P.Then the supply of liquefied product to the bag 14 is stopped and the product is allowed to cool and solidify (FIG. 6 b ). When the liquefied product is solidified in the form of a bread P contained in the casing 14, the mold is opened and the casing 14 containing the bread P is removed.

Avec le procédé de l'invention, lors du refroidissement du produit, la paroi de la poche, du fait de son élasticité, va suivre le produit, notamment le savon, en gardant les empreintes éventuelles du moule tout en restant collée au produit.With the method of the invention, during the cooling of the product, the wall of the pocket, because of its elasticity, will follow the product, in particular the soap, keeping any imprints of the mold while remaining stuck to the product.

L'orifice de remplissage de la poche, déterminé par le passage t, a une section réduite de sorte que la perte de produit correspondant à la partie de produit solidifié dans ce passage est réduite. En outre, la zone du produit fini non recouverte par la poche, correspondant à la suppression de ladite partie de goulot g, est également réduite. L'existence de cette zone est cependant avantageuse car elle constitue une amorce de découpe facilitant le retrait de l'enveloppe au moment où le produit va être utilisé.The pouch filling orifice, determined by the passage t , has a reduced section so that the loss of product corresponding to the part of product solidified in this passage is reduced. In addition, the area of the finished product not covered by the pocket, corresponding to the removal of said neck portion g , is also reduced. The existence of this zone is however advantageous since it constitutes a cutting initiation facilitating the withdrawal of the envelope when the product is going to be used.

Selon le mode de réalisation illustré sur les figures 1c à 4c, les parois 24a, 24b de la chambre R sont constituées par deux feuilles, ou plaques, ou membranes de matière élastique, notamment matière élastomère. Ces feuilles (ou plaques) sont placées dans l'empreinte respective des deux demi-coquilles 22, 23 du moule. Lorsque le moule 20 est fermé, les bords des parois élastiques 24a, 24b sont jointifs et la chambre R ne communique avec l'extérieur que par le passage t formé par des évidements prévus dans les faces en regard des demi-coquilles 22, 23. Chaque demi-coquille est munie d'une tubulure 26 traversant l'épaisseur de sa paroi dans une zone centrale.According to the embodiment illustrated in FIGS. 1 c to 4 c , the walls 24 a , 24 b of the chamber R are constituted by two sheets, or plates, or membranes of elastic material, in particular elastomer material. These sheets (or plates) are placed in the respective imprint of the two half-shells 22, 23 of the mold. When the mold 20 is closed, the edges of the elastic walls 24 a , 24 b are joined and the chamber R communicates with the outside only through the passage t formed by recesses provided in the opposite faces of the half-shells 22, 23. Each half-shell is provided with a tube 26 passing through the thickness of its wall in a central zone.

Le cas échéant, on referme le moule de façon à chasser l'air de l'intérieur du moule en le mettant en communication avec une pompe à vide par l'intermédiaire de la tubulure t (figure 1c).If necessary, the mold is closed so as to expel the air from the interior of the mold by putting it in communication with a vacuum pump via the tube t (FIG. 1 c ).

Lorsque le vide est atteint, on met la tubulure t en communication avec une source de produit liquéfié 25 (figure 2c). On exerce une pression sur le produit liquéfié de façon à remplir le moule jusqu'à ce que les deux parois élastiques 24a, 24b, collent parfaitement aux parois du moule. On peut relier les tubulures 26 à l'aspiration d'une pompe à vide pour faciliter l'application des parois élastiques 24a, 24b contre les parois du moule.When the vacuum is reached, the tube t is placed in communication with a source of liquefied product 25 (FIG. 2 c ). Pressure is exerted on the liquefied product so as to fill the mold until the two elastic walls 24 a , 24 b , adhere perfectly to the walls of the mold. The tubes 26 can be connected to the suction of a vacuum pump to facilitate the application of the elastic walls 24 a , 24 b against the walls of the mold.

Avant remplissage, le volume intérieur de la chambre R, délimité par les parois élastiques 24a, 24b, non dilatées, est inférieur d'environ 5 % à 7 % au volume total des empreintes du moule 20.Before filling, the interior volume of the chamber R, delimited by the elastic walls 24 a , 24 b , unexpanded, is approximately 5% to 7% less than the total volume of the mold cavities 20.

Au fur et à mesure que les parois élastiques 24a, 24b se dilatent, l'air contenu dans l'interstice entre les membranes et la paroi interne du moule est chassé par la tubulure 26. Dans un mode de réalisation, non illustré, la tubulure 26 est constituée par un évidement (ou une ouverture) de dimensions relativement grandes (par exemple d'un diamètre de l'ordre de 2 cm ou 3 cm), communiquant avec l'extérieur à travers la paroi latérale du moule ; la paroi élastique est ainsi en communication directe avec l'atmosphère. Cet évidement permet la dilatation de la feuille élastique lors du remplissage à chaud sous pression.As the elastic walls 24 a , 24 b expand, the air contained in the gap between the membranes and the internal wall of the mold is expelled by the tubing 26. In one embodiment, not illustrated, the tubing 26 is constituted by a recess (or an opening) of relatively large dimensions (for example with a diameter of the order of 2 cm or 3 cm), communicating with the outside through the side wall of the mold; the elastic wall is thus in direct communication with the atmosphere. This recess allows the elastic sheet to expand during hot filling under pressure.

