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    • 专利摘要:
    POLYETHYLENE JOINT BY RETICULATED RADIATION Durable polyethylene joints used as "press top" caps for condiments and the like that can be irradiated by electronic beam effecting a partial crosslinking of the polyethylene to produce a joint featuring an improvement in number of opening and closing cycles until failure is not less than 30%. Irradiated lids can be used instead of polypropylene lids intended for condiment containers.
    公开号:BR112016020055B1
    申请号:R112016020055-1
    申请日:2015-01-29
    公开日:2021-07-06
    发明作者:Jason Rycroft；Gilbert Arnould；Matthew Botros；William McGrory
    申请人:Nova Chemicals (International) S.A.；
    IPC主号:
    专利说明:

    Technical Field
    [001] The present invention relates to polyethylene joints by crosslinked radiation intended for lids facing dosage containers, such as for condiments, spices, soups, shampoos, oils and pills. Such joints need to have a lifetime of at least around 300 openings and closings before they cease to function (eg, joint rupture). In some embodiments, the lid closes when brought towards the gently closed position and remains open when brought towards the fully open position. These covers contain a hinge around where the cover or cover pivot can open and close. These caps are sometimes referred to as snap-top caps. The hinge element is sometimes referred to as a "durable hinge". Fundamentals of Technique
    [002] There is an extensive technique in this field.
    [003] U.S. Patent 4047,495, issued September 13, 1997, to O'Brien, assigned to Polytop Corporation, describes a child-proof “push-top” type cap facing a container. The patent specification shows that the durable joint is preferably injection molded from polypropylene due to the well known durable joint properties of polypropylene. Other olefin polymers can be used, but are not preferred (Col. 4, lines 41-50). The patent does not teach or suggest that other types of polyolefins can be modified by cross-linking radiation to provide improved properties.
    U.S. Patent 4,638,916 issued January 27, 1987 and co-workers assigned to Owens-Illinois, Inc. describes a pressure-type hinge cover. The structural elements of the lid are described, but there is no description of what material the lid is to be made of. An expert in the field would later select polypropylene as the material of choice. Furthermore, there is no suggestion regarding the use of reticulated radiation to improve the properties of the joint.
    [005] U.S. Patent 5,148,912 issued September 22, 1992 to Nozawa et al. assigned to Yoshino Kogyosho Co., Ltd. shows a lid with a slightly different pressure top where there are two separate strips or hinges. Again, no description is present of what kind of material the lid is to be made. An expert in the field would later select polypropylene as the material of choice. Furthermore, there is no suggestion of using crosslinked radiation to improve joint properties.
    [006] U.S. Patent 6041477 issued on March 28, 2000 to Rentsch et al., further describes the structural elements of a lid with pressure top differing from the prior art. While the patent contains a warning about the residual stress near the pressure top lids presenting opposite effects with the injection of plastic molding material, (Col.3, lines 28 to 35), no part of the descriptive report is present any suggestion as to the use of reticulated radiation to improve joint properties.
    [007] US Patent 6766926 issued on July 27, 2004 from Elchert assigned to Owens-Illinois Inc., describes the most common type of closure observed today. The structural elements of the roof are clearly described. However, once again, the form of material through which the roof is constructed is not discussed. Furthermore, there is no suggestion regarding the use of reticulated radiation to improve the properties of the joint.
    [008] Cross-linked polyethylene (PEX) is well known. In some applications there is the use of tube and wire inclusion and tube coating. U.S. Patent 8192,813 issued June 5, 2012 to Runyan et al., assigned to Exxon Mobil Chemical Patents, Inc. and Zun Pex, Inc. describes modifiers that can be added to polyethylene to improve the properties of polyethylene. cross-linked polyethylene. The present invention does not contemplate the use of additives to enhance the lattice, particularly in view of the fact that many durable joints are employed in conjunction with food dosing containers. Interestingly, the 813 patent does not describe or suggest the use of cross-linked polyethylene in pressure caps or acting joints.
