EP1527999B1 - A container for product with less packaging material - Google Patents
A container for product with less packaging material Download PDFInfo
- Publication number
- EP1527999B1 EP1527999B1 EP03024855A EP03024855A EP1527999B1 EP 1527999 B1 EP1527999 B1 EP 1527999B1 EP 03024855 A EP03024855 A EP 03024855A EP 03024855 A EP03024855 A EP 03024855A EP 1527999 B1 EP1527999 B1 EP 1527999B1
- Authority
- EP
- European Patent Office
- Prior art keywords
- container
- comprised
- packaging assembly
- assembly according
- product
- 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.)
- Expired - Lifetime
Links
- 239000005022 packaging material Substances 0.000 title 1
- 238000004806 packaging method and process Methods 0.000 claims description 16
- 239000007788 liquid Substances 0.000 claims description 13
- 238000000034 method Methods 0.000 claims description 6
- 238000000071 blow moulding Methods 0.000 claims description 4
- 238000004519 manufacturing process Methods 0.000 claims description 4
- 235000011837 pasties Nutrition 0.000 claims description 4
- 238000007649 pad printing Methods 0.000 claims description 2
- 238000007639 printing Methods 0.000 claims description 2
- 239000000047 product Substances 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 17
- 239000004033 plastic Substances 0.000 description 15
- 229920003023 plastic Polymers 0.000 description 15
- 229920000139 polyethylene terephthalate Polymers 0.000 description 13
- 239000005020 polyethylene terephthalate Substances 0.000 description 13
- 239000000463 material Substances 0.000 description 9
- 230000009969 flowable effect Effects 0.000 description 7
- 229910052500 inorganic mineral Inorganic materials 0.000 description 7
- 239000011707 mineral Substances 0.000 description 7
- 235000013361 beverage Nutrition 0.000 description 6
- ZCCIPPOKBCJFDN-UHFFFAOYSA-N calcium nitrate Chemical compound [Ca+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ZCCIPPOKBCJFDN-UHFFFAOYSA-N 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- 238000003860 storage Methods 0.000 description 4
- 235000013305 food Nutrition 0.000 description 3
- 239000003643 water by type Substances 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000007664 blowing Methods 0.000 description 2
- 230000015556 catabolic process Effects 0.000 description 2
- 238000011109 contamination Methods 0.000 description 2
- 238000002425 crystallisation Methods 0.000 description 2
- 230000008025 crystallization Effects 0.000 description 2
- 238000006731 degradation reaction Methods 0.000 description 2
- 239000012263 liquid product Substances 0.000 description 2
- 239000012528 membrane Substances 0.000 description 2
- -1 polyethylene terephthalate Polymers 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000219198 Brassica Species 0.000 description 1
- 235000003351 Brassica cretica Nutrition 0.000 description 1
- 235000003343 Brassica rupestris Nutrition 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- QKSKPIVNLNLAAV-UHFFFAOYSA-N bis(2-chloroethyl) sulfide Chemical compound ClCCSCCCl QKSKPIVNLNLAAV-UHFFFAOYSA-N 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 235000014171 carbonated beverage Nutrition 0.000 description 1
- 238000004140 cleaning Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000006835 compression Effects 0.000 description 1
- 238000007906 compression Methods 0.000 description 1
- 235000013409 condiments Nutrition 0.000 description 1
- 230000003750 conditioning effect Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 239000002537 cosmetic Substances 0.000 description 1
- 238000005520 cutting process Methods 0.000 description 1
- 239000008367 deionised water Substances 0.000 description 1
- 229910021641 deionized water Inorganic materials 0.000 description 1
- 239000003599 detergent Substances 0.000 description 1
- 235000015071 dressings Nutrition 0.000 description 1
- 239000003651 drinking water Substances 0.000 description 1
- 235000020188 drinking water Nutrition 0.000 description 1
- 239000000686 essence Substances 0.000 description 1
- 230000007717 exclusion Effects 0.000 description 1
- 239000000835 fiber Substances 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 229920002457 flexible plastic Polymers 0.000 description 1
- 229940068517 fruit extracts Drugs 0.000 description 1
- 235000015203 fruit juice Nutrition 0.000 description 1
- 230000009477 glass transition Effects 0.000 description 1
- 235000008960 ketchup Nutrition 0.000 description 1
- 235000010746 mayonnaise Nutrition 0.000 description 1
- 239000008268 mayonnaise Substances 0.000 description 1
- 235000020124 milk-based beverage Nutrition 0.000 description 1
- 235000010460 mustard Nutrition 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 239000002304 perfume Substances 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 229940127557 pharmaceutical product Drugs 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001105 regulatory effect Effects 0.000 description 1
- 230000002787 reinforcement Effects 0.000 description 1
- 230000003014 reinforcing effect Effects 0.000 description 1
- 235000015067 sauces Nutrition 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 229940088594 vitamin Drugs 0.000 description 1
- 229930003231 vitamin Natural products 0.000 description 1
- 235000013343 vitamin Nutrition 0.000 description 1
- 239000011782 vitamin Substances 0.000 description 1
- 238000003466 welding Methods 0.000 description 1
Images
Classifications
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- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
-
- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0223—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by shape
-
- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/02—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents
- B65D1/0223—Bottles or similar containers with necks or like restricted apertures, designed for pouring contents characterised by shape
- B65D1/023—Neck construction
-
- 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
- B65D1/00—Containers having bodies formed in one piece, e.g. by casting metallic material, by moulding plastics, by blowing vitreous material, by throwing ceramic material, by moulding pulped fibrous material, by deep-drawing operations performed on sheet material
- B65D1/22—Boxes or like containers with side walls of substantial depth for enclosing contents
- B65D1/26—Thin-walled containers, e.g. formed by deep-drawing operations
Definitions
- the present invention relates to the field of the packaging of flowable products such as liquids or pasty products , particularly that of containers intended to contain beverages and more especially mineral water.
