巴西专利BR112015004491B1 BOTTLE, METHOD OF MANUFACTURING A BOTTLE

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专利摘要:
bottle, method of making a bottle and using at least one thermoplastic polymer. the present invention relates to a bottle (1) comprising an envelope (2) defining a housing, said bottle being molded from at least one thermoplastic polymer of at least one furanedicarboxylic acid (fdca) monomer, preferably 2,5-furandicarboxylic acid monomer (2,5-fdca), and at least one diol monomer, preferably monoethylene glycol monomer (meg), the envelope being provided with at least one imprint (10a, 10b) .
公开号:BR112015004491B1
申请号:R112015004491-3
申请日:2012-08-31
公开日:2021-07-27
发明作者:Marie-Bernard Bouffand；Alain Colloud；Philippe REUTENAUER
申请人:SOCIETE ANONYME DES EAUX MINERALES D'EVIAN et en abrégé "S.A.E.M.E."；
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专利说明:

Technical Field
[0001] The invention relates to a bottle, a method for making the same and a use of FDCA monomers and diol in such a bottle. Technical Background and Technical Problems
[0002] Bottles made of plastic comprise impressions, such as grooves, grooves, clamping elements, indications or others, for technical or visual reasons, for example, to provide an improved strength. Corresponding print members are present in a mold used during a blow molding process, generally implemented to make the bottle, to impart prints to the bottle envelope.
[0003] PolyEthylene Terephthalate (PET) is a polymer generally used to make bottles, typically by the blow molding process. There is a demand for polymers based on renewable sources, for example, which can efficiently be of biological origin, to replace PET.
[0004] Polyethylene Furanoate (PEF) is a polymer that can be at least partially of biological origin. WO 2010/077133 describes, for example, processes suitable for preparing a PEF polymer having a 2,5-furandicarboxylate moiety within the polymer backbone. This polymer is prepared by esterifying the 2,5-furandicarboxylate [2,5-furanedicarboxylic acid (FDCA) or dimethyl-2,5-furanddicarboxylate (DMF)] group and condensing the ester with a diol or polyol (ethylene glycol, 1, 3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, poly(ethylene glycol), poly(tetrahydrofuran), glycerol , pentaerythritol). Some of these acid and alcohol groups can be obtained from renewable raw material crops.
[0005] It has been described that some bottles made from PEF were made. However, these bottles are believed to be quite basic. There is a need for advanced bottles.
[0006] The invention aims to solve at least one of the above problems and/or needs. Brief description of the invention The bottle
[0007] For this purpose, according to a first aspect, the invention proposes a bottle comprising an envelope that defines a housing, said bottle being molded from at least one thermoplastic polymer of at least one furanedicarboxylic acid (FDCA) monomer ), preferably 2,5-furandicarboxylic acid (2,5-FDCA) monomer, and at least one diol monomer, preferably monoethylene glycol (MEG) monomer, wherein the housing is provided with at least one imprint.
[0008] Thermoplastic polymer made from FDCA and diol monomers, such as polyethylene furanoate (PEF), has surprisingly been found to allow improved printing compared to PET. In particular, the thermoplastic polymer of the invention showed an increased ability to follow a profile of a print element of a mold thus making it possible to obtain some smaller and more accurate features printed on the bottle. Without wishing to be bound by any theory, it is believed that due to its flow and regularity characteristics, PET limits the type of prints that can be molded, especially for small print sizes. In particular, it is not possible to have text printed in small characters on PET bottles. The PEF surprisingly solves this.
[0009] In embodiments, the invention may comprise one or more of the following features:
[0010] - the print is selected from the group consisting of striations, grooves, ribs, reliefs, decorative patterns, gripping elements, brand indications, production indications, Braille characters, and a combination of these,
[0011] - the impression has two coplanar edges and an intermediate portion between the two edges, said intermediate portion presenting a vertex displaced in relation to the two edges (internally by a recess impression, such as a groove, groove or the like, and outwardly by an overhanging impression, such as a rib or the like), the impression having a width (w) measured between the two edges and a maximum height (h) measured between the edges and the apex,
[0012] - the print comprises a groove whose apex is displaced inwards with respect to the two edges,
[0013] - the width (w) and the maximum height (h) are such that the ratio between the maximum height to the width (h/w) is - in ascending order of preference - greater than or equal to 0.8; 1.0; 1,2; and preferably comprised between 1.2 and 200; 1,2 and 50; 1,2 and 20,
[0014] - the envelope is provided with at least two adjacent prints spaced apart along an axis according to a pitch (Pi), pitch (Pi) and the maximum height (h) of the print being such that:
[0015] when the maximum height is equal to 2 mm, then the pitch is less than or equal to 5 mm, preferably 4 mm, more preferably 3 mm, more preferably 2 mm, more preferably 1 mm,
[0016] when the pitch is equal to 5 mm, then the maximum height is greater than or equal to 2 mm, preferably 3 mm, more preferably 4 mm, more preferably 6 mm, more preferably 8 mm,
[0017] - the print has a print profile in a plane transverse to the edges, the print profile comprising a plurality of dots, each having a radius of curvature (RcPEF), the radius of curvature (RcPEF) at each point of the profile of print being less than 1 mm, preferably less than 0.7 mm, more preferably less than 0.5 mm, most preferably less than 0.3 mm,