    [009] The present invention seeks to provide with a durable crosslinked polyethylene web by electronic beam suitable for use in a joint for containers. Description of the Invention
    [010] In the broader scope of this modality of the present invention there is the provision of one or more flexible joints of polyethylene molded by injection or by compression of crosslinked radiation of electronic beam (irradiation), comprising one or more wefts having a thickness ranging from 0.1 to 1 mm, preferably 0.2 to 0.5 mm, joining a cover containing a rim, optionally a flat panel having at least one opening therethrough and a flat closure cooperating member secured to the cover by means of one or more of said flexible joints where the number of opening and closing cycles that break with a radial curvature of 90° ± 20° for a temperature of 25° of the flexible joint is increased by not less than 30 %, in relation to the number of opening and closing cycles for rupture with a radial curvature of 90° ± 20° at a temperature of 25°C of a flexible joint made of the same polyethylene and presenting the same model without having been subjected to cross-linked irradiation.
    [011] In an additional modality, one or more of said wefts present an increase in the number of burst opening and closing cycles along with a radial curvature of 90° ± 20° at a temperature of 25°C of not less than 100 %, in relation to the number of rupture opening and closing cycles with a radial curvature of 90° ± 20° at a temperature of 25°C of a flexible joint of the same polyethylene and presenting the same model without having been subjected to cross-linked irradiation.
    [012] In an additional modality, the number of opening and closing cycles of rupture of a radial curvature of 90° ± 20° at a temperature of 25°C is not less than 280 cycles, preferably greater than 400, more preferably greater than 800 cycles.
    [013] In an additional modality, said one or more frames came to be irradiated with at least 20 to 140 kGy (w-14 Mrads (MR)), preferably ranging from 30 to 100 kGy (3 to 10 MR) of electronic beam radiation.
    [014] In a further modality, the web consists of a simple web, the cover comprises a flat panel continuously fixed to said rim, and the web connects the panel to the flat closing member.
    [015] In an additional modality, the coverage consists of a parallelogram.
    [016] In an additional modality, the coverage is circular.
    [017] In an additional embodiment, the flat closure member further comprises a continuous ring extending downwards.
    [018] In an additional embodiment, two webs connect the rim of the flat closure member to the rim of the cover.
    [019] In an additional modality, the outer edges of the two said wefts imply an angle from the central part of the flat panel going from 20 to 75°.
    [020] In an additional modality, the outer edges of two said wefts imply an angle from the central part of the flat panel going from 50 to 75°.
    [021] In an additional modality, the passage through the flat panel comprises of a gargoyle extending upwards.
    [022] In a further embodiment, the flat closure member comprises a plug extending downwardly along its lower surface cooperating with said gargoyle for its sealing.
    [023] In an additional modality, there is an opening of the flat closure member articulating together with said wefts through a region of higher tension for the "instant pressure" of the open lid and preserving it open.
    [024] In an additional modality, there is the closure of the flat closure member articulating with said wefts through a region of higher tension for the "instant pressure" of the lid closed and keeping it closed.
    [025] In an additional modality, there is the provision of additional elements next to the rim of the cover for engaging the rim of the flat closure member when it is being closed.
    [026] In a further embodiment, the polyethylene comprises one or more ethylene polymers comprising from 100% by weight to 80% by weight of ethylene and ranging from 0 to 20% by weight of one or more alpha olefin monomers of C4-8 of said polyethylene having a density of 0.920 g/cm3 to 0.970 g/cm3, typically not less than 0.94 g/cm3.
    [027] In an additional modality, the uncrosslinked polyethylene has a melt index (MI) (ASTM D 1238 -2.16 kg and 190°C) ranging from 5 to 80, typically ranging from 5 to 55 g/10 min .
    [028] In an additional modality, flexible joints are injection molded.
    [029] In an additional modality, said polyethylene has a melt index (MI) (ASTM D 1236 - 2.16 kg and 190°C) ranging from 0.25 to 50, typically ranging from 0.5 to 30.
    [030] In an additional modality, the flexible joints are molded by compression.
    [031] In a further embodiment, the present invention provides with the above articulation, where the polyethylene comes to be selected from the group consisting of polyethylene under high pressure, the Ziegler Natter catalyst polyethylene, the chromium catalyst polyethylene, and the single site catalyst polyethylene.