- One topic in the packaging area, especially for water is to reduce the weight of the plastic material used, and more particularly to reduce the weight of the bottom of the container.
- the first danger is that said bottom is less resistant because of the fact that the bottom is really the part of the container , which is the more submitted to constraints, due to the contact of said bottom with the place where it is disposed.
- the FR Patent No. 2772720 concerns such a container, wherein the bottom is thinner.
- FR 2 830 844 is a French patent application that describes a container with walls made of flexible plastic that can be deformed for constant surface area, particularly under the weight of they flowable product contained in the container, when the wall(s) encounter a point or bearing surface to form non-planar wall portion.
- the container comprises a body with greater section of dimension (dl) and a neck with internal diameter (d2).
- the ratio of d2 on d1 is comprised within the range of 1:3 to 1:10.
- the objective of the present invention is to have a container for a flowable product with a bottom allowing said container to stand and which for the same volume requires less plastic than a standard container while at the same time having comparable or higher mechanical properties.
- the object of the present invention is a container comprising a body formed by walls and a bottom, having in his greater section a dimension d 1 and a neck with an internal diameter d 2 , said container being made from a semi-crystalline PET , the body of said container comprising at its bottom at least three feet spaced from each other and being integral with said body, wherein for the body, the ratio weight of the walls on weight of the bottom is comprised between 3 and 4 and wherein the ratio volume of the body of the container per gram of PET of the body is comprised between 80 and 120 and wherein :
- Semi-crystalline PET means in the present specification a PET having a crystallinity comprised between 10 and 60 %. More preferably, the crystallinity is comprised between 20 and 40 %.
- the container has feet at the bottom, which are integral with said body.
- the presence of three feet is a good solution, but for greater volume a presence of 4 or 5 feet is preferred.
- the geometry of said feet is not critical. Preferably, these feet have a spherical geometry.
- Concerning the bottom of the container, it has preferably a non flat form.
- the bottom has a convex form, like a semi-spherical form.
- the container of the invention either to have a neck with a small height, like a couple of millimeters, or to have a neck with a greater height.
- the ratio height of the neck on the height of the body is comprised between 1:1 and 1:4. This allows for the consumer a better gripping of said container.
- the walls of the body have a thickness of less than 100 ⁇ m.
- the neck of the container has preferably a wall thickness comprised between 150 and 250 ⁇ m.
- Each foot of the bottom of the body has a thickness comprised between 50 and 150 ⁇ m, also as an essential feature of the invention.
- the part of the bottom between the feet has a greater thickness of that of the walls, for example around 100-200 ⁇ m.
- the present invention concerns further a packaging assembly comprising
- incompressible means that when squeezed the filled container only deforms very slightly and then will recover its original shape. In contrast, a standard bottle will buckle and deform.
- the container comprises on its outside a printing made by pad printing.
- the volume of the container used according to the invention can have all type of capacity, comprised between 5 cl and 20 1 capacity.
- the container is intended to contain all type of product, like pasty, liquid, semi-liquid, granular or powdered product. Under liquid product,we understand water or a still liquid beverage, particularly still mineral waters, carbonated water or a carbonated liquid beverage, particularly sparkling mineral water. Other types of liquid products are also possible, like chemical products, oil, essence, perfumes, pharmaceutical products. Under pasty products, we understand food and non food products, like mayonnaise, cosmetic compounds and others.
- the means of closing are either a cap, or sealed membrane.
- the caps can be used for any diameter of opening of the neck.
- the sealed membranes are preferred with smaller diameter of the neck, for example in the area of 10 mm.
- the container can support high compressions, for example by the storage and by the transportation. For diameters of around 10 mm, the container can support an internal pressure of the order of 5 bar. It is also possible to close the container by sealing or welding the neck, wherein a cutting object or similar is provided for the opening.
- the container has an ovoid or substantially ovoid overall shape.
- This natural shape derived from an egg represents a structure whose resistance to vertical and/or transversal loads is optimized, thus making it possible, for a given volume and a given amount of material, to achieve mechanical properties which are equivalent to or even better than the cylindrical or roughly cylindrical shapes customarily encountered in this domain.
- the container according to the invention has a three dimensional shape convenient for gripping, a spherical , substantially spherical or cylindrical overall shape.
- the geometry with symmetry of revolution is particularly easy and therefore economical to manufacture and has the advantage of allowing the container to be filled with products which can emit gaseous substances, such as carbonated beverages (sparkling waters, sodas, etc.) in particular, which are widely consumed worldwide these days.
- gaseous substances such as carbonated beverages (sparkling waters, sodas, etc.) in particular, which are widely consumed worldwide these days.
- Such a shape is therefore particularly well suited to these liquids in that the release of carbon dioxide or other gas has a tendency to deform the bodies of bottles which do not have symmetry of revolution, having a negative impact on their stability, grasp and ease of handling, appearance, etc.
- the ratio d2 on d1 of the container is comprised between 1:3 and 1:10.
- the ratio weight of the walls on weight of the bottom is comprised between 3.4 and 3.8.
- the ratio volume of the body of the container per gram of PET of the body is comprised between 90 and 110.
- the plastic used to form the wall or walls is a semicrystalline plastic with a slow rate of crystallization, the glass transition temperature (T g ) of which is 70°C or higher and the cristallisation temperature Tc is around 140 °C.
- T g glass transition temperature
- Tc cristallisation temperature
- the plastic used to form the wall or walls is PET (polyethylene terephthalate) . It has been noted that the drawing of the PET has no negative influence on the water barrier properties of the obtained container and that also a thickness of around 50 ⁇ m and less guarantees a good safety of the container itself and of the storage.
- the container according to the invention is further characterized in that the thickness of the wall or walls forming the body of the container is between 30 ⁇ m and 100 ⁇ m, preferably between 50 ⁇ m and 70 ⁇ m.