On cesse ensuite l'alimentation en produit liquéfié et on ferme hermétiquement la tubulure t. On laisse le produit se refroidir et se solidifier (figure 3c). On peut exercer entre la paroi intérieure du moule et le film ou la plaque d'élastomère une légère pression en introduisant un gaz sous pression à travers les tubulures 26 de façon à décoller la membrane d'élastomère du moule et à accompagner le produit pendant son rétreint lors de son refroidissement.The supply of liquefied product is then stopped and the tube t is hermetically closed. The product is allowed to cool and solidify (Figure 3 c ). A slight pressure can be exerted between the interior wall of the mold and the film or the elastomer plate by introducing a pressurized gas through the pipes 26 so as to peel off the elastomer membrane from the mold and to accompany the product during its shrinks when it cools.

Lorsque le produit liquéfié est solidifié sous forme d'un pain P, on ouvre le moule et on sort le pain P (figure 4c).When the liquefied product is solidified in the form of a bread P, the mold is opened and the bread P is removed (FIG. 4 c ).

Pour finir, on coupe au niveau de l'orifice t de remplissage l'excès de produit restant et la carotte g.Finally, the excess product remaining and the carrot g are cut at the filling orifice t .

Le pain de savon obtenu peut ensuite être gravé par frappe.The bar of soap obtained can then be engraved by striking.

De préférence, les deux parois élastiques 24a, 24b restent attachées aux demi-coquilles 22, 23 du moule ouvert. On pourrait cependant prévoir que les parois élastiques 24a, 24b demeurent autour du pain de savon P pour constituer un emballage.Preferably, the two elastic walls 24 a , 24 b remain attached to the half-shells 22, 23 of the open mold. However, provision could be made for the elastic walls 24 a , 24 b to remain around the bar of soap P to form a package.

Dans le mode de réalisation illustré sur la figure 1d, la chambre R est limitée d'un seul côté du plan de joint des demi-coquilles 32, 33 du moule 30 par une paroi élastique 34 constituée par une feuille, ou analogue, de matière élastique, notamment matière élastomère disposée dans l'empreinte de la demi-coquille 33. La paroi rigide w de l'empreinte de l'autre demi-coquille 32 vient directement au contact du produit moulé. Cette paroi w comporte avantageusement des motifs, lettres etc...en relief ou en creux, propres à réaliser directement la gravure sur le produit P1 en cours de moulage, sans nécessiter une frappe ultérieure.In the embodiment illustrated in FIG. 1 d , the chamber R is limited on one side of the joint plane of the half-shells 32, 33 of the mold 30 by an elastic wall 34 constituted by a sheet, or the like, of elastic material, in particular elastomeric material placed in the cavity of the half-shell 33. The rigid wall w of the cavity the other half-shell 32 comes directly into contact with the molded product. This wall w advantageously comprises patterns, letters, etc., in relief or in hollow, suitable for directly etching the product P1 during molding, without requiring a subsequent striking.

Du fait de la présence de la seule paroi 34 de suivi du rétreint, on obtient un pain de savon P1 légèrement dissymétrique, comme illustré sur la figure 8.Due to the presence of the single wall 34 for monitoring the constriction, a bar of slightly asymmetrical soap P1 is obtained, as illustrated in FIG. 8.

Une tubulure 36 est prévue dans la paroi de la seule demi-coquille 33 dont l'empreinte est équipée de la paroi élastique 34. La pression de suivi du rétreint est localisée uniquement sur la face du pain P1 en contact avec la paroi élastique 34.Tubing 36 is provided in the wall of the single half-shell 33, the imprint of which is equipped with the elastic wall 34. The pressure for following the constriction is located only on the face of the bread P1 in contact with the elastic wall 34.

Le volume intérieur enfermé par la paroi élastique 34, non dilatée, et la paroi w, lorsque le moule 30 est fermé, est inférieur d'environ 5 à 7 % au volume total des empreintes du moule 30.The internal volume enclosed by the elastic wall 34, not expanded, and the wall w , when the mold 30 is closed, is approximately 5 to 7% less than the total volume of the mold cavities 30.