    [032] In a further embodiment, the present invention provides with a device for determining the flexibility durability of a thinned or fluted region in a molded polyethylene part comprised in a cooperating arrangement: a) a plate comprising an edge of path, two parallel sides, and a body having a rounded leading edge with said body containing one or more mechanisms for attaching said part to the body, which enables the polyethylene part to be attached to the body so that the region The thinned or fluted polyethylene portion is aligned with the rounded front edge, a grounded top bar, typically, next to a frame having two parallel legs, between the swivel plates adjacent the rounded front edge for retaining the thinned region of the thinned portion in close contact with the rounded edge; b) two rotating discs in parallel cooperation arrangement fixed to each side of the plate near the rounded edge, connected to each other through a central bar below and close to said rounded edge next to the central holes in their foci around which the discs rotate; c) two parallel contact bars fixed to each other through holes spaced within a perimeter of 2 to 10 mm of each of the discs of said contact bars being rotatable above and below said rounded edge in order to engage the inside of a shape that enables the curvature of the tapered or fluted region around said rounded edge during rotation; d) a pair of cylinders fixed to the legs along the opposite sides of the plate and still connected through the holes displaced around 1 to 5 cm from the respective central hole to each one of the discs; e) a pair of cam pins projecting, respectively, from the outer trim of each disc, located in a position within the same radius, but offset at an angle to each other; f) a pair of valves in sequence next to each leg; g) a steering valve controlling the flow of fluid with the pneumatic cylinders, causing the reversal of the flow of fluid with the pneumatic cylinders when an actuation switch is connected with a actuation pin; and h) a counter to count the number of bending cycles the part has completed.
    [033] In a further embodiment, the present invention provides with a compressible container featuring a cover of the type described above. Brief Description of Drawings
    [034] Figure 1 consists of a top plan view for the presentation of a closure member by cap of the first preferred embodiment.
    [035] Figure 2 consists of a side elevation view of Figure 1.
    [036] Figure 3 consists of a drawing of the automated tester used in the examples.
    [037] Figure 4 consists of a graph of the average cycle per failure as a function of radiation treatment for the examples. Best Mode of Practice of the Invention
    [038] In addition to the operational examples or wherever any indication to the contrary occurs, all identification numbers or expressions referring to the quantities of ingredients, reaction conditions, etc., are used in the descriptive report and table of claims must be interpreted as modified in all circumstances by the expression “around”. Accordingly, unless otherwise indicated, numerical parameters may vary depending on the properties that the present invention desires to achieve. In the worst case, and not as an attempt to limit the application of the doctrine of equivalents to the scope of the claims, each numerical parameter must be constructed at least in view of the number of significant digits mentioned and through the application of techniques of Ordinary rounding.
    [039] Notwithstanding the numerical ranges that establish the broad scope of the invention are presented as approximations, the numerical values established in the specific examples are communicated as precisely as possible. Any numerical values, however, inherently contain certain errors necessarily resulting from the standard deviation found in their respective test measurements.
    [040] In addition, it should be understood that any numerical range referred to in this report is intended to include all sub-ranges implied by it. For example, a range going from “1 to 10” is intended to include all sub-ranges between and including the minimum mentioned value of 1 and the maximum mentioned value of 10; that is, presenting a minimum value equal to or greater than 1 and a maximum value equal to or less than 10. Because the numerical ranges described are continuous, they include each value present between the minimum and maximum values. Unless expressly stated otherwise, the various numerical ranges specified in this document comprise approximations.
    [041] All ranges of compositions expressed in this report are limited in their total and do not exceed 100 percent (percentage of volume or weight) in practice. Where multiple components are present in a composition, the sum of the maximum amounts of each component may exceed 100 percent, with the understanding that, and for those skilled in the art to readily understand, the amounts of components currently employed come to meet the maximum of 100 percent.
    [042] The joints of the present invention can be used with covers for containers facing dosing products, such as for condiments including: mustards, salad dressings, honey, corn syrups, barbecue sauces, yogurts, and things of gender; soups; shampoos; oils; cleaning products; capsules (drugs); dehydrated spices and the like. In some circumstances, the contents flow under pressure, such as in the form of a liquid, dispersion, paste or gel, and the container appears as a compressible container (eg bottle or tube) of an olefin polymer. If joints are used in conjunction with covers to be used with food, care should only be taken with the use of food contact additives approved (eg by the FDA). Most people have used several of these types of joints.
    [043] In the prior art, the joints comprise of polypropylene, since this has the capacity to withstand not less than 1000 cycles of openings and closings before there is the rupture. However, this most likely consists of an over-engineered hinge as the container contents are typically consumed after around a 200 open and close cycle. Non-crosslinked polyethylene wefts or joints generally cannot meet this requirement.