- small thicker areas or portions of walls may also be provided on the body of the said container, particularly in close proximity to the neck and/or the bottom , so as to reinforce these parts locally. Such reinforcements may in particular be useful to facilitate the filling of the said containers or to increase their stability during storage.
- the container is further characterized in that the body and the neck of the container are made as a single piece. This makes it possible to avoid any join or weld which may constitute a region of greater weakness.
- the container according to the invention is characterized in that, it has a high resistance to vertical and/or transverse loads allowing good resistance to transportation.
- the amount of PET used to produce the said container is about 30 g. for resistance to a vertical load of about 65 kg. This represents a significant saving in plastic, the few 5-litre containers that are currently on the market requiring an amount of polymer which, for comparable mechanical strength, is over two times greater than the amount needed to manufacture a container according to the present invention.
- the quantity of plastic material is of the order of 3-4 g, in comparison with a bottle of the same volume, wherein the amount of plastic is of the order of at least 12 g.
- This type of container supports a vertical loading of more than about 100 kg. That the container supports a vertical or transverse loading means that the weight given does not deteriorate the package integrity, that is does not lead to a risk of breaking said container.
- the container according to the invention is characterized in that the neck is fitted with a closure and/or distribution means produced in the form of a distribution tap which can be operated with one hand.
- Such distribution taps which are known per se, advantageously allow the distribution of the flowable product contained in the container to be regulated in a particularly convenient way, for example when this container is stored horizontally on the shelves of a refrigerator, the other hand holding the container into which the said flowable product is to be transferred, for example with a view to consuming it.
- the geometry of the container can also adapt more readily to that of the storage place, as opposed to the rigid cans currently available which need to observe very specified dimensions in order to be able to be stored in restricted spaces such as the internal compartments of refrigerators.
- the space freed as a container according to the invention is emptied can also be put to use for storing objects the size or shape of which can vary, which is not the case with rigid containers in which the volume of liquid removed is systematically replaced with air.
- the volume initially occupied remains so until the empty container is removed from the refrigerator.
- Another subject of the present invention is the use of the container by way of large-capacity, at least 5-litre capacity, container intended to contain water or a still liquid beverage, particularly still mineral water.
- Another subject of the present invention is the use of the container according to the invention by way of large-capacity, at least 5-litre capacity, container intended to contain carbonated water or a carbonated liquid beverage, particularly sparkling mineral water.
- the containers of the present invention are not in any way limited to flat or sparkling mineral waters but can be intended to contain all sorts of flowable products, edible or inedible liquids of greater or lesser fluidity such as, for example, fruit juices, milk-based beverages, etc., and also sauces or condiments (ketchup, mustard, dressing, etc.) or non-food liquids (deionized water, cleaning products, detergents, etc.).
- the packaging assembly according to the invention can also contain a functional component.
- the functional component is taken from the group consisting of a fibre, plant extract, fruit extracts, vitamins and flavors.
- the assembly is pasteurised or sterilised at a temperature in excess of 60 °C.
- another object of the present invention is a method for manufacturing a body of a container according to the invention, characterized in that the said body is obtained by stretch blow forming of a PET preform with high stretch index in comparison with the classical stretching of a preform.
- the blow forming can be also a blow molding.
- the blowing pressure is comprised between 30 and 40 bar, according to the process of the invention, it is sufficient to blow at a pressure of around 2 times less. This reduces the cost of the process and also of the machine which is used.
- Concerning the stretch index it is depending on the volume of the final container. For example , in the case of a container having a volume of less than 100cl, the stretch index is between 100 and 300 cm. In the case of a container having a volume of 500 to 1000 cl, the stretch index is comprised between 500 and 700 cm. In the case of container having volume of 2000 cl or more , the stretch index is around and more than 1000 cm.
- the measure of the crystallinity is made on a density column from Lloyd-Davenport, according to following procedure.
- the column is filled with a salted solution (calcium nitrate) having a density gradient.
- the column is calibrated with balls having known density between 1.335 and 1.455.
- small pieces of the container of the invention are immerged in the column and after a certain time, they stay at a certain height of the column corresponding to a certain density.
- the measures are made at 23 °C.
- the following correspondance table with ⁇ c of 1.455 gives the cristallinity container is that it can be emptied without air coming in and this reduces the risk of contamination or odours entering the product that may cause taste changes or degradation.
- the measure of the crystallinity is made on a density column from Lloyd-Davenport, according to following procedure.
- the column is filled with a salted solution (calcium nitrate) having a density gradient.
- the column is calibrated with balls having known density between 1.335 and 1.455.
- small pieces of the container of the invention are immerged in the column and after a certain time, they stay at a certain height of the column corresponding to a certain density.
- the measures are made at 23 °C.
- the following correspondance table with ⁇ c of 1.455 gives the cristallinity
- the container for a flowable product essentially consists of a body 1, formed by walls 2 and a bottom 3 and a neck 4.
- the body is made of a semi-crystalline PET.
- the neck presents a screw 5 for receiving a cap (not shown).
- the bottom 3 presents three feet 6 integral with the body.
- the volume of the container is of 1000 ml.
- the ratio weight of the walls on weight of the bottom is of 3.5 and the ratio volume of the body of the container per gram of PET is of 100. This means that for the volume of 1000 ml, there is 10 g of PET for the body (neck excluded).
- the thickness of the walls is around 70 ⁇ m.
- the neck has a height which is minimised and said neck has a wall thickness of around 200 ⁇ m.
- the wall thickness is around 150 ⁇ m.
- the feet have a semi-spherical shape.
- the x axis represents the volume of the container in ml and the y axis represents the ratio volume of the container in ml per g of the plastic material of said container.
- the graph 1 shows a bottle used on the market for sparkling water.
- the graph 2 shows a bottle used on the market for still water and the graph 3 shows a container according to the invention.
