EP1765685A1 - Tubes souples legers en matiere plastique et leur procede de fabrication - Google Patents
Tubes souples legers en matiere plastique et leur procede de fabricationInfo
- Publication number
- EP1765685A1 EP1765685A1 EP05786072A EP05786072A EP1765685A1 EP 1765685 A1 EP1765685 A1 EP 1765685A1 EP 05786072 A EP05786072 A EP 05786072A EP 05786072 A EP05786072 A EP 05786072A EP 1765685 A1 EP1765685 A1 EP 1765685A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- skirt
- tube
- weight
- capsule
- flexible tube
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 229920002457 flexible plastic Polymers 0.000 title abstract description 4
- 238000000034 method Methods 0.000 title description 12
- 229920001903 high density polyethylene Polymers 0.000 claims abstract description 14
- 239000004700 high-density polyethylene Substances 0.000 claims abstract description 14
- 239000004698 Polyethylene Substances 0.000 claims description 106
- 239000002775 capsule Substances 0.000 claims description 54
- 238000004519 manufacturing process Methods 0.000 claims description 24
- 239000000463 material Substances 0.000 claims description 22
- 229920003023 plastic Polymers 0.000 claims description 19
- 239000004033 plastic Substances 0.000 claims description 19
- 239000011324 bead Substances 0.000 claims description 11
- 229920001684 low density polyethylene Polymers 0.000 claims description 7
- 239000004702 low-density polyethylene Substances 0.000 claims description 7
- 238000001125 extrusion Methods 0.000 claims description 6
- 230000005484 gravity Effects 0.000 claims description 6
- 238000000465 moulding Methods 0.000 claims description 6
- 238000005520 cutting process Methods 0.000 claims description 3
- 229920000092 linear low density polyethylene Polymers 0.000 claims 1
- 239000004707 linear low-density polyethylene Substances 0.000 claims 1
- 239000010410 layer Substances 0.000 description 18
- 239000000203 mixture Substances 0.000 description 14
- 238000005336 cracking Methods 0.000 description 11
- 239000007788 liquid Substances 0.000 description 7
- 230000006399 behavior Effects 0.000 description 6
- -1 polyethylene copolymer Polymers 0.000 description 5
- 239000004604 Blowing Agent Substances 0.000 description 4
- 230000004888 barrier function Effects 0.000 description 4
- 230000007423 decrease Effects 0.000 description 4
- 238000004806 packaging method and process Methods 0.000 description 4
- 230000035699 permeability Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 3
- 208000021017 Weight Gain Diseases 0.000 description 3
- 238000007664 blowing Methods 0.000 description 3
- 239000000470 constituent Substances 0.000 description 3
- 239000002537 cosmetic Substances 0.000 description 3
- 229920000573 polyethylene Polymers 0.000 description 3
- 238000007493 shaping process Methods 0.000 description 3
- 238000012546 transfer Methods 0.000 description 3
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 3
- 230000004584 weight gain Effects 0.000 description 3
- 235000019786 weight gain Nutrition 0.000 description 3
- 230000004580 weight loss Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 229920000219 Ethylene vinyl alcohol Polymers 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 239000004743 Polypropylene Substances 0.000 description 2
- 230000009471 action Effects 0.000 description 2
- 239000012790 adhesive layer Substances 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000005452 bending Methods 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000000295 complement effect Effects 0.000 description 2
- 238000000748 compression moulding Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 230000007547 defect Effects 0.000 description 2
- UFRKOOWSQGXVKV-UHFFFAOYSA-N ethene;ethenol Chemical compound C=C.OC=C UFRKOOWSQGXVKV-UHFFFAOYSA-N 0.000 description 2
- 239000004715 ethylene vinyl alcohol Substances 0.000 description 2
- 238000010101 extrusion blow moulding Methods 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000003921 oil Substances 0.000 description 2
- 229920001155 polypropylene Polymers 0.000 description 2
- 238000007639 printing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 230000037303 wrinkles Effects 0.000 description 2
- VXNZUUAINFGPBY-UHFFFAOYSA-N 1-Butene Chemical compound CCC=C VXNZUUAINFGPBY-UHFFFAOYSA-N 0.000 description 1
- LIKMAJRDDDTEIG-UHFFFAOYSA-N 1-hexene Chemical compound CCCCC=C LIKMAJRDDDTEIG-UHFFFAOYSA-N 0.000 description 1
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- IMROMDMJAWUWLK-UHFFFAOYSA-N Ethenol Chemical compound OC=C IMROMDMJAWUWLK-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 240000007594 Oryza sativa Species 0.000 description 1
- 235000007164 Oryza sativa Nutrition 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 235000019568 aromas Nutrition 0.000 description 1
- 239000012298 atmosphere Substances 0.000 description 1
- 230000004323 axial length Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- IAQRGUVFOMOMEM-UHFFFAOYSA-N butene Natural products CC=CC IAQRGUVFOMOMEM-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 230000015556 catabolic process Effects 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 238000004891 communication Methods 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 230000001143 conditioned effect Effects 0.000 description 1
- 230000008094 contradictory effect Effects 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 229920001577 copolymer Polymers 0.000 description 1
- 239000007799 cork Substances 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 238000006731 degradation reaction Methods 0.000 description 1
- 238000000113 differential scanning calorimetry Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000605 extraction Methods 0.000 description 1
- 238000007647 flexography Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000002347 injection Methods 0.000 description 1
- 239000007924 injection Substances 0.000 description 1
- 238000001746 injection moulding Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 238000007645 offset printing Methods 0.000 description 1
- 235000011837 pasties Nutrition 0.000 description 1
- 230000035515 penetration Effects 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 230000002093 peripheral effect Effects 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 229920000058 polyacrylate Polymers 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 238000003825 pressing Methods 0.000 description 1
- 230000000750 progressive effect Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000004064 recycling Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 230000003252 repetitive effect Effects 0.000 description 1
- 235000009566 rice Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 238000005204 segregation Methods 0.000 description 1
- 238000005476 soldering Methods 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000003860 storage Methods 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000008961 swelling Effects 0.000 description 1
- 238000013519 translation Methods 0.000 description 1
- 239000013585 weight reducing agent Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
- 239000004711 α-olefin Substances 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D35/00—Pliable tubular containers adapted to be permanently or temporarily deformed to expel contents, e.g. collapsible tubes for toothpaste or other plastic or semi-liquid material; Holders therefor
- B65D35/02—Body construction
- B65D35/10—Body construction made by uniting or interconnecting two or more components
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
- B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
- B65D47/00—Closures with filling and discharging, or with discharging, devices
- B65D47/04—Closures with discharging devices other than pumps
- B65D47/06—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages
- B65D47/08—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages having articulated or hinged closures
- B65D47/0804—Closures with discharging devices other than pumps with pouring spouts or tubes; with discharge nozzles or passages having articulated or hinged closures integrally formed with the base element provided with the spout or discharge passage
Definitions
- the invention relates to the field of flexible plastic tubes for storing and dispensing liquid to pasty products. It relates more particularly to flexible plastic tubes of large capacity, typically having a capacity greater than or equal to 150 ml.