[0018] - the envelope is cylindrical along an axis and comprises a side wall extending along the axis, said at least one print comprising at least one circumferential print extending at least partially around the axis on the wall side,
[0019] - the envelope additionally comprises a bottom extending transversely to the axis, the side wall extending from the bottom to a free end,
[0020] - said at least one impression comprises a dome impression extending centrally at the bottom, said dome impression having an outwardly facing concavity,
[0021] - said at least one print comprises at least one radial print extending radially with respect to the axis at the bottom,
[0022] - the envelope has an inner surface that delimits the housing and an outer surface opposite the inner surface, the impression consisting of a local deformation of both the inner and outer surfaces of the envelope between two adjacent parts of the envelope, said local deformation being chosen between a recess deformation with respect to the two adjacent portions and an relief deformation with respect to the two adjacent portions,
[0023] - the impression is different from the petal bottom of plastic bottles molded especially for carbonated liquids,
[0024] - the bottle is filled with a liquid, for example, a beverage or a non-food liquid, such as a home care product or a personal care product, preferably a beverage,
[0025] - the bottle, filled or empty, is closed by a closure, for example, a cap. The method of making the bottle
[0026] According to a second aspect, the invention proposes a method of manufacturing a bottle as defined above, comprising the steps of:
[0027] - provide a preform consisting of at least one thermoplastic polymer of at least one furanedicarboxylic acid (FDCA) monomer, preferably 2,5-furanedicarboxylic acid (2,5-FDCA) monomer, and at least one diol monomer, preferably monoethylene glycol (MEG) monomer,
[0028] - placing the preform in a mold having a cavity comprising at least one impression member,
[0029] - blowing the preform in the mold to form the bottle comprising an envelope defining a housing and provided with at least one imprint.
[0030] It is mentioned that the method according to the invention may also comprise an additional step of filling the bottle with a liquid, for example a beverage or a non-food liquid, such as a home care product or a health product. personal hygiene, preferably a drink. It is mentioned that the method according to the invention can also comprise a step of closing the bottle, filled or empty, with a closure, for example a cap.
[0031] In particular, in the step of providing a preform, the preform may comprise a hollow tube extending along an axis and having a closed lower end and an open upper end, the preform blowing step. - mold comprising blowing the preform through the open upper end and at a blowing pressure equal to or less than 35 bar, preferably 30 bar, more preferably 25 bar, more preferably 20 bar, more preferably 15 bar, more preferably 10 bar .
[0032] The ability of the thermoplastic polymer of the invention to follow the profile of the impression element of the mold additionally makes it possible to lower the blow pressure required in the blow molding step.
[0033] According to a third aspect, the invention proposes the use of at least one thermoplastic polymer of at least one furanedicarboxylic acid monomer (FDCA), preferably 2,5-furanedicarboxylic acid monomer (2,5), and at least one diol monomer, preferably monoethylene glycol (MEG) monomer, in a bottle as defined above.
[0034] The drink that can be filled in the bottles can be, for example, water, for example, purified water, mineral water, natural mineral water, optionally flavored, optionally carbonated. The drink can be an alcoholic beverage such as beer. The drink can be a soft drink, for example a cola drink, preferably carbonated. The drink can be a fruit juice, optionally carbonated. The drink can be vitamin water or an energy drink. The beverage can be a milk-based product such as milk or fermented dairy drink products such as yoghurt. The polymer making up the bottle: structure-preparation
[0035] The polymer comprises units corresponding to an FDCA monomer, preferably 2,5-FDCA, and units corresponding to a diol monomer, preferably a monoethylene glycol. The polymer is typically obtained by polymerizing monomers that provide such units in the polymer. For this purpose, FDCA can be used as monomers, preferably 2,5-FDCA or a diester thereof. Thus, polymerization can be either an esterification or a trans-esterification, both of which are also referred to as (poly)condensation reactions. One can preferably use dimethyl-2,5-furandicarboxylate (DMF) as a monomer.
[0036] The 2,5-FDCA group or monomer can be obtained from an ester of 2,5-furandicarboxylate and is an ester of a volatile alcohol or phenol or ethylene glycol, preferably having a boiling point of less than 150 °C, more preferably having a boiling point of less than 100 °C, even more preferably methanol or ethanol diester, most preferably methanol. 2,5-FDCA or DMF are typically considered to be of biological origin.
[0037] The 2,5-FDCA or ester can be used in combination with one or more other dicarboxylic acid, esters or lactones.
[0038] The diol monomer can be an aromatic, aliphatic or cycloaliphatic diol. Examples of suitable monomers of diols and polyols therefore include ethylene glycol, diethylene glycol, 1,2-propanediol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 1, 4-cyclohexanedimethanol, 1,1,3,3-tetramethylcyclobutanediol, 1,4-benzenedimethanol, 2,2-dimethyl-1,3-propanediol, poly(ethylene glycol), poly(tetrahydrofuran), 2.5 -di(hydroxymethyl)tetrahydrofuran, isosorbide, glycerol, pentaerythritol, sorbitol, mannitol, erythritol, threitol. Ethylene glycol, 1,3-propanediol, 1,4-butanediol, 1,4-cyclohexanedimethanol, 1,6-hexanediol, 2,2-dimethyl-1,3-propanediol, poly(ethylene glycol), poly(tetrahydrofuran) , glycerol, and pentaerythritol are particularly preferred diols.