- This graph shows very clearly one of the specificities of the invention, which is that less plastic material is needed for conditioning the same volume of product. Taking an example of the graph : according to the invention 1 g of plastic material is needed for 100 ml of product, whereas for products now on the market 1 g of plastic material is needed for only around 40 to 60 ml of product. That means that according to the invention, the need of plastic material is divided by 2.
Description
- The present invention relates to the field of the packaging of flowable products such as liquids or pasty products , particularly that of containers intended to contain beverages and more especially mineral water.
- One topic in the packaging area, especially for water is to reduce the weight of the plastic material used, and more particularly to reduce the weight of the bottom of the container. By reducing the weight of the bottom, the first danger is that said bottom is less resistant because of the fact that the bottom is really the part of the container , which is the more submitted to constraints, due to the contact of said bottom with the place where it is disposed. There are already some solutions to that problem, like the container with petaloid bottom : the
FR Patent No. 2772720 FR 2 830 844 - The container comprises a body with greater section of dimension (dl) and a neck with internal diameter (d2). The ratio of d2 on d1 is comprised within the range of 1:3 to 1:10.
- This document does not disclose nor suggest the possibility of having feet for placing the container in an upright position. On the contrary, it discloses that the container is self-stable by deformation of its wall(s) under its own weight.
- The objective of the present invention is to have a container for a flowable product with a bottom allowing said container to stand and which for the same volume requires less plastic than a standard container while at the same time having comparable or higher mechanical properties.
- The object of the present invention is a container comprising a body formed by walls and a bottom, having in his greater section a dimension d1 and a neck with an internal diameter d2 , said container being made from a semi-crystalline PET , the body of said container comprising at its bottom at least three feet spaced from each other and being integral with said body, wherein for the body, the ratio weight of the walls on weight of the bottom is comprised between 3 and 4 and wherein the ratio volume of the body of the container per gram of PET of the body is comprised between 80 and 120 and wherein :
- the body walls hare a thickness less than 100 µm,
- the bottom has a thickness between 100 and 200 µm,
- each foot has a wall thickness of 50 to 150 µm.
- Under bottom in the present application, we understand all the part of the body comprising the space of said body between the feet, said feet being taken from their most external position.
- Semi-crystalline PET means in the present specification a PET having a crystallinity comprised between 10 and 60 %. More preferably, the crystallinity is comprised between 20 and 40 %.
- One specificity of the invention is that the container has feet at the bottom, which are integral with said body. The presence of three feet is a good solution, but for greater volume a presence of 4 or 5 feet is preferred. The geometry of said feet is not critical. Preferably, these feet have a spherical geometry. Concerning the bottom of the container, it has preferably a non flat form. The bottom has a convex form, like a semi-spherical form.
- It is possible for the container of the invention, either to have a neck with a small height, like a couple of millimeters, or to have a neck with a greater height. In this case, the ratio height of the neck on the height of the body is comprised between 1:1 and 1:4. This allows for the consumer a better gripping of said container.
- As an essential characteristic of the invention, the walls of the body have a thickness of less than 100 µm. The neck of the container has preferably a wall thickness comprised between 150 and 250 µm. Each foot of the bottom of the body has a thickness comprised between 50 and 150 µm, also as an essential feature of the invention.
- In the container of the invention, the part of the bottom between the feet has a greater thickness of that of the walls, for example around 100-200 µm.
- The present invention concerns further a packaging assembly comprising
- a container as described above,
- a product in the container and
- closing means for closing off or distributing the product from the neck,
- This incompressibility applies for all types of products, even for a still product. In the present specification, incompressible means that when squeezed the filled container only deforms very slightly and then will recover its original shape. In contrast, a standard bottle will buckle and deform.
- According to a feature of the invention, the container comprises on its outside a printing made by pad printing. The advantage of this solution, is that it suppresses the need of having a paper stuck around the container.
- The volume of the container used according to the invention can have all type of capacity, comprised between 5 cl and 20 1 capacity. The container is intended to contain all type of product, like pasty, liquid, semi-liquid, granular or powdered product. Under liquid product,we understand water or a still liquid beverage, particularly still mineral waters, carbonated water or a carbonated liquid beverage, particularly sparkling mineral water. Other types of liquid products are also possible, like chemical products, oil, essence, perfumes, pharmaceutical products. Under pasty products, we understand food and non food products, like mayonnaise, cosmetic compounds and others.
- The means of closing are either a cap, or sealed membrane. The caps can be used for any diameter of opening of the neck. On the contrary, the sealed membranes are preferred with smaller diameter of the neck, for example in the area of 10 mm. In this case, the container can support high compressions, for example by the storage and by the transportation. For diameters of around 10 mm, the container can support an internal pressure of the order of 5 bar. It is also possible to close the container by sealing or welding the neck, wherein a cutting object or similar is provided for the opening.
- As a preference, the container has an ovoid or substantially ovoid overall shape. This natural shape derived from an egg represents a structure whose resistance to vertical and/or transversal loads is optimized, thus making it possible, for a given volume and a given amount of material, to achieve mechanical properties which are equivalent to or even better than the cylindrical or roughly cylindrical shapes customarily encountered in this domain.
- In another embodiment , the container according to the invention has a three dimensional shape convenient for gripping, a spherical , substantially spherical or cylindrical overall shape.
- This is because the geometry with symmetry of revolution is particularly easy and therefore economical to manufacture and has the advantage of allowing the container to be filled with products which can emit gaseous substances, such as carbonated beverages (sparkling waters, sodas, etc.) in particular, which are widely consumed worldwide these days. Such a shape is therefore particularly well suited to these liquids in that the release of carbon dioxide or other gas has a tendency to deform the bodies of bottles which do not have symmetry of revolution, having a negative impact on their stability, grasp and ease of handling, appearance, etc.