- a flexible tube is made by assembling two separately manufactured parts: a flexible cylindrical skirt of given length (typically 3 to 5 times the diameter) and a head comprising a neck provided with a dispensing orifice and a shoulder connecting said neck with cylindrical skirt.
- the plastic head can be molded separately and then welded to one end of the skirt but it is advantageously molded and welded autogenously to the skirt using either an injection molding technique (FR 1 069 414) or a technique compression molding of an extruded blank (FR 1 324 471).
- the cylindrical skirt can be obtained industrially in two different ways.
- tubes intended for storing and dispensing cosmetic products it is generally obtained by extrusion or direct coextrusion of several plastics, in the form of a cylindrical hollow extrudate.
- the tube having such a skirt is in this case called "plastic tube”.
- a plastic strip is generally used which is shaped into a cylinder by matching (contact or superimposition) of its two longitudinal edges ( see for example US 1,007,779) and then longitudinal weld along these edges.
- the tube having such a skirt - which is often made of a multilayer plastic material with a barrier layer - is in this case called "rolled tube".
- the tube is delivered to the conditioner, the head down and the dispensing orifice closed - for example by a cap screwed onto the neck - so that it fills the tube by the open end of the tube.
- the tubes are placed vertically, grouped and sheaves. The sheaves are stacked on one another forming a large number of layers whose thickness corresponds to the axial length of the tube, which typically leads to stack of about fifteen layers for truck transport.
- the tube is filled, its open end is flattened so as to perform a weld which, by the meeting of wall portions facing each other following the flattening, seals the product thus conditioned (so-called transversal or final weld).
- the diameter of the skirt is typically between 40 mm and 60 mm
- the thickness of the skirt of the prior art is systematically greater than 0.5 mm, that it is (co ) extruded ,. laminated, or obtained by extrusion blow molding.
- the embodiment of the skirt it must undergo a large number of manipulations until the filled tube has been sealed by the final weld, These manipulations are necessary firstly to perform transfers between different manufacturing stations and secondly to ensure sufficient mechanical support during manufacturing operations or shaping (assembly of the head and the skirt, printing on the skirt, corking, ).
- the tube Upon arriving at a manufacturing or forming station, the tube is driven from a holding device mounted on a transfer chain (for example a pin, a nacelle or a mandrel) to a mandrel on which it is fitted most of time without play and even with a slight tightening.
- a transfer chain for example a pin, a nacelle or a mandrel
- the operation is complete, it is extracted from the mandrel and directed to a new holding device associated with another transfer chain to drive it to another manufacturing station.
- Flexible tubes that have skirts large diameter do not have sufficient rigidity if the thickness of said skirts is less than 0.5 mm. They are exposed, particularly at their open end, to a high risk of folding either during the fitting on the mandrel, or during the extraction of the mandrel. To limit this risk, it could increase the clearance between the skirt and the mandrel but this would result in less good maintenance of the skirt during the manufacturing operation or shaping and could result in insufficient quality: less accuracy the positioning of the head on the skirt which can lead to a defect of welding between the head and the skirt, bad plating of the skirt on the mandrel causing printing defects (offset printing or flexography on cylindrical wall of tubular bodies), etc.
- the stacked tubes located in the lower layers must support the weight of the sheaves stacked above and they are often deteriorated at the open end of their skirt if it does not have the desired rigidity.
- the open end of the tube has a geometry which is less repetitive since the thickness is small (greater influence of the residual stresses on the shape of the free end of the skirt), which leads to difficulties when automatically filling the tube.
- bottles are made in one piece by extrusion-blow molding: one extrudes a thick tube that is clamped away from the die (obtaining a parison) and then inflates the inside of the parison by sending air under low pressure through the axis of the die, the wall of the parison tapering and coming to press against the walls of a mold that gives the final shape of the bottle.
- extrusion-blow molding US Pat. No.
- WELLA 6,082,563
- WELLA describes a manufacturing process by which the constituent plastic material of the wall of the parison is partially modified by adding blowing agents.
- the blowing agents are introduced into an intermediate layer during coextrusion.
- the thickness of the expanded layer is, after extrusion and before blowing, equal to or greater than 3 mm. After blowing it is of the order of 500 microns, that is to say close to the thickness of a flexible tube skirt.
- the lightening of an expanded layer with a blowing agent is only possible in this case because a thick parison of at least 3 mm is extruded.