    [044] The joints of the present invention consist of one or more wefts or strips by crosslinked radiation of thin polyethylene electronic beam joined to a closure member together with a cover. There are two fundamental locations for the joint to be fixed to a closure. The closure member can be attached to the collar containing an optional cover panel also attached to the collar, typically continuously attached, having an opening generally in the form of an annular gargoyle. Typically, the closure member has a cap or gargoyle that cooperates with the gargoyle seal. Alternatively, the hinge may be secured to the cover panel, typically along a diameter or close to a diameter, and the opening in the panel typically consists of a wide opening opening. In this mode, the closing member fits inside the opening. An example of this model consists of the spice container where the lid is rectangular and the articulation works between two parallel sides of the lid.
    [045] In some embodiments, the lid comprises only a rim, a hinge, and a flat panel (for example, a fixed lid), such as that described in WO2010/10915 A2 published on September 10, 2010 (corresponds to to published US patent application 2010/224646).
    [046] In some modalities, the cap presents a model comparable to that described in the U.S. patent application 2004/0118846, granted by Merola to Unilever, which was later abandoned. Figure 1 of the published deposit shows a wide opening lid where the web joins the flat closing member next to the flat panel (paragraph [0040]), preferably adjacent to an edge near the opening or mouth.
    [047] The articulation can also be used on pressure tops. Rather than a pivot and pin arrangement when the top cover articulates beyond a specified point, the swivel passes through a high stress zone where the swivels are under maximum stress (stretching), so the swivel "locks" into the open position with the joint forming an inverted “V” in a lower tension position. Upon closing, the cover passes again through a region of high tension (elongation) and then the hinge is re-attached to a lower tension position, typically flat and seated in the grooves in the rim attached to the cover.
    [048] In the following description, words with a directional sense, such as "upward" and "downward" are employed as descriptive rather than limiting with respect to upright orientation. of the closure and packaging and the words in a directional sense, such as "in axial direction" and "in radial direction" are used as forms of description and not limitation with respect to the central axis of the container or closing edge (rim) according to application.
    [049] A fundamental embodiment of the invention is shown in figures 1 and 2 of U.S. Patent 5,148,912 expired on September 22, 1992 to Nozawa assigned to Yoshino Kogyosho Co., Ltd, of Tokyo, Japan.
    [050] The entire roof is made of polyethylene. The cover or only the hinge portions thereof are exposed to electron beam radiation after formation. Cover 1 has a circular side wall or rim extending downwardly in cooperation with the mouth of the dosing container. Cover 1 features a horizontal panel or wall incorporating a gargoyle 2 in the central region of the cover. The closure member or cap 3 has a cap 4 installed in the recessed portion of the closure member 5 (liner, panel, or top plate) of the cover so that it sealingly engages (closing) with the gargoyle 2. The cap or closure member 3 has a side wall 6 having a depth greater than the elevation of the gargoyle 2. The joints 7 comprise of polyethylene strips having a thickness ranging from 0.1 to 1 mm, preferably from 0.2 to 0.5 mm, which have been subjected to an electron beam reticulated radiation. The hinges 7 are trapezoidal in shape having parallel side walls and inwardly sloping end walls. The end walls are attached to cover 1 and cover 3 in grooves 8 and 9 along pairs of anchor points 10 and 11. The groove is configured so that the bottom edge slopes inward and inward direction. outside. The inner edge of joint 7 is shorter than the outer edge. The result is that there is tension or fatigue at the joint 7 once it is open and there is a pivot point where the tension at the joint, once it is released, is released as the joint locks open along a lower tension position where the outer surface of the joint forms an inverted truncated “V”.
    [051] Typically, the outer edges of the hinges 7 along the pair of anchor points 10 imply an angle from the center of the flat panel ranging from 20° to 75°, preferably from 50 to 75°, most preferably from 60° to 75°.
    [052] A more recent model of a covering where the joints of the present invention are shown to be adequate is presented in the relevant figures in US Patent 6766926, issued on July 27, 2004 to Elchert assigned to Owens-Illinois Closure Inc., whose text is incorporated into this report for reference. The model contains additional elements such as a lid close to the frame, a sealing edge projecting upwards from the cover panel and several additional clamping mechanisms, for example, internal ridges present in the cover or some other part.