- In a preferred feature of the invention, the ratio d2 on d1 of the container is comprised between 1:3 and 1:10. According to a preferred embodiment of the packaging assembly, the ratio weight of the walls on weight of the bottom is comprised between 3.4 and 3.8. According to a further preferred feature of the invention, the ratio volume of the body of the container per gram of PET of the body is comprised between 90 and 110.
- According to another feature, the plastic used to form the wall or walls is a semicrystalline plastic with a slow rate of crystallization, the glass transition temperature (Tg) of which is 70°C or higher and the cristallisation temperature Tc is around 140 °C. A slow rate of crystallization is to be understood as meaning a rate which makes it possible to have an amorphous state by quick cooling.
- Advantageously, the plastic used to form the wall or walls is PET (polyethylene terephthalate) . It has been noted that the drawing of the PET has no negative influence on the water barrier properties of the obtained container and that also a thickness of around 50 µm and less guarantees a good safety of the container itself and of the storage. In order to guarantee both the flexibility needed for the aforementioned deformation and sufficient mechanical strength, the container according to the invention is further characterized in that the thickness of the wall or walls forming the body of the container is between 30 µm and 100 µm, preferably between 50 µm and 70 µm. As already mentioned, small thicker areas or portions of walls may also be provided on the body of the said container, particularly in close proximity to the neck and/or the bottom , so as to reinforce these parts locally. Such reinforcements may in particular be useful to facilitate the filling of the said containers or to increase their stability during storage. As a preference, the container is further characterized in that the body and the neck of the container are made as a single piece. This makes it possible to avoid any join or weld which may constitute a region of greater weakness.
- Indeed, according to another feature, the container according to the invention is characterized in that, it has a high resistance to vertical and/or transverse loads allowing good resistance to transportation. For example, for a working volume of 5 litres, the amount of PET used to produce the said container is about 30 g. for resistance to a vertical load of about 65 kg. This represents a significant saving in plastic, the few 5-litre containers that are currently on the market requiring an amount of polymer which, for comparable mechanical strength, is over two times greater than the amount needed to manufacture a container according to the present invention. When containers of lower volumes are used, for example of the order of 33 cl, the quantity of plastic material is of the order of 3-4 g, in comparison with a bottle of the same volume, wherein the amount of plastic is of the order of at least 12 g. This type of container supports a vertical loading of more than about 100 kg. That the container supports a vertical or transverse loading means that the weight given does not deteriorate the package integrity, that is does not lead to a risk of breaking said container.
- These simple shapes also allow the container according to the invention to be used as a refill or recharge for water coolers, for which a flat bottom is not necessary, these refills generally being used by inserting the container, head (neck) downmost, into the accomodation device of the said water cooler. In addition, this type of surface geometry also makes it possible to increase the area of heat exchange between the said container and the chilling device usually present in the said water coolers.
- According to another alternative form, the container according to the invention is characterized in that the neck is fitted with a closure and/or distribution means produced in the form of a distribution tap which can be operated with one hand.
- Such distribution taps, which are known per se, advantageously allow the distribution of the flowable product contained in the container to be regulated in a particularly convenient way, for example when this container is stored horizontally on the shelves of a refrigerator, the other hand holding the container into which the said flowable product is to be transferred, for example with a view to consuming it. Because of its flexible nature, the geometry of the container can also adapt more readily to that of the storage place, as opposed to the rigid cans currently available which need to observe very specified dimensions in order to be able to be stored in restricted spaces such as the internal compartments of refrigerators. In addition, the space freed as a container according to the invention is emptied can also be put to use for storing objects the size or shape of which can vary, which is not the case with rigid containers in which the volume of liquid removed is systematically replaced with air. In this type of container, the volume initially occupied remains so until the empty container is removed from the refrigerator.
- Another subject of the present invention is the use of the container by way of large-capacity, at least 5-litre capacity, container intended to contain water or a still liquid beverage, particularly still mineral water. Another subject of the present invention is the use of the container according to the invention by way of large-capacity, at least 5-litre capacity, container intended to contain carbonated water or a carbonated liquid beverage, particularly sparkling mineral water. Of course, the containers of the present invention are not in any way limited to flat or sparkling mineral waters but can be intended to contain all sorts of flowable products, edible or inedible liquids of greater or lesser fluidity such as, for example, fruit juices, milk-based beverages, etc., and also sauces or condiments (ketchup, mustard, dressing, etc.) or non-food liquids (deionized water, cleaning products, detergents, etc.).
- The packaging assembly according to the invention can also contain a functional component. The functional component is taken from the group consisting of a fibre, plant extract, fruit extracts, vitamins and flavors. The assembly is pasteurised or sterilised at a temperature in excess of 60 °C.
- Finally, another object of the present invention is a method for manufacturing a body of a container according to the invention, characterized in that the said body is obtained by stretch blow forming of a PET preform with high stretch index in comparison with the classical stretching of a preform. The blow forming can be also a blow molding. Compared with the blowing of plastic bottles, wherein the blowing pressure is comprised between 30 and 40 bar, according to the process of the invention, it is sufficient to blow at a pressure of around 2 times less. This reduces the cost of the process and also of the machine which is used. Concerning the stretch index, it is depending on the volume of the final container. For example , in the case of a container having a volume of less than 100cl, the stretch index is between 100 and 300 cm. In the case of a container having a volume of 500 to 1000 cl, the stretch index is comprised between 500 and 700 cm. In the case of container having volume of 2000 cl or more , the stretch index is around and more than 1000 cm.
-
- Because of the substantial incompressibility of the filled container of the invention, there is no need to have reinforcing structures. The consequence is that it is possible to have simple shapes, which have the advantage of providing transparency and purity. This is particularly important for the consumer in the case of a container for drinking water. Another advantage of this container is that it can be emptied without air coming in and this reduces the risk of contamination or odours entering the product that may cause taste changes or degradation.