[0039] In the preferred embodiment, the diol is ethylene glycol (monoethylene glycol - MEG), preferably of biological origin. For example, biologically sourced MEG can be obtained from ethanol, which can also be prepared by fermentation of sugars, (eg glucose, fructose, xylose) that can be obtained from crops or agricultural by-products, forestry by-products or municipal solid waste by hydrolysis of starch, cellulose, or hemicellulose. Alternatively, biologically sourced MEG can be obtained from glycerol, which itself can be obtained in the form of biodiesel waste.
[0040] The thermoplastic polymer, which is the raw material of the bottle according to the invention, may also comprise other diacid monomers, such as dicarboxylic acid or polycarboxylic acid, for example, terephthalic acid, isophthalic acid, cyclohexane dicarboxylic acid, maleic acid, succinic acid, 1,3,5-benzenetricarboxylic acid. Lactones can also be used in combination with the 2,5-furandicarboxylate ester: Pivalo lactone, epsilon-caprolactone and lactides (L, L; D, D; D, L). Even though it is not the most preferred embodiment of the invention, the polymer can be non-linear, branched, thanks to the use of polyfunctional monomers (more than two acid or hydroxyl functions per molecule), both acidic and/or hydroxylic monomers, for example , polyfunctional aromatic, aliphatic or cycloaliphatic polyols, or polyacids.
[0041] According to a preferred embodiment of the invention, the polymer is a PEF material using 2,5-FDCA of biological origin and monoethylene glycol of biological origin. In fact, 2,5-FDCA comes from 5-hydroxymethylfurfural (5-HMF), which is produced from glucose or fructose (obtained from renewable resources). Monoethylene glycol can be obtained from ethanol, which can also be prepared by fermentation of sugars, (eg glucose, fructose, xylose) that can be obtained from crops or from agricultural by-products, forestry by-products or municipal solid waste by hydrolysis of starch, cellulose, or hemicellulose. Alternatively, monoethylene glycol can be obtained from glycerol, which itself can be obtained in the form of biodiesel residues.
[0042] This is referred to as a 100% biobased or biologically sourced PEF, as most of the monomers used are considered to be of biological origin. As some comonomers and/or some additives, and/or some impurities and/or some atoms may not be of biological origin, the actual amount of material of biological origin may be less than 100%, for example, between 75% and 99% by weight, preferably from 85 to 95%. PEF can be prepared according to the state of the art to make PEF, for example as described in WO 2010/077133. Bottles can be made from this material, for example, by injection blow molding (IBM) processes, preferably by injection and stretch blow molding (ISBM) processes. Such a bottle may have properties similar to those previously described publicly with PEF where 2,5-FDCA or monoethylene glycol are not of biological origin. Such properties, including mechanical properties, can be improved compared to PET.
[0043] The term "polymer" according to the present invention comprises homopolymers and copolymers, such as random or block copolymers.
[0044] The polymer has a number average molecular weight (Mn) of at least 10,000 Daltons (as determined by GPC based on polystyrene standards). Mn of the polymer is preferably comprised between - in daltons and an increasing order of preference - 10,000 to 100,000; 15000 and 90000; 20000 and 80000; 25000 and 70000; 28000 and 60000.
[0045] According to a remarkable feature of the invention, the polymer polydispersity index (PDI) = Mw/Mn (Mw = weight average molecular weight) is defined as follows - in ascending order of preference -: 1 < PDI < 5; 1.1 < PDI < 4; 1.2 < PDI < 3; 1.3 < PDI < 2.5; 1.4 < PDI < 2.6; 1.5 < PDI < 2.5; 1.6 < PDI < 2.3.
[0046] Generally, the process for the preparation of the polymer comprises the following steps: (trans)esterification of the dimethyl ester 2,5-FDCA, of the diglycerylester of 2,5-FDCA; (poly)condensation reaction in the presence of a tin (IV) based catalyst and, optionally, a purification step. The process for preparing PEF may comprise a Solid State Polymerization (SSP) step. Detailed description of the invention
[0047] Other objects and advantages of the invention will be more evident from the following description of a particular embodiment of the invention, given as a non-limiting example, the disclosure being made with reference to the attached drawings, in which:
[0048] - Figure 1 is a side view of a bottle comprising an envelope provided with grooves according to an embodiment of the invention,
[0049] - Figure 2 is an enlarged view of the detail referenced D in Figure 1 representing one of the bottle grooves,
[0050] - Figure 3 is an enlarged view of the detail referenced D in Figure 1 which represents a variant of one of the bottle grooves,
[0051] - Figure 4 is an underside view of the bottle in Figure 1,
[0052] - Figure 5 is a side view of a preform used in a blow molding process to make the bottle of Figure 1,
[0053] - Figure 6 is a schematic view of an experimental setup to obtain a groove profile of one of the bottle grooves,
[0054] - Figures 7a, 7b and 7c are respective representations of the groove profiles of the grooves referenced R1, R2 and R3 in Figure 1 obtained by the experimental set of Figure 6, the groove profiles being superimposed on corresponding groove groove profiles of a reference bottle identical to the bottle in Figure 1, except that the reference bottle is made of PET.