    [053] In other embodiments of the invention, a thin flexible polyethylene wall may be present between the joints, as described, for example, by means of US Patent 4638916 issued on January 27, 1987 to Beck et al., assigned to Owens-Illinois, Inc., the text of which is incorporated herein by reference. This provides with a simpler construction. Additionally, when such a wall consists of a reticulated radiation, its robustness is also improved.
    [054] The polyethylene usable in the present invention can consist of any polyethylene or polyethylene blend suitable for compression or injection molding.
    [055] Polyethylene can be selected from the group consisting of high pressure polyethylene, Ziegler Natter catalyst polyethylene, chromium catalyst polyethylene, single site catalyst polyethylene and mixtures thereof.
    [056] One or more of the polyethylenes consist of 100% by weight to 80% by weight of ethylene and contain from 0 to 20% by weight of C4-8 alpha olefin monomers with said polyethylenes having a density ranging from a density of from 0.920 g/cm3 to 0.970 g/cm3, typically not less than 0.94 g/cm3. In some embodiments, the polyethylene or polyethylene blend will consist of from about 90 to 99% by weight, preferably from 95 to 98.5% by weight of ethylene and from 10 to 1, preferably from 5 to 1.5% by weight of one or more C4-8 alpha olefins. Suitable alpha olefins include 1-butene, 1-hexene and 1-octene.
    [057] Depending on the method used for forming the cap, uncrosslinked polyethylene can have a melt index (MI) (ASTM D 1238 - 2.16 kg and 190°C) from around 0.5 to 80 g/10 min.
    [058] Polyethylene or non-crosslinked polyethylene blend may have a melt index (MI) (ASTM D 1238 - 2.16 kg and 190°C) ranging from 5 to 80, typically ranging from 5 to 55 g/ 10 min. These resins are suitable for joint and cover injection molding.
    [059] In injection molding, polyethylene or polyethylene blend is fed, typically along an extruder. Polyethylene enters a feed chamber where it is mixed by augers or screws and heated to its melting temperature. Then, it is fed together with a screw that pumps the molten polymer up to the barrel of the extruder and towards the sprue (ditches or channels) inside the molds destined for that part. The molds cool and the parts are released from the mold. Melt index is important for injection molding as low melt index materials are more difficult to pump and/or inject into the mold and this requires more energy (pressure) and time to fill the molds . In some circumstances, it is desirable to have faster cooling of the mold in the joint region to preserve the polyethylene in an amorphous state.
    [060] Polyethylene or non-crosslinked polyethylene blend may have a melt index (MI) (ASTM D 1238 - 2.16 kg and 190°C) ranging from 0.25 to 50, typically ranging from 0.5 to 30 g/10 min. These resins are suitable for joint and cap compression molding. In compression molding, a dry resin charge is fed into the mold in a partially closed state. The mold is heated to the resin sintering temperature of around 120°C. Then, the mold is pressed to be shut off under high pressure and the polyethylene sinters together to form the part. The mold is cooled, opened and the parts ejected.
    [061] Since some of the closures of the present invention are used in combination with feeders, the polymer or polymer mixture must have a low hexene extraction of less than 0.7% by weight, preferably less than 0. 6% by weight, more preferably less than 0.55% by weight, as determined by ASTM D5227 standard.
    [062] Polyethylene can be made if using one or more conventional platforms, such as gas phase, solution and slurry polymerization. The catalyst may comprise one or more conventional catalysts including single site catalysts, Ziegler-Natta catalysts and chromium based catalysts (for example, chromium oxide or silylchromate catalysts). Single site catalysts are well known in the art and include metallocenes, catalysts with constrained geometries and catalysts with hetero massive linkers, for example, catalysts containing a phosphinino linker. Polyethylene or its mixture can be formed in one reactor or in one or more reactors in series or in parallel.
    [063] The comonomer content in the polymer or polymer mixture can be determined by 13C NMR, or individually via Fourier Transform Infrared Spectroscopy (FTIR), or this in combination with gel permeation chromatography methods (GPC-FTIR). The comonomer content of a polyethylene blend in reactors can be determined through mathematical deconvolution methods applied to a bimodal polyethylene composition.