- The measure of the crystallinity is made on a density column from Lloyd-Davenport, according to following procedure. The column is filled with a salted solution (calcium nitrate) having a density gradient. The column is calibrated with balls having known density between 1.335 and 1.455. Then small pieces of the container of the invention are immerged in the column and after a certain time, they stay at a certain height of the column corresponding to a certain density.The measures are made at 23 °C. The following correspondance table with ρc of 1.455 gives the cristallinity container is that it can be emptied without air coming in and this reduces the risk of contamination or odours entering the product that may cause taste changes or degradation.
- The measure of the crystallinity is made on a density column from Lloyd-Davenport, according to following procedure. The column is filled with a salted solution (calcium nitrate) having a density gradient. The column is calibrated with balls having known density between 1.335 and 1.455. Then small pieces of the container of the invention are immerged in the column and after a certain time, they stay at a certain height of the column corresponding to a certain density.The measures are made at 23 °C.The following correspondance table with ρc of 1.455 gives the cristallinity
- Other features and advantages of the invention will become apparent from the description which follows, given by way of example and with reference to the appended drawings in which:
- Fig. 1 is a lateral perspective view of the container according to the invention,
- Fig. 2 is another perspective view of the container of the invention, seen from the bottom and
- Fig. 3 is a graph comparing the invention with the state of the art.
- In the embodiment described and depicted on figures 1 and 2, the container for a flowable product, particularly for a beverage and , in particular, for mineral water, essentially consists of a
body 1, formed bywalls 2 and abottom 3 and aneck 4. The body is made of a semi-crystalline PET. The neck presents a screw 5 for receiving a cap (not shown). The bottom 3 presents threefeet 6 integral with the body. The volume of the container is of 1000 ml. In this specific example the ratio weight of the walls on weight of the bottom is of 3.5 and the ratio volume of the body of the container per gram of PET is of 100. This means that for the volume of 1000 ml, there is 10 g of PET for the body (neck excluded). The thickness of the walls is around 70 µm. The neck has a height which is minimised and said neck has a wall thickness of around 200 µm. In thearea 7 of the feet, that means around the middle of said feet, the wall thickness is around 150 µm. The feet have a semi-spherical shape. Concerning now the limits of the wall and bottom for calculating the ratio weight of the walls on weight of the bottom, it is outside and inside of thecircle 8 of figure 2. - Concerning now the graph of figure 3, the x axis represents the volume of the container in ml and the y axis represents the ratio volume of the container in ml per g of the plastic material of said container. The
graph 1 shows a bottle used on the market for sparkling water. Thegraph 2 shows a bottle used on the market for still water and thegraph 3 shows a container according to the invention. This graph shows very clearly one of the specificities of the invention, which is that less plastic material is needed for conditioning the same volume of product. Taking an example of the graph : according to the invention 1 g of plastic material is needed for 100 ml of product, whereas for products now on the market 1 g of plastic material is needed for only around 40 to 60 ml of product. That means that according to the invention, the need of plastic material is divided by 2.
Claims (15)
- A container comprising a body formed by walls and a bottom having in his greater section a dimension d1 and a neck with an internal diameter d2 , said container being made from a semi-crystalline PET , the body of said container comprising at its bottom at least three feet spaced from each other and being integral with said body, wherein for the body, the ratio weight of the walls on weight of the bottom is comprised between 3 and 4 and wherein the ratio volume, in ml of the body of the container per gram of PET of the body is comprised between 80 and 120, and wherein:- the walls of the body have a thickness of less than 100 µm, and- the bottom has a thickness between 100 µm and 200 µm, and- each foot has a wall thickness of 50 µm to 150 µm.
- A container according to claim 1, wherein the neck has a wall thickness comprised between 150 and 250 µm.
- A container according to any of claims 1 or 2, wherein the part of the bottom between the feet has a greater thickness of that of the walls.
- A packaging assembly comprising- a container according to claim 1,- a product in the container and- closing means for closing off or distributing the product from the neck,the filled container being substantially incompressible by hand when filled with the product.
- A packaging assembly according to claim 4, wherein the product is taken from the group consisting of pasty, liquid, semi-liquid, granular or powdered product.
- A packaging assembly according to any of claims 4 or 5, wherein said assembly has a high resistance to vertical and/or transverse loads allowing good resistance to transportation.
- A packaging assembly according to claim 6, wherein said assembly supports a vertical and/or transverse loading of more than about 100 kg for a container having a weight of about 4 g.
- A packaging assembly according to any of claims 4 to 7, wherein the body of the container has a form taken from the group consisting of a three dimensional shape convenient for gripping, an ovoid, spherical, elliptical or cylindrical shape.
- A packaging assembly according to any of claims 4 to 8 , wherein the wall thickness of the body, substantially in the middle of its body is comprised between 30 and 70 µm.
- A packaging assembly according to any of claims 4 to 9 , wherein the container comprises on its outside a printing made by pad printing.
- A packaging assembly according to any of claims 4 to 10 , wherein the ratio d2 on d1 is comprised between 1:3 and 1:10.
- A packaging assembly according to any of claims 4 to 11 , wherein the ratio height of the neck on the height of the body is comprised between 1:1 and 1:4.
- A packaging assembly according to any of claims 4 to 12, the ratio weight of the walls on weight of the bottom is comprised between 3.4 and 3.8.
- A packaging assembly according to any of claims 4 to 13 , wherein the ratio volume of the body of the container per gram of PET of the body is comprised between 90 and 110.
- A process for manufacturing the container according to any of claims 1 to 3, wherein said container is obtained by stretch blow forming of a PET preform with high stretch index in comparison with the classical stretching of a preform.