[0055] In the Figures, like reference numerals refer to the same or similar elements.
[0056] Figure 1 represents a bottle 1 suitable for containing for example a liquid such as water. The bottle 1 is cylindrical along an axis A, of circular cross-section, and comprises an envelope 2. The envelope 2 comprises a bottom 3 perpendicular to the axis A, and a side wall 4 extending from the bottom 3 along of the axis A. At a free end, opposite the bottom 3, the sidewall 4 forms a neck 5 that narrows in the direction of the axis A. Both the bottom 3 and the sidewall 4 have inner surfaces that delimit a housing, and surfaces outer surfaces opposite inner surfaces. Following the description, the terms "inside", "inward", "inside" and the like will refer to an element situated near or directed towards the housing or axis, and the terms "outside", "outside", "outward" and the like refer to an element situated beyond or directed opposite the housing or shaft.
[0057] As a non-limiting example, bottle 1 may have a height H measured along axis A of 317.75 millimeters. The sidewall 4 may have a curved contour along axis A defining an intermediate narrow portion IB, which may have a maximum width Wb measured perpendicularly to axis A of 80 mm, between two large portions 1A, 1C, each of which it can have a maximum Wa width of 89 mm. A first 1A of the large portions, near the bottom 3, may have a height Ha of 148 mm and the intermediate narrow portion IB may have a height Hb of 56 mm. The neck 5 may have a frusto-conical portion connected to a second 1C of the large portions, in addition to the bottom 3, and a cylindrical portion. The cylindrical portion of the neck 5 is provided with a thread 6 on the outer surface to allow a cap to be screwed onto the neck 5 to close the bottle 1.
[0058] As can be seen in Figures 1 to 4, envelope 2 is provided with prints, each consisting of a local deformation of both the inner and outer surfaces of envelope 2 between two adjacent portions of envelope 2.
[0059] In the illustrated embodiment, the prints comprise a plurality of adjacent circumferential grooves 10a, 10b extending at least partially around axis A in sidewall 4. In particular, each circumferential groove 10b of the intermediate narrow portion IB is annular and it extends circumferentially substantially in a plane perpendicular to axis A, whereas each circumferential groove 10a of the large portions 1A, 1C is annular and undulating circumferentially with respect to a plane perpendicular to axis A. The circumferential grooves 10a, 10b are regularly arranged in each portion of the sidewall 4 according to a pitch Pi along axis A. Two adjacent circumferential grooves 10a of the large portions 1A, 1C are therefore separated from each other by a distance measured along axis A corresponding to a first step Pi1. Two adjacent circumferential grooves 10b of the intermediate narrow portion IB are separated from each other by a distance measured along axis A which corresponds to a second pitch Pi2.
[0060] In particular, as can be seen in Figure 2, each circumferential groove 10a, 10b consists of a local deformation at recess with respect to the two adjacent portions of the envelope 2. Each circumferential groove 10a, 10b then has two coplanar edges 11, i.e. is substantially arranged in a plane parallel to the axis A of the bottle 1, and an intermediate portion 12 between the two edges 11. The intermediate portion 12 of each groove has a curved apex 13 displaced inwards, i.e., in the direction of axis A, with respect to the two edges 11. In a variant shown in Figure 3, the vertex 13 may be flat. Each circumferential groove 10 has a width w measured between the two edges 11 and a maximum height h measured between the edges 11 and the apex 13.
[0061] As a non-limiting example, the width w and the maximum height h can be such that the ratio h/w of the maximum height to the width is - in ascending order of preference - greater than or equal to 0.8; 1.0; 1,2; and preferably comprised between 1.2 and 200; 1,2 and 50; 1,2 and 20.
[0062] In addition, the pitch Pi and the maximum height h of the circumferential groove can be such that:
[0063] - when the maximum height is equal to 2 mm, then the pitch is less than or equal to, in ascending order of preference, 5 mm, 4 mm, 3 mm, 2 mm or 1 mm,
[0064] - when the pitch is equal to 5 mm, then the maximum height is greater than or equal to, in ascending order of preference, 2 mm, 3 mm, 4 mm, 6 mm or 8 mm.
[0065] As can be seen in Figure 4, at the bottom 3, the impressions also comprise a central impression of dome 15 and radial grooves 16 that extend radially with respect to axis A. The impression of dome 15 extends inwardly to from an annular edge to an apex arranged on axis A. The dome impression 15 thus presents an outwardly oriented concavity. As for the circumferential grooves 10a, 10b, each radial groove 16 curves inwardly from two coplanar edges.