Claims (16)

  1. A method for moulding a liquefiable product, in particular soap wherein:
    - a chamber (R) is made which is bounded by at least one wall (4; 14; 24a, 24b; 34) made of an elastic material withstanding the temperature of the liquefied product;
    - the air is evacuated from the chamber (R);
    - the chamber (R) is filled with the liquefied product;
    - the product contained in the chamber (R) is cooled;
    - and the product (P, P1) is removed from the mould;
    characterized in that
    - the chamber (R) is obtained inside a rigid mould (1, 10, 20, 30). the internal volume of the chamber (R), at rest, being smaller than that of the mouldy in such a proportion that, in order to attain the volume of the mould by inflation, the wall of the chamber must be subjected to an elongation at least equal to the contraction of the product to be moulded in absolute terms;
    - that the chamber (R) is filled with the liquefied product until the chamber (R) fills the whole of the internal volume (V) of the mould, thanks to the elasticity of its wall;
    - and that the product contained in the chamber (R) is cooled in the mould (1, 10, 20, 30).
  2. A moulding method according to claim 1, characterized in that the internal volume of the chamber (R) at rest is such that the elongation of the wall of the chamber is at least 50% at the time of its filling against the walls of the mould.
  3. A moulding method according to claim 1 or 2, characterized in that the shape of the chamber (R) at rest is substantially similar to that of the mould, so that the elongation in the different directions of space is substantially constant.
  4. A moulding method according to one of the preceding claims, characterized in that, in order to fill the chamber (R) from a source (15) of the liquefied product, pressure is exerted on the liquefied product.
  5. A moulding method according to one of the preceding claims, characterized in that a mould (1, 10, 20, 30) is used whose wall includes at least one small tube (6, 16, 26, 36) which makes it possible in the course of the cooling to exert slight pressure between the internal wall of the mould (1) and the elastic wall (4, 14; 24a, 24b; 34) of the chamber (R).
  6. A method according to one of the preceding claims, characterized in that the chamber (R) is constituted by a pouch (4, 14) made of an elastic material, in particular of latex.
  7. A method according to one of claims 1 to 5, characterized in that the elastic wall (24a, 24b; 34) of the chamber (R) comprises at least one sheet or plate made of an elastic material, in particular an elastomeric material, placed into the recess of at least one half-shell (22, 23; 33) of the mould.
  8. A method according to claim 7, characterized in that the wall made of an elastomer is constituted by silicone.
  9. A method according to claim 7 or 8, characterized in that the wall made of an elastomer has a thickness of approximately 0.6 to 0.7 mm.
  10. A method according to one of the preceding claims, characterized in that the mould has at least one opening in its side wall permitting the dilatation during the filling.
  11. A method according to one of claims 7 to 9, characterized in that a sheet or plate of an elastic material constituting an elastic wall (24a, 24b) is provided in each cavity of the half-shell of the mould (20).
  12. A method according to claim 7 or 11, characterized in that the internal volume enclosed by the undilated elastic wall (24a, 24b; 34) is less than approximately 5 to 7% of the total volume of the recesses of the mould (20; 30).
  13. A moulding method according to one of the preceding claims, characterized in that a mould (1, 10, 20, 30) is used having an internal volume comprised between 1 ml and 100 ml.
  14. A moulding method according to one of the preceding claims, characterized in that a mould is used constituted by a rigid box which serves as packing for the tablet (P) of the product contained in the pouch.
  15. A transparent or translucent soap, characterized in that it is wrapped up in a pouch (4, 14) made of an elastic material having been subjected to elongation.
  16. A soap according to claim 15, characterized in that the pouch enfolding the soap has an incipient cut.
EP91403438A 1990-12-20 1991-12-18 Process for molding a liquefiable material, especially soaps, and transparent or translucent soaps Expired - Lifetime EP0493197B1 (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
FR9016037A FR2670795B1 (en) 1990-12-20 1990-12-20 PROCESS FOR MOLDING LIQUEFIABLE MATERIAL, IN PARTICULAR SOAP, AND TRANSPARENT OR TRANSLUCENT SOAP.
FR9016037 1990-12-20

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EP0493197A1 EP0493197A1 (en) 1992-07-01
EP0493197B1 true EP0493197B1 (en) 1996-04-17

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EP (1) EP0493197B1 (en)
AT (1) ATE136928T1 (en)
DE (1) DE69118855T2 (en)
ES (1) ES2085450T3 (en)
FR (1) FR2670795B1 (en)

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US6676872B2 (en) 1997-12-30 2004-01-13 Lever Brothers Company, Division Of Conopco, Inc. Die and process especially for stamping detergent bars
WO2003025110A1 (en) * 2001-09-18 2003-03-27 Unilever N.V. Solid detergent composition
RU2508432C1 (en) * 2012-11-06 2014-02-27 Юлия Алексеевна Щепочкина Divided mould for production of columns
JP2014139307A (en) * 2012-12-22 2014-07-31 Neige Corporation:Kk Method for producing gelled detergent

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FR2443324A1 (en) * 1978-12-04 1980-07-04 Bertin & Cie Dilatant rubber moulds for fragile castings such as lipsticks - for ease of disengaging and cooling the moulding
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DE69118855D1 (en) 1996-05-23
ATE136928T1 (en) 1996-05-15
DE69118855T2 (en) 1996-11-28
EP0493197A1 (en) 1992-07-01
FR2670795A1 (en) 1992-06-26
ES2085450T3 (en) 1996-06-01
FR2670795B1 (en) 1993-04-09

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