Priority Applications (17)
Application Number | Priority Date | Filing Date | Title |
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ES03024855T ES2289226T3 (en) | 2003-10-31 | 2003-10-31 | PRODUCT CONTAINER MANUFACTURED WITH LESS MATERIAL. |
AT03024855T ATE365683T1 (en) | 2003-10-31 | 2003-10-31 | CONTAINERS MADE OF LESS PACKAGING MATERIAL |
DE60314637T DE60314637T2 (en) | 2003-10-31 | 2003-10-31 | Containers of less packaging material |
PT03024855T PT1527999E (en) | 2003-10-31 | 2003-10-31 | A container for product with less packaging material |
EP03024855A EP1527999B1 (en) | 2003-10-31 | 2003-10-31 | A container for product with less packaging material |
SI200330947T SI1527999T1 (en) | 2003-10-31 | 2003-10-31 | A container for product with less packaging material |
CNB2004800354439A CN100545046C (en) | 2003-10-31 | 2004-10-15 | The container for product that packing are less |
CA2544044A CA2544044C (en) | 2003-10-31 | 2004-10-15 | A container for product with less packaging material |
KR1020067008431A KR20060111469A (en) | 2003-10-31 | 2004-10-15 | A container for product with less packaging material |
EP04790459A EP1682416A1 (en) | 2003-10-31 | 2004-10-15 | A container for product with less packaging material |
PCT/EP2004/011606 WO2005047120A1 (en) | 2003-10-31 | 2004-10-15 | A container for product with less packaging material |
US10/595,618 US20070108156A1 (en) | 2003-10-31 | 2004-10-15 | Container for product with less packaging material |
BRPI0416065-7A BRPI0416065A (en) | 2003-10-31 | 2004-10-15 | container for product with less packing material |
TW093132832A TW200526473A (en) | 2003-10-31 | 2004-10-28 | A container for product with less packaging material |
ARP040103998A AR047623A1 (en) | 2003-10-31 | 2004-10-29 | AN ECONOMIC CONTAINER |
EGNA2006000402 EG24116A (en) | 2003-10-31 | 2006-04-03 | A container for product with less packaging material |
ZA200604430A ZA200604430B (en) | 2003-10-31 | 2006-05-30 | A container for product with less packaging material |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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EP03024855A EP1527999B1 (en) | 2003-10-31 | 2003-10-31 | A container for product with less packaging material |
Publications (2)
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EP1527999A1 EP1527999A1 (en) | 2005-05-04 |
EP1527999B1 true EP1527999B1 (en) | 2007-06-27 |
Family
ID=34400489
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EP03024855A Expired - Lifetime EP1527999B1 (en) | 2003-10-31 | 2003-10-31 | A container for product with less packaging material |
EP04790459A Withdrawn EP1682416A1 (en) | 2003-10-31 | 2004-10-15 | A container for product with less packaging material |
Family Applications After (1)
Application Number | Title | Priority Date | Filing Date |
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EP04790459A Withdrawn EP1682416A1 (en) | 2003-10-31 | 2004-10-15 | A container for product with less packaging material |
Country Status (16)
Country | Link |
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US (1) | US20070108156A1 (en) |
EP (2) | EP1527999B1 (en) |
KR (1) | KR20060111469A (en) |
CN (1) | CN100545046C (en) |
AR (1) | AR047623A1 (en) |
AT (1) | ATE365683T1 (en) |
BR (1) | BRPI0416065A (en) |
CA (1) | CA2544044C (en) |
DE (1) | DE60314637T2 (en) |
EG (1) | EG24116A (en) |
ES (1) | ES2289226T3 (en) |
PT (1) | PT1527999E (en) |
SI (1) | SI1527999T1 (en) |
TW (1) | TW200526473A (en) |
WO (1) | WO2005047120A1 (en) |
ZA (1) | ZA200604430B (en) |
Cited By (3)
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WO2014101956A1 (en) | 2012-12-28 | 2014-07-03 | Sa Des Eaux Minerales D'evian Saeme | Self collapsible blow moulded plastic thin-walled container |
WO2014101957A1 (en) | 2012-12-28 | 2014-07-03 | Sa Des Eaux Minerales D'evian Saeme | Retractable blow moulded plastic thin-walled container |
EP3953262B1 (en) * | 2019-04-12 | 2024-03-06 | Société Anonyme des Eaux Minérales d'Evian et en abrégé "S.A.E.M.E" | Thin wall container made with a recycled material |
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AR050681A1 (en) * | 2004-07-14 | 2006-11-15 | Nestec Sa | A CONTAINER OR CONTAINER FORMED BY A SINGLE PART OR EXPRESSIBLE PART FOR REFRIGERATED OR FROZEN PRODUCTS |
US20060118560A1 (en) * | 2004-12-03 | 2006-06-08 | Schur Warren M | Water shedding designs for receptacle bottoms |
ES2309665T3 (en) * | 2005-10-20 | 2008-12-16 | NESTLE WATERS MANAGEMENT & TECHNOLOGY | VERY LIGHT CONTAINER FOR DRINKS. |
EP2361875B1 (en) * | 2005-11-29 | 2016-05-11 | Petainer Lidköping AB | System and method for distribution and dispensing of beverages |
US8857637B2 (en) | 2006-03-06 | 2014-10-14 | Plastipak Packaging, Inc. | Lightweight plastic container and preform |
US10214312B2 (en) | 2006-03-06 | 2019-02-26 | Plastipak Packaging, Inc. | Lightweight plastic container and preform |
FR2922147B1 (en) | 2007-10-10 | 2010-01-01 | Tecsor | METHOD FOR MANUFACTURING A THIN-FILM CONTAINER, METHOD FOR PRESSING THE CONTAINER |