- the skirt of the tube must be obtained directly by extrusion with a thickness at least six times lower, under conditions such that it is difficult or impossible, to control the action of the swelling agent in the screw and then in the convergent zone of the extruder, so that a skirt is obtained with an expanded extruded layer with irregularities of large thickness, which does not allow to provide acceptable industrial packaging.
- blowing agents entails an additional cost.
- the Applicant has sought to obtain a flexible tube of great capacity as light as possible, which has a cylindrical skirt as strong and rigid as that of standard tubes, while offering the user a comfortable grip and resistance to stress cracking comparable to that of standard tubes.
- the goal is to significantly reduce (at least 30%) the weight of the tubes while maintaining an acceptable mechanical behavior compatible with the constraints of manufacture and with its use by the consumer.
- these tubes are mainly intended for the cosmetics market, they must also have equivalent compatibility to these products, in particular to guarantee a low permeability to liquids (water, alcohols, oils and other fatty substances, etc.). ), and this low permeability to liquids should result in limited weight losses. It is also desirable that they have an acceptable permeability to water vapor and flavorings.
- a first object of the invention is a method of manufacturing a flexible tube comprising a cylindrical skirt and a dispensing head (that is to say provided with a dispensing orifice), comprising at least the following steps: a) extruding a cylindrical sleeve b) cutting the sleeve so as to produce a tube skirt to the desired length; c) molding of the flexible tube head; d) fixing the head on one end of the skirt; characterized in that the extruded sleeve has a thickness of between 0.2 and 0.4 mm, preferably between 0.25 mm and 0.35 mm and in that it comprises high density polyethylene (PE, HD), with a density of between 0.935 g / cm 3 and 0.97 g / cm 3, preferably greater than 0.945 g / cm 3, in a proportion by weight greater than 55%, preferably 70%.
- PE high density polyethylene
- the sleeve also comprises low-density polyethylene (PE, BD) with a density of between 0.86 g / cm 3 and 0.93 g / cm 3, in a proportion by weight of less than 45%, preferably 30%, and of which more than 50%, preferably more than 90% by weight, is a PE.
- PE low-density polyethylene
- BDL Linear BD
- This method incorporates the conventional steps of manufacturing a plastic tube, the skirt of which comes from the cutting of an extruded sleeve, but this sleeve is particularly thin and comprises a plastic material different from that of plastic tubes of the prior art.
- the sleeve is obtained by extrusion of a mixture PE, HD + PE, BD (more than half being PE, BDL) or by coextrusion of several coaxial layers, PE, HD, PE. BD (more than half being PE, BDL), or layers of PE mixtures.
- the plastic tubes. thus_ realized offer . the best characteristics (with respect to all the manufacturing and use constraints) when the sleeve has been made with more than 90% by weight of PE. HD and less than 10% by weight of PE.BDL.
- Another object of the invention is a flexible tube having a dispensing head and a cylindrical skirt of plastic or metalloplastic material, of diameter greater than 44 mm, more particularly greater than 49 mm, characterized in that said cylindrical skirt has a thickness between 0.2 mm and 0.4 mm, preferably between 0.25 mm and 0.35 mm, in that it comprises high-density polyethylene (PE HD) with a density of between 0.935 g / cm 3 and 0.97 g / cm 3, preferably greater than 0.945 g / cm 3, in a weight proportion greater than 55%, preferably 70%.
- PE HD high-density polyethylene
- the cylindrical skirt also comprises low density polyethylene (PE, BD) with a density of between 0.86 g / cm3 and 0.93 g / cm3, in a proportion by weight of less than 45%, preferably 30%, and of which more than 50%, preferably more than 90% by weight, is a PE.
- PE low density polyethylene
- BDL Linear DB
- the tube according to the invention is a plastic tube or a rolled tube having a head provided with a dispensing orifice and a cylindrical skirt of large diameter, typically greater than 44 mm.
- the head generally comprises a neck which encloses the dispensing orifice and a shoulder which connects the neck to the skirt.
- the skirt is cylindrical but its section is not necessarily circular. In fact, the tube is here described in its filling configuration, before completion of the final transversal weld which seals the packaged product.
- the skirt may have a circular or elliptical orthogonal section or any other shape
- flexible tubes have skirts composed mainly or entirely of PE. BD.
- a tube according to the invention having the same diameter as a traditional tube has a thinner skirt but composed predominantly - or in full - of PE.HD. If the PE.HD is not alone, the skirt may be made of a single material, for example a blend resulting from a mixture according to the invention of PE.HD and PE.BD, the major part of which is a Linear PE.BD.
- PE.BDL and the percentage of PE.HD within such a blend can be determined for example using two complementary techniques: Fourier transform infrared spectroscopy (FTIR), for example using a spectrometer FTIR Nicolet 510P and Differential Scanning Calorimetry, for example using a complete Perkin Elmer DSC 7 analysis system, this method can itself be implemented in a conventional manner (up-down cycle - temperature rise), that is, when necessary, according to the method SIST (Stepwise Isothermal Technical Segregation.
- FTIR Fourier transform infrared spectroscopy
- SIST Stepwise Isothermal Technical Segregation.
- the skirt, laminated or coextruded may also be made of a multilayer material comprising PE.HD layers, PE.BD layers, the major part of which is a PE.Bpjinéaire, and / or layers of PE mixtures. HD + PE.BD.
- the skirt may have, due to its lower thickness, a resistance to radial penetration identical or lower than that of a skirt of the prior art while by presenting, despite this lower thickness, a similar or better resistance to buckling and bending under the effect of the same compressive axial force.
- the PE.BD was supposed to be the only material capable of satisfy, provided however that it is in the form of a sufficiently thick layer. Contrary to appearances, the use of a material more rigid than the PE. BD to compensate for loss of rigidity due to thinning is not obvious.