[0066] Although the invention has been described with a cylindrical bottle comprising several grooves as prints, the invention is not limited to this. In particular, the bottle may be of any other suitable shape, such as cylindrical, elliptical, polygonal or other cross-section. In addition, the envelope can be provided with one or more prints consisting of a recessed local deformation, as described above in relation to the grooves, or a raised local deformation, i.e. protruding, in relation to the two adjacent portions . In the last case, the intermediate portion of such impression has a vertex displaced outwards, that is, opposite axis A, in relation to the two edges. Thus, the print can be of any type, in particular selected from the group consisting of striations, grooves, ribs, embossing, decorative patterns, gripping elements, mark indications, production indications, Braille characters, and a combination of same.
[0067] The bottle 1 can be molded, for example, by a blow molding process, from a plastic material chosen according to the content with which the bottle is intended to be filled. In particular, the plastic material is preferably at least in part of biological origin and the bottle is filled with a liquid, such as water or other beverage, before the cap is screwed on and sealed to the neck 5.
[0068] According to the invention, the bottle 1 described above is made of a thermoplastic polymer of at least one furandicarboxylic acid (FDCA) monomer and at least one diol monomer. In particular, the thermoplastic polymer is a PolyEthylene Furanoate (PEF) based on biobased 2,5-FDCA and biobased monoethylene glycol (MEG). Polymer preparation and bottle fabrication are detailed below in the following example. Example Materials
[0069] - 2,5-furanedicarboxylic acid (2,5-FDCA) and dimethyl-2,5-furanedicarboxylate (DMF), for example, prepared according to WO 2011/043660.
[0070] - MEG: MEG of biological origin, such as diol.
[0071] - PET (comparative): PET wl70 supplied by Indorama, with the following characteristics:
[0072] - glass transition temperature, Tg = 75°C,
[0073] - melting temperature, Tf = 235°C,
[0074] - density (amorphous), d = 1.33. PEF polymer preparation
[0075] The polymerizations are carried out in a 15 L stirred batch reactor. Dimethyl 2,5-furandicarboxylate (5.0 kg; 27.17 mol), bio-ethylene glycol (4.02 kg; 64.83 mol) and acetate of Ca monohydrate (8.48 g; 10.4 mmol) are mixed under nitrogen atmosphere in the pre-dried reactor, while heating to a temperature of 130°C when methanol begins to distill. The temperature is maintained at about 130°C until most of the methanol is removed by distillation. Subsequently, the temperature is increased to 190°C (mantle temperature) under nitrogen discharge for 2 hours. Then, Sb glycolate (3.48 g Sb203) dissolved in 200 ml of bioethylene glycol was added under stirring at 40 rpm. The temperature is increased to 210°C while vacuum is applied slowly. At 300 mbar most of the ethylene glycol is distilled off. Finally, the vacuum is reduced as much as possible, but definitely less than 1 mbar. The mantle temperature is raised to 240°C and the increase in molecular weight was monitored by measuring the stirring torque. The polymer that is obtained from the reactor is shown to have a Mn value of 16000 g/mol. And a Mw/Mn of 2.5. Solid state polymerization is carried out in a dryer. During the first 12 hours, crystallization of the polymer is carried out at 145°C. Subsequently, over a period of 72 hours, the temperature is slowly raised to above 200°C. Care is taken that polymer particles do not stick together. After 72 hours, the polymer has:
[0076] - Number average molecular weight measured by GPC, Mn = 30000,
[0077] - glass transition temperature, Tg = 85°C,
[0078] - melting temperature, Tf = 210°C,
[0079] - density (amorphous), d = 1.42,
[0080] - polydispersity index, Mw/Mn PDI = 2.1.
[0081] GPC measurements are performed on a Merck Hitachi LaChrom-HPLC system equipped with two PLgel 10 mm MIXED-C columns (300 x 7.5 mm). A 7:3 chloroform:2-chlorophenol solvent mixture was used as the eluent. Molecular weight calculation was based on polystyrene standards and performed by Cirrus™ PL DataStream software. UV-visible spectra and absorbances were recorded on a Helios (ThermoSPectronic = spectrophotometer). Bottle manufacturing method
[0082] The bottle according to the invention is preferably manufactured by a blow molding process implementing a mold, such as a Sidel SBO 1 machine, having a cavity comprising one or more impression members, and a blowing device adapted to supply the cavity with a fluid at a blowing pressure. Each printing element has two coplanar edges and an intermediate portion, between the two edges, shaped so as to form the desired print on the envelope 2 of the bottle 1. In particular, the intermediate portion of each printing element has an apex offset relative to to both edges. In the illustrated embodiment, for the formation of grooves in the envelope 2 of the bottles 1, the intermediate portion is in relief in relation to the two edges and has a apex, preferably flat, displaced inwards (with regard to the cavity, i.e. towards a central axis of the cavity) in relation to the two edges. For example, the print members have a width w = 2.5 mm between the two coplanar edges and a height h = 6.5 mm between the edges and the vertex.
[0083] The blow molding process implements a 30 g preform 20 made of the appropriate thermoplastic polymer, such as the PEF thermoplastic polymer, the preparation of which was described above. As can be seen in Figure 5, the preform 20 comprises a hollow tube 21 which extends along an axis A0 and has a closed lower end 22 and an open upper end 23. The upper portion 25 of the preform 20 near the open upper end 23 is shaped as the neck 5 of the bottle 1. The remaining portion of the tube 21 is cylindrical of circular cross section with a diameter substantially equal to that of the upper portion 25.