AU2011212990B2 (en) * | 2010-02-03 | 2015-05-21 | Paha Designs, Llc | Pressure equalization apparatus for a bottle and methods associated therewith |
US8857639B2 (en) | 2010-02-03 | 2014-10-14 | Paha Designs, Llc | Pressure equalization apparatus for a bottle and methods associated therewith |
US8684205B2 (en) * | 2010-02-03 | 2014-04-01 | Paha Designs, Llc | Pressure equalization apparatus for a bottle and methods associated therewith |
US9796506B2 (en) | 2010-02-03 | 2017-10-24 | Paha Designs, Llc | Pressure equalization apparatus for a bottle and methods associated therewith |
GB2479360A (en) * | 2010-04-06 | 2011-10-12 | Petainer Lidkoeping Ab | Petaloid Container Base with Reduced Diameter Contact Circle |
US9783339B1 (en) * | 2011-07-25 | 2017-10-10 | LJA Companies, LLC | Reusable dispensing apparatus |
EP2554486A1 (en) * | 2011-08-04 | 2013-02-06 | Nestec S.A. | A packaging with a spout for flowable products |
US9649606B2 (en) * | 2012-02-06 | 2017-05-16 | Jason Ruff | Method and apparatus for aerating liquid |
CA2859379A1 (en) | 2013-08-15 | 2015-02-15 | Paha Designs, Llc | Pressure equalization apparatus for a bottle and methods associated therewith |
US10889411B2 (en) | 2017-02-03 | 2021-01-12 | Berry Plastics Corporation | Container with lid and detachable lid collar |
USD945274S1 (en) | 2017-11-09 | 2022-03-08 | Robert David Sager | Water bottle |
WO2019228741A1 (en) | 2018-05-31 | 2019-12-05 | Societe Des Produits Nestle S.A. | Bottle with grip portion |
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US3733309A (en) * | 1970-11-30 | 1973-05-15 | Du Pont | Biaxially oriented poly(ethylene terephthalate)bottle |
EP0521212A1 (en) * | 1991-07-03 | 1993-01-07 | Toyo Seikan Kaisha Limited | Highly drawn and blow-molded polyester bottle and method of manufacturing thereof |
US5614148A (en) * | 1995-01-30 | 1997-03-25 | Dtl Technology Limited Partnership | One piece self-standing blow molded plastic containers made from a monobase preform |
FR2772720B1 (en) | 1997-12-23 | 2000-03-17 | Sidel Sa | PETALOID BASED THERMOPLASTIC CONTAINER |
AU2001253915A1 (en) * | 2000-04-28 | 2001-11-12 | Advanced Plastics Technologies, Ltd. | Bottles and preforms having a crystalline neck |
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FR2830844A1 (en) * | 2001-10-12 | 2003-04-18 | Perrier Vittel Man Et Technolo | Container for flowable product e.g., beverage and mineral water, includes walls made of flexible plastic that can be deformed for constant surface area, particularly under weight of flowable product |
-
2003
- 2003-10-31 SI SI200330947T patent/SI1527999T1/en unknown
- 2003-10-31 EP EP03024855A patent/EP1527999B1/en not_active Expired - Lifetime
- 2003-10-31 ES ES03024855T patent/ES2289226T3/en not_active Expired - Lifetime
- 2003-10-31 AT AT03024855T patent/ATE365683T1/en not_active IP Right Cessation
- 2003-10-31 PT PT03024855T patent/PT1527999E/en unknown
- 2003-10-31 DE DE60314637T patent/DE60314637T2/en not_active Expired - Lifetime
-
2004
- 2004-10-15 WO PCT/EP2004/011606 patent/WO2005047120A1/en not_active Application Discontinuation
- 2004-10-15 CA CA2544044A patent/CA2544044C/en active Active
- 2004-10-15 US US10/595,618 patent/US20070108156A1/en not_active Abandoned
- 2004-10-15 CN CNB2004800354439A patent/CN100545046C/en not_active Expired - Fee Related
- 2004-10-15 BR BRPI0416065-7A patent/BRPI0416065A/en active Search and Examination
- 2004-10-15 KR KR1020067008431A patent/KR20060111469A/en not_active Application Discontinuation
- 2004-10-15 EP EP04790459A patent/EP1682416A1/en not_active Withdrawn
- 2004-10-28 TW TW093132832A patent/TW200526473A/en unknown
- 2004-10-29 AR ARP040103998A patent/AR047623A1/en unknown
-
2006
- 2006-04-03 EG EGNA2006000402 patent/EG24116A/en active
- 2006-05-30 ZA ZA200604430A patent/ZA200604430B/en unknown
Cited By (3)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2014101956A1 (en) | 2012-12-28 | 2014-07-03 | Sa Des Eaux Minerales D'evian Saeme | Self collapsible blow moulded plastic thin-walled container |
WO2014101957A1 (en) | 2012-12-28 | 2014-07-03 | Sa Des Eaux Minerales D'evian Saeme | Retractable blow moulded plastic thin-walled container |
EP3953262B1 (en) * | 2019-04-12 | 2024-03-06 | Société Anonyme des Eaux Minérales d'Evian et en abrégé "S.A.E.M.E" | Thin wall container made with a recycled material |
Also Published As
Publication number | Publication date |
---|---|
PT1527999E (en) | 2007-10-04 |
CN100545046C (en) | 2009-09-30 |
WO2005047120A1 (en) | 2005-05-26 |
ATE365683T1 (en) | 2007-07-15 |
DE60314637D1 (en) | 2007-08-09 |
ZA200604430B (en) | 2007-09-26 |
SI1527999T1 (en) | 2008-04-30 |
EG24116A (en) | 2008-07-02 |
KR20060111469A (en) | 2006-10-27 |
CN1886301A (en) | 2006-12-27 |
ES2289226T3 (en) | 2008-02-01 |
CA2544044A1 (en) | 2005-05-26 |
EP1682416A1 (en) | 2006-07-26 |
DE60314637T2 (en) | 2007-10-25 |
US20070108156A1 (en) | 2007-05-17 |
TW200526473A (en) | 2005-08-16 |
AR047623A1 (en) | 2006-02-01 |
CA2544044C (en) | 2012-05-22 |
EP1527999A1 (en) | 2005-05-04 |
BRPI0416065A (en) | 2007-01-02 |
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