- This shape memory is often characterized by the angle obtained after folding and elastic return of a band of constant thickness: the larger the angle, the higher the shape memory is important; conversely, the weaker the angle, the better is its ability to keep the new form, translated by the Anglo-Saxon term of "dead fold".
- the metal tubes have a very good ability to wrinkle while the plastic tubes have a wrinkle ability generally poor or poor.
- the Applicant has found that, thanks to the significant decrease in the thickness of its wall, the tube has a better property at "dead fold", that is to say a better ergonomics of use despite the use of a material (PE.HD) more rigid than PE. BD.
- the outer layers are preferably PE. HD: this results in slightly better axial buckling resistance.
- the PE.HD outer layers are less sensitive to stress cracking.
- the EP. HD has a much lower liquid permeability than PE. BD, in a ratio such that the decrease in thickness does not cause a degradation of the liquid barrier properties (water, alcohols, oils and other fatty substances that may be contained in the cosmetic product to be packaged), which maintains the performance in terms of acceptable weight losses.
- the liquid barrier properties water, alcohols, oils and other fatty substances that may be contained in the cosmetic product to be packaged
- PE.BD if it exists in the skirt, is a minor constituent material, limited to 30% by weight, preferably 10%. It consists for the most part of linear PE.BD (or PE.BDL), that is to say a polyethylene copolymer comprising non-polar alphaolefins (such as butene or hexene) whose molecules have only side chains short and regular.
- linear PE.BD is recommended to improve on the one hand the weldability of the skirt and on the other hand the resistance to stress cracking.
- Stress cracking is a property related to long-term behavior: by immersing the material under stress in a surfactant liquid, cracking appears after a certain time. This phenomenon, very important in the case of polyethylene, strongly depends on the surface tension exerted by the medium, the molecular weight and the morphology of the polymer. It is known that cracking occurs all the more quickly as the stress is high and that the material (polyethylene in this case) has a significant melt index (“melt index").
- the linear PE.BDL (PE.BDL) is in a proportion by weight greater than 50%.
- This proportion is preferably higher as the proportion of PE.BD is important in the material of the skirt. This makes it possible to improve the weldability and resistance to stress cracking of the skirt. So, for a melange 70% PE. HD + 30% PE. BD, the latter should preferably be greater than 90% by weight of PE.BDL.
- the plastic and laminated tubes offer the best characteristics relating to all the constraints of manufacture and use when the skirt comprises more than 90% by weight of PE . HD and less than 10% by weight of PE.BDL.
- the flexible tube also has a lightened dispensing head to which must be attached a plug or a dispensing tip, such as a service capsule.
- the tube head comprises a neck surrounding the dispensing orifice and a shoulder connecting said neck to the skirt and it is on said neck that is fixed that plug or this capsule-service.
- a neck provided with a securing means such as a snap-fitting bead is preferred to a neck provided with a screw thread, which is more sensitive to stress cracking.
- the thickness of the goulpt and. of . the shoulder at a value typically less than 1 . mm.
- Said head is preferably made of a material which comprises high density polyethylene (HDPE), with a density of between 0.935 g / cm 3 and 0.97 g / cm 3, preferably greater than 0.945 g / cm 3, in a proportion by weight greater than 55%, preferably 70%.
- the head also comprises low density polyethylene (PE, BD) with a specific gravity of between 0.86 g / cm 3 and 0.93 g / cm 3, in a proportion by weight of less than 45%, preferably 30%, and more than 50%, preferably more than 90% by weight, is a linear PE.BD (PE.BDL)
- the tube has a head composed predominantly - or totally - of PE. HD.
- the head may be made of a single material, for example a blend resulting from a mixture according to the invention of PE. HD and PE.BD, most of which is a linear PE.BD.
- the head can also have a multi-layer wall with PE layers. HD and / or PE. BD, most of which is an EP. BD linear, and / or mixtures PE.HD + PE.BD.
- the head can be molded separately and then welded to one end of the skirt, but it can also be molded and welded autogenously to the skirt.
- This multilayer head can be obtained either by co-injection according to a process such as that described in EP 1 123 241, or by compression molding of a coextruded blank.
- the head may have a neck and a shoulder less than 1 mm thick.
- a te! tube has a substantial saving in weight: while a standard tube typically weighs between 0.80 and 1.10 g per centilitre of useful volume, a tube according to the invention of the same capacity weighs between 0.55 and 0.80 g by cl of useful volume. Thus, only with the flexible tube, a weight gain of 30% is obtained. .. _This gain can. to be, still increased if one continues the effort of lightening on the cork.
- Another object of the invention is a tube such as the flexible tube described above, also provided with a stopper,
- This stopper can be a lighter service capsule so that the tube + capsule-service assembly has a mass between 0.80 and 1.10 g / cl of useful volume of product to be dispensed against a value of between 1.20 and 1.80 g / cl for the prior art dispensing tubes.
- the new tube provided with its new service capsule has a weight approximately identical to that of the tube alone of the prior art: the gain is reflected in a weight reduction equivalent to the weight of the capsule. service!
- the capsule-service itself has been designed in a particular way, with a thickness and height as low as possible.
- the capsule-service has an overall structure identical to that of the service capsules of the prior art, which comprise a base intended to be fixed irreversibly on the head of the tube and a cap pivoting around a hinge located at the periphery of the base and the cap, the cap from closing a hole formed on the base and in communication with the dispensing orifice of the tube head.
- the base comprises a tray, provided with said orifice, a fixing skirt and an outer lateral skirt, generally cylindrical and configured so that it is approximately in the extension of the skirt of the tube, when the service capsule is fixed. on said tube.