[0084] As a non-limiting example, preform 20 may have a height Hp measured along axis A0 of 121 mm and an inner diameter ranging from 21 mm near the closed lower end 22 to 25 mm near the upper end open 23.
[0085] To manufacture 30g preforms of the type described above, a 20 kg sample of thermoplastic polymer PEF described above is used in an 800 Netstal Elion injection molding machine. The matter was heated to 250°C, with a cycle time of 19.92 s. The PEF 20 preforms were heated to a surface temperature of 120°C. After the preforms 20 have been placed in the mold at a cold temperature (10°C - 13°C), the preforms 20 can be blown by means of injection of the fluid at the blowing pressure into the interior of the preform through the open top end 23. Thanks to the use of the PEF thermoplastic polymer, the blowing pressure can be reduced to 35 bar or less, and especially in order increasing preferably at 30 bar, 25 bar, 20 bar, 15 bar or 10 bar. In particular, the preforms 20 were cast with a blowing pressure of 34 bar for bottles 1 of the type described above, i.e. a 1.5 L type with a typical still water design, featuring grooves.
[0086] The preforms were similarly made with PET wl70 from Indorama with a weight of 30 g for comparison with the thermoplastic polymer PEF. The matter was heated to 265°C, with a cycle time of 20.04 s. The PET preforms were heated to a surface temperature of 108°C - 110°C, placed in the mold at cold temperature (10°C - 13°C) and blown, with a blowing pressure greater than 35 bar, to the same 1.5 L type bottles with a typical still water design, featuring grooves, hereinafter referred to as reference bottles. A good distribution of material was achieved in all cases.
[0087] The bottles thus produced are identical to bottle 1 described above. Tests and results
[0088] In order to assess the amazing moldability improvement brought by PEF against PET, some tests are performed.
[0089] The grooves of each bottle each have a printing profile, here a groove profile, in a plane transverse to the edges, such as a plane parallel to a median longitudinal plane containing the axis A. The groove profile is constituted by a plurality of points, each having a radius of curvature.
[0090] A comparison of groove profiles of the grooves of a test bottle 1 molded from PEF and the grooves of a reference bottle molded from PET is made. As explained above, the PEF test bottle 1 and the PET reference bottle were molded by the same mold having the same printing members. Therefore, each printing member can form corresponding grooves on the PEF test bottle 1 and the reference PET bottle.
[0091] For comparison, the groove profiles, and especially the radius of curvature at each point of the groove profiles, are measured according to a protocol described below implementing an experimental set 30 shown in figure 6.
[0092] Firstly, enlarged projections of the groove profiles of the corresponding prints of the PEF test and PET reference bottles are obtained.
[0093] As shown in figure 6, these enlarged projections are made using a profile projector 31 which is a device that projects an enlarged profile image of an area or feature of a workpiece onto a screen 32. Here, the projector of profile 31 and screen 32 were used for measuring the groove profiles of the bottles. They could, however, be used for measuring any other structural and/or decorative feature printed on the bottles. Measurements were taken using a Deltronic DH350.
[0094] Marks are given to the PEF test and PET reference bottles to differentiate them, and their orientation in relation to the mold is checked. The positions of the grooves to be measured are precisely identified. In particular, in the illustrated embodiment, the grooves identified in Figure 1, R1 (in the second large portion 1C), R2 (in the intermediate portion IB) and R3 (in the first large portion 1A) are measured for the PEF test bottle 1 and the PET reference bottle.
[0095] The PEF test and PET reference bottles are cut along a transverse joint plane using a cutter with a blade oriented orthogonally to the envelope and moved from the outside to the inside, to avoid creating any external surface defect that may alter the quality of the groove profile measurement. A portion of the PEF test bottles and PET reference bottles corresponding to a sector of about 90° is removed to allow measurement.
[0096] The measurement of the groove profile of each groove is made using an appropriate magnification, so that the groove is displayed over the entire screen 32. For example, the magnification is at least 10 times.
[0097] The PEF 1 test bottle is placed on a measuring table and its stability is checked. The PEF test bottle 1 is oriented relative to the profile projector 31 so that the plane that has been cut is orthogonal to an incident light beam emitted by the profile projector 31. The groove R1 of the PEF test bottle 1 it is measured by vertical translation of the object. The focusing of an image on the screen 32 representing the enlarged print profile of slot R1 is ensured. When the image is sharp, a transparent sheet is attached to the screen 32, and held in place. The image projected on screen 32 is hand-drawn, and accurately identified. The enlarged groove profiles of the other grooves R2 and R3 of the PEF test bottle 1 are successively drawn in the same way.
[0098] The enlarged groove profiles of the corresponding grooves R1, R2 and R3 of the PET reference bottle are successively extracted in the same way. Also for the mold, a similar measurement is made using the reflection of a light that shone on the insert mold.