- the service capsule has a thick and rigid base, in particular to have a clear opening, the cap pivoting about a fixed axis connected to the tube.
- the rigidity of the base also made it possible to rapidly unmold the capsule-service using the conventional positioning of the extractor assisting the demolding of the capsule-service: the latter comes into abutment on the open end of the outer side skirt.
- the rigidity was ensured on the one hand by the thickness of the walls of the base and on the other hand by the presence of radial ribs, at least 6, typically 8, attached to the inner surface of the outer side skirt and to the surface internal plateau. These notably prevented the outer side skirt from deforming, or even turning around like a sock, when the extractor was activated to demold the entire capsule-service.
- the service capsule has been designed in order to reduce the weight, reduce the cooling times after molding and facilitate demolding. This is why the thickness of the wall of the plate, that of the outer lateral skirt and that of the cap has been decreased, especially at the level of the upper part of the finger grip.
- the extractor is placed differently and bears on the open end of the fixing skirt which has not not thinned.
- the capsule-service according to the invention thus has at least one, and preferably all, of the following geometrical features:
- the inner surface of the base is free from any stiffening radial rib; it contains at most one longitudinal rib which serves for the angular orientation of the service capsule relative to the decoration of the skirt of the flexible tube (indexing);
- the fixing skirt is relatively thicker than the rest of the service capsule: by applying to the mold the extractor on the open end of the said fixing skirt, the entire capsule can be demolded easily despite its thinned portions; and although it is not supported by radial ribs; thus, the fixing skirt is thicker, typically a few tenths of a millimeter, than the rest of the capsule service, including the tray and the outer side skirt.
- the cap has on its inner face an undercut wall at the upper part of the fingertip; in the prior art, there was defined at this location a vertical wall, which had the advantage of facilitating demolding and disadvantage of greatly increase the thickness and thus weigh down the cap.
- the wall is in cant and if one seeks to maintain a constant thickness, this part in cant results in an undercut difficult to unmold if one uses a standard tool, that is to say in the absence of slide-type sliding tool or upward shim.
- the Applicant has found that it is still possible to achieve an undercut with a slope less than 35 ° without having any particular difficulty in demolding with a standard mold, but using an extractor acting in the center of the cap.
- the cap has, facing the upper part of the finger grip, a wall inclined at an angle less than 35 ° - with respect to the axis of the capsule - towards the inside of the base of the capsule.
- the geometry of the outer side skirt is preferably defined, in particular its height, so that when the service capsule is fastened to the tube head, the open end of said outer side skirt is a distance d as small as possible from the shoulder of the tube, typically a mean distance of between 0.1 and 0.7 mm, preferably between 0.2 and 0.5 mm.
- the dimensional manufacturing tolerances imposed on the tube head and the service capsule are suitably defined.
- the minimum distance LI between the end of the outer side skirt and the point of contact on the bead of the fixing skirt is made to be greater than L2-d, L2 being the maximum distance between the contact on the bead of the neck and the point of the shoulder being in line with the axial extension of the outer side skirt of the capsule-service.
- the shoulder of the tube is advantageously provided with a sidewalk around which the open end of the outer side skirt engages with a radial clearance as low as possible, typically an average radial clearance less than 0.5 mm, preferably 0.3 mm.
- the capsule-service must be generally indexed, namely placed in a precise angular position relative to a decoration of the skirt of the tube.
- the very reliable but rather heavy indexing means described in EP-B-0 633 197 may, where possible, be replaced by a single longitudinal rib attached to the inner surface of the outer side skirt which is trapped between two studs of low extent and low height, located on the shoulder.
- the attachment of the service capsule on the tube is effected by a driving movement and rotation.
- the capsule is immobilized in axial displacement, for example by means of complementary snap-fastening means of the fixing skirt and the neck described above.
- the base of the longitudinal rib comes into contact with the top wall of the first stud which slopes gently in the circumferential direction.
- the longitudinal rib follows the top wall which, like a cam surface, imposes a certain axial translation to the outside of the tube. Arriving at the end of the cam path, the end of the longitudinal rib is no longer supported, elastically releases and is trapped in the interval between the two pads.
- the relief of the second stud is less progressive so that the latter acts as a stop and prevents the longitudinal rib from continuing to move angularly.
- the upper part of the mandrel which serves as a mold part at the tube head advantageously has two protuberances which serve as "cores" for the formation of these pads, so that these are made with a constant thickness and have a hollow towards the inside of the tube.
- the longitudinal rib attached to the inner surface of the outer side skirt and used for indexing is advantageously located in the median plane of the hinge: this facilitates the feeding of the narrow channels defining the different parts of the hinge (tensioning elements and ch ⁇ rayne proper) and this improves the mechanical strength of the capsule when the cap is requested at the opening.
- Figure 1 illustrates, in diametral section, a 150 ml tube of the prior art, provided with a service capsule, for the storage and distribution of shamp ⁇ ing.
- Figure 2 illustrates, in diametral section, a tube according to the invention of the same capacity as that of Figure 1, and for the same application.
- FIG. 3 illustrates, in diametral section, a detail of the tube of FIG. 2.
- FIG. 4 illustrates, in diametral section, a detail of the molding tool of a lighter service capsule according to the invention, situated at the level of the cap.
- the flexible tubes presented in this example offer a useful volume of 150 ml for the shower gel that they are intended to contain.
- a tube of the prior art is illustrated in FIG. 1.
- a particular tube according to the invention is illustrated in FIG. 2.
- This tube may be equipped with a service capsule such as that illustrated in FIG. 3 and molded in a tooling of which a detail is illustrated in Figure 4.
- the tube 110 of the prior art has a diameter D of 50 mm and an overall height (greater than H + h) close to 175 mm. It has a skirt 120 and a dispensing head 130 provided with a neck 131 and a shoulder 132 for connecting said neck to said skirt.
- the skirt 120 is PE.BD. It has a thickness ei of 0.6 mm, which gives the tube dispenser shower gel a certain rigidity.
- the head 130 is also in PE.BD.
- the shoulder 132 has a thickness e2 of 1.1 mm.
- the weight of the tube according to the prior art is 16.4 g.
- the service capsule 140 comprises a base 141 intended to be fixed irreversibly on the neck 131 of the tube and a cap 142 pivoting about a hinge 143 located at the periphery of the base and the cap, the cap sealing a orifice 150 formed on the base 141.
- the base 141 comprises a plate 1411, provided with the dispensing orifice and an outer lateral skirt 1410 cylindrical and configured so that it is approximately in the extension of the skirt 120 of the tube .
- the service cap 140 according to the prior art has a thick and rigid base.
- the rigidity is supported by the presence of 8 radial ribs 144, attached to the inner surface of the outer side skirt 1410 and to the inner surface of the plate 1411.
- the lip 142 has, at the top portion 147 of the fingertip , a vertical wall 148.
- the tube + capsule-service set weighs 26 g.
- the tube 210 has a diameter D 1 of 50 mm neighbor and an overall height (H + h ') close to 173 mm. It has a skirt 220 and a dispensing head 230 provided with a neck 231 of diameter approximately 20 mm and a shoulder 232 intended to connect said neck to said skirt.
- the skirt 220 is PE.HD. It has a thickness é1 of 0.35 mm, which gives the shower gel dispenser tube a greater flexibility, acceptable by all users.
- the head 230 is also PE.HD.
- the shoulder 232 has a thickness e2 of 1 mm.
- the weight of this tube is 1 1 g.
- the centering studs 235 are made with a constant thickness, that is to say having a hollow towards the inside of the tube.
- This tube is provided with a service capsule 240 made of polypropylene, with a height h equal to 22.7 mm.
- the service capsule 240 comprises a base 241 intended to be fixed irreversibly on the neck 231 of the tube and a cap 242 pivoting about a hinge 243 located at the periphery of the base and the cap, the cap closing off a orifice 250 formed on the base 241.
- the cap 242 pivots around the hinge 243 when the user exerts a force in the upper part 247 of the finger grip located on the cap.
- the base 241 comprises a plate 2411 surrounded by an outer cylindrical lateral skirt 2410, configured so that it is approximately in line with the skirt 220 of the tube.
- the service capsule 240 does not have 8 radial ribs to improve its rigidity, but only one longitudinal rib 245, thin and of low radial height, attached to the inner surface of the outer lateral skirt 2410.
- This longitudinal rib 245 allows indexing the capsule-service relative to the tube skirt, by trapping between two small and low-height studs located on the shoulder 230.
- One of these pads is illustrated in Figure 2 with the reference 235.
- the capping 242 has, at the level of the upper portion 247 of the finger grip, a wall 248 in a slope, inclined at about 25 ° with respect to the axis of the capsule and oriented towards the inside of the base 241 of the capsule 240.
- the axis of the capsule is the axis of the mounting skirt 246. It coincides with the axis of the tube when the service capsule is fixed on said tube.
- the attachment means of the service capsule on the tube head are snap beads disposed on the one hand on a fastening skirt 246 attached to the plate 2411 and on the other hand on the neck 231 of the tube head.
- the geometry of the outer side skirt 241 has been defined, in particular its height h 1 , so that when the service capsule 240 is fixed on the tube head, the open end of the outer side skirt 2410 is close of the shoulder 230 of the tube, typically at a distance of less than 0.5 mm from the
- the manufacturing dimensional tolerances imposed on the tube head and the capsule service are defined so that the distance minimum LI between the end of the outer side skirt 2410 and the point of contact on the bead 2460 of the skirt of
- fixation 246 is greater than L2-d, where L2 is the maximum distance between the point of contact on the bead 2310 of the neck 231 and the point of the shoulder 2320.
- the tube + capsule-service assembly weighs 16.7 g.
- the fixing skirt 246 on the neck 231 has a thickness of 0 1, 2 mm, greater than that of the rest of the service capsule, in particular the outer side wall 2410 (0.9 mm).
- the fastening skirt 246 also has a discontinuous snap-in bead (in the form of regularly distributed grains of rice) cooperating with the snap-fitting bead 2310 of the neck 231.
- PE.HD 120 ⁇ m
- PE.BDL 1 10 ⁇ m
- PE.HD 120 ⁇ m
- the flexibility of the tube skirt is characterized by the value of a force necessary to obtain a certain radial depression after a certain time. The lower this value, the more flexible the tube. Moreover, by comparing the values corresponding to two different radial depressions, one can evaluate the comfort of use (of "grip") by noting the difference to the proportionality: if the value corresponding to a double radial depression is greater at double the corresponding effort, the tube opposes increasing resistance to the action of the user. The more the difference between these values is import ⁇ nt, the more the tube is difficult to empty. Conversely, if the value corresponding to a double radial depression is less than twice the corresponding effort, the tube empties easily. The greater the difference between these values, the more the tube tends to collapse abruptly, which may surprise the user with a larger output stream than expected.
- the flexibility can be measured with standardized bending tests using the method of the support blade: a skirt half is cut in a diametral plane and then recessed at its ends on a support. The top of the arch thus formed is driven by an axial device bearing on the generatrix of the top of the arch. The value of the driving force corresponding to two given deflections is measured: for example 5 mm and 10 mm.
- the skirts of the tubes B to D according to the invention are more flexible than the skirts of the prior art (Tube A), on the other hand that the gap to the proportionality is of the same order of magnitude (ratios between forces of between 2.6 and 2.8 for a double depression): the tubes according to the invention are more flexible than that of the prior art while presenting a comfort of use identical.