[0099] Secondly, the images of the groove profiles enlarged from the corresponding grooves of the PEF test bottles and the PET reference bottles are overlaid for the comparison of groove profiles and determination of a print quality. Especially:
[0100] - Figure 7a represents the superimposed images of the enlarged groove profiles of the corresponding grooves R1 of the PEF test and reference PET bottles,
[0101] - Figure 7b represents the superimposed images of the enlarged groove profiles of the corresponding grooves R2 of the PEF test and PET reference bottles,
[0102] - Figure 7c represents the superimposed images of the enlarged groove profiles of the corresponding grooves R3 of the PEF test and PET reference bottles.
[0103] From the superimposed images of each corresponding slot, pairs of corresponding points can be defined. For example, each pair of corresponding points comprises a point of the enlarged projection of one of the groove profile of the PEF test bottle 1 and a point of the enlarged projection of the corresponding groove profile of the PET reference bottle arranged on the same perpendicular line to the axis of the bottles.
[0104] Thus, to determine the print quality, the radii of curvature of each pair of corresponding points of the enlarged projections of the groove profiles are measured. Therefore, for each pair of corresponding points, the radius of curvature RcPEF of the groove profile of the groove profile of the PEF test bottle 1 and the radius of curvature RcPET of the groove profile of the corresponding groove profile of the PET reference bottle are measured.
[0105] As can be seen in Figures 7a to 7c, the radius of curvature RcPEF of the groove profile of the PEF test bottle 1 at each point is capable of reaching values lower than the radius of curvature RcPET of the corresponding point of the groove profile of the PET reference bottle. For example, the radius of curvature RcPEF at each point of the groove profile of the PEF test bottle 1 may be less than 1 mm, preferably less than 0.7 mm, more preferably less than 0.5 mm, most preferably less to 0.3mm.
[0106] Therefore, the profile of the grooves generated by the PEF test bottle can precisely follow a contour of the impression members of the mold, while the reference PET bottle systematically exhibits a less accurate impression.

权利要求:
Claims (41)
[0001]
1. Bottle (1) characterized in that it comprises an envelope (2) defining a housing, said bottle being molded from at least one thermoplastic polymer of at least one 2,5-furanedicarboxylic acid (2,5-FDCA) monomer and at least one diol monomer, wherein the envelope is provided with at least one print (10a, 10b, 15, 16).
[0002]
2. Bottle (1), according to claim 1, characterized in that the diol monomer is monoethylene glycol (MEG) monomer.
[0003]
3. Bottle (1), according to any one of claims 1 and 2, characterized in that the print is selected from the group consisting of grooves, grooves, ribs, reliefs, decorative patterns, gripping elements, marking indications, production directions, Braille characters, and a combination thereof.
[0004]
4. Bottle (1) according to any one of claims 1 to 3, characterized in that the print (10a, 10b) has two coplanar edges (11) and an intermediate portion (12) between the two edges (11), the said intermediate portion (12) having an apex (13) displaced in relation to the two edges (11), the print (10a, 10b) having a width (w) measured between the two edges (11) and a maximum height (h) measured between the edges (11) and the apex (13).
[0005]
Bottle (1) according to claim 4, characterized in that the impression comprises a groove (10a, 10b) whose apex (13) is displaced inwardly with respect to the two edges (11).
[0006]
Bottle (1) according to any one of claims 4 and 5, characterized in that the width (w) and the maximum height (h) are such that the ratio of the maximum height to the width (h/w) is greater than or equal to 0.8.
[0007]
Bottle (1) according to any one of claims 4 and 5, characterized in that the width (w) and the maximum height (h) are such that the ratio between the maximum height and the width (h/w) is greater than or equal to 1.0.
[0008]
Bottle (1) according to any one of claims 4 and 5, characterized in that the width (w) and the maximum height (h) are such that the ratio between the maximum height to the width (h/w) is greater than or equal to 1.2.
[0009]
Bottle (1) according to any one of claims 4 and 5, characterized in that the width (w) and the maximum height (h) are such that the ratio of the maximum height to the width (h/w) is between 1.2 and 200.
[0010]
Bottle (1) according to any one of claims 4 and 5, characterized in that the width (w) and the maximum height (h) are such that the ratio of the maximum height to the width (h/w) is between 1.2 and 50.
[0011]
Bottle (1) according to any one of claims 4 and 5, characterized in that the width (w) and the maximum height (h) are such that the ratio of the maximum height to the width (h/w) is between 1.2 and 20.
[0012]
Bottle (1) according to any one of claims 4 to 11, characterized in that the envelope (2) is provided with at least two adjacent prints (10a, 10b) spaced from one another along an axis (A) according to a step (Pi), the maximum height (h) being equal to 2 mm and the step (Pi) being less than or equal to 5 mm.
[0013]
Bottle (1) according to claim 12, characterized in that the pitch (Pi) is less than or equal to 4 mm.
[0014]
Bottle (1) according to claim 12, characterized in that the pitch (Pi) is less than or equal to 3 mm.
[0015]
Bottle (1) according to claim 12, characterized in that the pitch (Pi) is less than or equal to 2 mm.
[0016]
Bottle (1) according to claim 12, characterized in that the step (Pi) is less than or equal to 1 mm.
[0017]
Bottle (1) according to any one of claims 4 to 11, characterized in that the envelope (2) is provided with at least two adjacent prints (10a, 10b) spaced from one another along an axis (A) according to a pitch (Pi), the pitch (Pi) being equal to 5 mm and the maximum height (h) being greater than or equal to 2 mm.