- the machinability of the tube is characterized by the ability of the skirt to withstand an axial compressive force.
- the skirt is cut to a given length (80 mm in this case), one of the free ends of the sleeve thus obtained is fitted and a force distributed over the circumference is applied to the other free end, with the aid of a plateau that sinks at a constant speed in the axial direction of the sleeve.
- the value of the compression peak is measured just before folding or buckling of the sleeve.
- PE.BD tube of thickness 0.5 has a lot of memory (it comes back to 128 ° (for a complete memory, the angle after elastic return would be 180 °), whereas for the tube in PE.HD 0.35 thickness, the angle after elastic return is equal to only 61. It is close to the behavior of the flexible metal tube.
- a standard (non-lowered) truck can carry 66 pallets of 50 mm diameter tubes (150 ml capacity), or about 140,000 tubes.
- FIG. 4 illustrates, in diametral section, a detail of the molding tool 300 of a lighter service capsule according to the invention such as the capsule 240.
- the tooling is in several parts: an upper part 310, a part lower part 320 provided with an extractor 330.
- the pivoting cap of the service capsule is made by molding in the cavity 342.
- the lower part 320 of the mold comprises a wall 321 which delimits the upper part 2421 (external) of the fingertip and a wall 322 located on the other side of the wall 321 and facing the inside of the cap.
- the wall 322 was vertical, which had the advantage of facilitating demolding and the disadvantage of greatly increasing the thickness and thus weigh down the cap.
- the Applicant has found that one could still achieve a wall 322 with an undercut of less than 35 ° slope without having difficulty in demolding with a standard mold, that is to say without drawer or shim, but using an extractor 330 acting in the center of the cap.
- the cap has, facing the upper part 247 of the finger grip, an inclined wall - an angle less than 35 ° with respect to the axis of the capsule-service - to the inside of the base of the capsule.
- the axis of the service capsule is the axis 250 of the fixing skirt whose cavity is indicated by the reference 346. It coincides with the axis of the tube when the service capsule is fixed on said tube.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Closures For Containers (AREA)
- Tubes (AREA)
- Rigid Pipes And Flexible Pipes (AREA)
Abstract
Description
Claims
Priority Applications (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PL05786072T PL1765685T3 (pl) | 2004-07-06 | 2005-07-04 | Lekkie kapsle zamykające z tworzywa sztucznego i giętkie lekkie tubki wyposażone w takie lekkie kapsle zamykające |
PL08017038T PL2022724T3 (pl) | 2004-07-06 | 2005-07-04 | Giętkie tubki z tworzywa sztucznego i sposób ich wytwarzania |
EP08017038A EP2022724B1 (fr) | 2004-07-06 | 2005-07-04 | Tubes souples en matière plastique et leur procédé de fabrication |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR0407471A FR2872792B1 (fr) | 2004-07-06 | 2004-07-06 | Tubes souples legers en matiere plastique et leur procede de fabrication |
PCT/FR2005/001708 WO2006013276A1 (fr) | 2004-07-06 | 2005-07-04 | Tubes souples legers en matiere plastique et leur procede de fabrication |
Related Child Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08017038A Division EP2022724B1 (fr) | 2004-07-06 | 2005-07-04 | Tubes souples en matière plastique et leur procédé de fabrication |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1765685A1 true EP1765685A1 (fr) | 2007-03-28 |
EP1765685B1 EP1765685B1 (fr) | 2008-11-26 |
Family
ID=34949575
Family Applications (2)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08017038A Revoked EP2022724B1 (fr) | 2004-07-06 | 2005-07-04 | Tubes souples en matière plastique et leur procédé de fabrication |
EP05786072A Active EP1765685B1 (fr) | 2004-07-06 | 2005-07-04 | Capsules-services legeres en matiere plastique et tubes souples legers munis desdites capsules-services legeres. |
Family Applications Before (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP08017038A Revoked EP2022724B1 (fr) | 2004-07-06 | 2005-07-04 | Tubes souples en matière plastique et leur procédé de fabrication |
Country Status (10)
Country | Link |
---|---|
US (1) | US8365955B2 (fr) |
EP (2) | EP2022724B1 (fr) |
CN (1) | CN101001789B (fr) |
BR (1) | BRPI0513140A (fr) |
DE (2) | DE602005011293D1 (fr) |
FR (1) | FR2872792B1 (fr) |
MX (1) | MX2007000233A (fr) |
PL (2) | PL1765685T3 (fr) |
RU (1) | RU2007104344A (fr) |
WO (1) | WO2006013276A1 (fr) |
Families Citing this family (12)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP2036697A1 (fr) * | 2007-09-13 | 2009-03-18 | Aisapack Holding SA | Procédé de fabrication de tubes par soudage |
FR2949761B1 (fr) | 2009-09-10 | 2011-12-02 | Oreal | Dispositif de conditionnement et de distribution d'un produit |
EP2718076B1 (fr) | 2011-06-09 | 2018-01-03 | Essel Propack Ltd. | Composition de polymères pour la production d'articles biodégradables et procédé correspondant |
FR2984092B1 (fr) * | 2011-12-16 | 2014-04-04 | Oreal | Dispositif de conditionnement et de distribution |
US9470213B2 (en) * | 2012-10-16 | 2016-10-18 | Raytheon Company | Heat-actuated release mechanism |
CH707854A2 (de) * | 2013-03-20 | 2014-09-30 | Alpla Werke | Extrusionsblasgeformte Tube. |
FR3016613A1 (fr) * | 2014-01-17 | 2015-07-24 | Cep Tubes | Tube souple injecte a base de polyethylene haute densite |
US9505534B2 (en) * | 2014-01-28 | 2016-11-29 | Mead Johnson Nutrition (Asia Pacific) Pte. Ltd. | Resealable container with collar and lid |
ES2966154T3 (es) * | 2019-11-07 | 2024-04-18 | Aptar Freyung Gmbh | Dispositivo de cierre |
EP3822075A1 (fr) | 2019-11-15 | 2021-05-19 | TUPACK Verpackungen Gesellschaft m.b.H. | Tube |
CN111923372A (zh) * | 2020-09-09 | 2020-11-13 | 广州市瑞高包装工业有限公司 | 一种塑料软管制备方法及软管 |
KR102353294B1 (ko) * | 2021-01-14 | 2022-01-19 | 제이씨텍(주) | 마개 조립 척 및 이를 이용한 마개 조립 방법 |
Family Cites Families (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB8625169D0 (en) * | 1986-10-21 | 1986-11-26 | Duma Packaging As | Closure assembly |
US5547091A (en) * | 1991-11-27 | 1996-08-20 | Colgate-Palmolive Company | Dispensing container snap hinge closure |
DE69311497T2 (de) * | 1992-10-26 | 1997-11-06 | Mitsui Petrochemical Ind | Zusammendrückbarer rohrförmiger Behälter und Verfahren zu seiner Herstellung |
FR2736621B1 (fr) * | 1995-07-10 | 1997-08-22 | Oreal | Recipient comportant un orifice de distribution muni d'un systeme de fermeture |
DE19603906A1 (de) | 1996-02-03 | 1997-08-07 | Wella Ag | Flaschenartiger Behälter aus Kunststoff und Verfahren zu seiner Herstellung |
FR2752818B1 (fr) * | 1996-08-29 | 1998-10-16 | Oreal | Capsule articulee a element de liaison ameliore |
GB2337035B (en) * | 1998-05-08 | 2002-12-04 | Courtaulds Packaging Ltd | Containers |
FR2784657B1 (fr) | 1998-10-19 | 2000-11-17 | Cebal | Tube a tete en materiaux multicouches et procede de fabrication |
WO2002044055A1 (fr) * | 2000-11-30 | 2002-06-06 | Cebal S.A. | Recipients ayant une paroi contenant des agents biocides |
US6631833B2 (en) * | 2001-02-16 | 2003-10-14 | Ccl Container Corporation | Oval-shaped tube closure |
CN100415495C (zh) * | 2002-05-15 | 2008-09-03 | 中国石化集团齐鲁石油化工公司 | 医用吹塑成型聚烯烃中空容器和制备工艺 |
US6848603B2 (en) * | 2002-07-17 | 2005-02-01 | Crown Cork & Seal Technologies Corporation | Closure having improved tamper evident features |
AU2003217987A1 (en) * | 2002-11-20 | 2004-06-18 | Cosmolab, Inc. | Cosmetic container, cosmetic applicator, and methods of making the same |
US7404495B2 (en) * | 2003-07-28 | 2008-07-29 | Rexam Closure Systems Inc. | Child-resistant flip-top dispensing closure and package |
US7128227B2 (en) * | 2003-09-22 | 2006-10-31 | Polytop Corporation | Dispensing closure with stop wall for positive alignment on container |
US7255250B2 (en) * | 2004-06-22 | 2007-08-14 | Owens-Illinois Closure Inc. | Dispensing closure, package and method of manufacture |
-
2004
- 2004-07-06 FR FR0407471A patent/FR2872792B1/fr not_active Expired - Lifetime
-
2005
- 2005-07-04 US US11/571,291 patent/US8365955B2/en active Active
- 2005-07-04 RU RU2007104344/12A patent/RU2007104344A/ru not_active Application Discontinuation
- 2005-07-04 PL PL05786072T patent/PL1765685T3/pl unknown
- 2005-07-04 DE DE602005011293T patent/DE602005011293D1/de active Active
- 2005-07-04 CN CN200580027314XA patent/CN101001789B/zh not_active Expired - Fee Related
- 2005-07-04 DE DE602005025548T patent/DE602005025548D1/de active Active
- 2005-07-04 PL PL08017038T patent/PL2022724T3/pl unknown
- 2005-07-04 WO PCT/FR2005/001708 patent/WO2006013276A1/fr active Application Filing
- 2005-07-04 EP EP08017038A patent/EP2022724B1/fr not_active Revoked
- 2005-07-04 EP EP05786072A patent/EP1765685B1/fr active Active
- 2005-07-04 BR BRPI0513140-5A patent/BRPI0513140A/pt not_active Application Discontinuation
- 2005-07-04 MX MX2007000233A patent/MX2007000233A/es not_active Application Discontinuation
Non-Patent Citations (1)
Title |
---|
See references of WO2006013276A1 * |
Also Published As
Publication number | Publication date |
---|---|
DE602005025548D1 (de) | 2011-02-03 |
CN101001789A (zh) | 2007-07-18 |
RU2007104344A (ru) | 2008-08-20 |
PL2022724T3 (pl) | 2011-05-31 |
WO2006013276A1 (fr) | 2006-02-09 |
US8365955B2 (en) | 2013-02-05 |
BRPI0513140A (pt) | 2008-04-29 |
EP1765685B1 (fr) | 2008-11-26 |
US20070210103A1 (en) | 2007-09-13 |
MX2007000233A (es) | 2007-03-21 |
DE602005011293D1 (de) | 2009-01-08 |
FR2872792B1 (fr) | 2006-08-11 |
CN101001789B (zh) | 2010-12-08 |
PL1765685T3 (pl) | 2009-05-29 |
EP2022724B1 (fr) | 2010-12-22 |
EP2022724A1 (fr) | 2009-02-11 |
FR2872792A1 (fr) | 2006-01-13 |
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