[0018]
18. Bottle (1) according to claim 17, characterized in that the maximum height (h) is greater than or equal to 3 mm.
[0019]
19. Bottle (1) according to claim 17, characterized in that the maximum height (h) is greater than or equal to 4 mm.
[0020]
20. Bottle (1) according to claim 17, characterized in that the maximum height (h) is greater than or equal to 6 mm.
[0021]
21. Bottle (1) according to claim 17, characterized in that the maximum height (h) is greater than or equal to 8 mm.
[0022]
22. Bottle (1) according to any one of claims 2 to 21, characterized in that the print has a print profile in a plane transverse to the edges (11), the print profile comprising a plurality of dots, each having a radius of curvature (RcPEF), the radius of curvature (RcPEF) at each point of the print profile being less than 1 mm.
[0023]
Bottle (1) according to claim 22, characterized in that the radius of curvature (RcPEF) at each point of the print profile is less than 0.7 mm.
[0024]
Bottle (1) according to claim 22, characterized in that the radius of curvature (RcPEF) at each point of the print profile is less than 0.5 mm.
[0025]
Bottle (1) according to claim 22, characterized in that the radius of curvature (RcPEF) at each point of the print profile is less than 0.3 mm.
[0026]
26. Bottle (1) according to any one of claims 1 to 25, characterized in that the envelope (2) is cylindrical along an axis (A) and comprises a side wall (4) extending along the axis (A), said at least one print comprising at least one circumferential print (10a, 10b) extending at least partially around the axis in the sidewall (4).
[0027]
27. Bottle (1) according to claim 26, characterized in that the envelope (2) further comprises a bottom (3) extending transversely to the axis (A), the side wall (4) extending from from the bottom (3) to a free end.
[0028]
Bottle (1) according to claim 27, characterized in that said at least one impression comprises a dome impression (15) extending centrally over the bottom (3), said dome impression (15) having an outwardly oriented concavity.
[0029]
Bottle (1) according to claim 27 or 28, characterized in that said at least one imprint comprises at least one radial imprint (16) extending radially with respect to the axis (A) in the bottom (3).
[0030]
30. Bottle (1) according to any one of claims 1 to 29, characterized in that the envelope (2) has an inner surface that delimits the housing and an outer surface opposite the inner surface, the impression consisting of a local deformation of both inner and outer surfaces of the envelope (2) between two adjacent portions of the envelope, said local deformation being chosen between a recess deformation with respect to the two adjacent portions and a relief deformation with respect to the two adjacent portions.
[0031]
Bottle (1) according to any one of claims 1 to 30, characterized in that it is filled with a liquid.
[0032]
Bottle (1) according to claim 31, characterized in that the liquid is a beverage.
[0033]
33. Method of manufacturing a bottle (1) as defined in any one of claims 1 to 32, characterized in that it comprises the steps of: - providing a preform (20) consisting of at least one thermoplastic polymer of acid 2 monomer, 5- furanedicarboxylic acid (2,5-FDCA) and at least one diol monomer, - place the preform (20) in a mold having a cavity comprising at least one impression member, - blow the preform (20) ) in the mold to form the bottle (1) comprising an envelope (2) defining a housing and provided with at least one imprint (10a, 10b, 15, 16).
[0034]
The method of claim 33, characterized in that in the step of providing a preform (20), the preform comprises a hollow tube (21) which extends along an axis (A0), and has a lower closed end (22) and an upper open end (23), the step of blowing the preform (20) comprising blowing the preform (20) through the upper open end (23) at a lower blowing pressure or equal to 3.5 MPa (35 bar).
[0035]
The method of claim 34, characterized in that the blowing pressure is less than or equal to 3.0 MPa (30 bar).
[0036]
The method of claim 34, characterized in that the blowing pressure is less than or equal to 2.5 MPa (25 bar).
[0037]
The method of claim 34, characterized in that the blowing pressure is less than or equal to 2.0 MPa (20 bar).
[0038]
The method of claim 34, characterized in that the blowing pressure is less than or equal to 1.5 MPa (15 bar).
[0039]
The method of claim 34, characterized in that the blowing pressure is less than or equal to 1.0 MPa (10 bar).
[0040]
A method according to any one of claims 33 to 39, characterized in that it further comprises a step of filling the bottle with a liquid.
[0041]
The method of claim 40, characterized in that the liquid is a beverage.

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法律状态:
2019-10-22| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|

2020-08-04| B06A| Notification to applicant to reply to the report for non-patentability or inadequacy of the application [chapter 6.1 patent gazette]|

2020-11-24| B07A| Technical examination (opinion): publication of technical examination (opinion) [chapter 7.1 patent gazette]|

2021-05-18| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|

2021-07-27| B16A| Patent or certificate of addition of invention granted|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 31/08/2012, OBSERVADAS AS CONDICOES LEGAIS. |

优先权:

申请号 | 申请日 | 专利标题

PCT/EP2012/066996|WO2014032730A1|2012-08-31|2012-08-31|Bottle, method of making the same and use of fdca and diol monomers in such bottle|

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