    [064] The short chain branching in polyethylene consists of the branching in function of the presence of alpha-olefin comonomer in the ethylene copolymer and will, for example, present two carbon atoms for a 1-butene comonomer, four atoms carbon for a 1-hexene comonomer, or six carbon atoms for a 1-octene comonomer, etc. The number of short chain branches in a polyethylene copolymer can be gauged using 13C NMR, or FTIR or GPC-FTIR methods. Alternatively, the number of short chain branches in the second ethylene copolymer of a reactor mixture can be determined by mathematical deconvolution methods applied to one or more methods such as 13C NMR or FTIR or GPC-FTIR for a bimodal polyethylene composition. .
    [065] Polyethylene or its mixture can have an almost wide distribution of molecular weight (Mw/Mn) from around 4 to 15, preferably less than around 10.
    [066] The polyethylene or its mixture can be bi- or tri-modal as determined by gel permeation chromatography (GPC).
    [067] In a further modality, the polymer may comprise a mixture containing: (1) 30 to 60% by weight of a first ethylene copolymer having a melt index, I2, less than 4.0 g/10 min; a molecular weight distribution, Mw/Mn, of less than 3; and a density ranging from 0.925 to 0.950 g/cm3; and (2) 70 to 40% by weight of a second ethylene copolymer having a melt index, I2, ranging from 10 to 100 g/10min; a molecular weight distribution, Mw/Mn, from 3 to 8; and a density higher than the density of said first ethylene copolymer, but less than 0.966 g/cm3 . Preferably, the density of said second ethylene copolymer is less than 0.966 g/cm3 . Preferably, the density of said second ethylene copolymer is less than 0.037 g/cm3 of the highest density of said first ethylene copolymer; the ratio (SCB1/SCB2) of the number of short chain branches per thousand carbon atoms in said first ethylene copolymer (SCB1) to the number of short chain branches per thousand carbon atoms in said second ethylene copolymer (SCB2) is greater than 0.5.
    [068] In an additional modality, the mixture has a molecular weight distribution, Mw/Mn, ranging from 4.0 to 10.0; a density ranging from 0.910 to 0.970 g/cm3, preferably ranging from 0.940 to 0.957 g/cm3; a melt index, I2, ranging from 0.4 to 5.0 g/10 min; a comonomer content of less than 0.75% by moles, as determined by the 13C NMR method; a Mz of less than 400000. Preferably, the polymer or polymer mixture, before being irradiated, has a Condition B ESCR (10% IGEPAL) of less than 8 hours, preferably 10 hours, more preferably 15 hours and before crosslinking the Condition B ESCR (10% IGEPAL) should not be less than around 20 hours, preferably longer than around 35 hours.
    [069] The coverings of the present invention can be prepared through compression molding or injection molding, preferably injection molding. The polymer charge is fed to an extruder, where it is melted and calibrated within a group of molds, then cooled and adjusted to the required part. Such techniques are well known to those skilled in the art. For compression molding, polymer is gauged and fed to compression molds where the polymer is compressed and heated to melt into a solid part.
    [070] The joint in the resulting cover is then subjected to radiation to cause the joint to present reticulated. In practice, it is often simpler to subject the entire coating to radiation in order to crosslink the entire coating. Devices which must subject plastic parts to radiation are well known in the state of the art. The crosslinking can be carried out at the site where the coverings are being manufactured or the coverings can be processed via third parties in relation to the crosslinking. Typically, the radiation will comprise high-energy electron beam radiation, but other types of sources such as x-ray, and possibly radio isotype radiation, are feasible.
    [071] Typically, the coverage will be subjected to a radiation dose from around 20 to 40 Kgy(K Gray) (2-14 Mrads), preferably from 30 to 100 Kgy (3-10 Mrads).
    [072] After radiation, the joint must be able to withstand at least 280, preferably more than 400, more preferably more than 800, desirably at least 1000 cycles of opening and closing before it fails. This type of testing has been done manually in the past. Owners of the invention have developed a machine to test covers or joint simulations (eg, a bar having a thickness ranging from 5 to 7 thousand inches (0.125 mm to 0.175 mm).
    [073] It is important to note that radiation causes crosslinking of polyethylene, which ultimately can lead to polymer brittleness. Consequently, care is needed to avoid excessive crosslinking indicated by gel formation. Typically, gel levels in irradiated polyethylene should not exceed around 35%, preferably less than around 15%. At higher levels of gel, the joint becomes brittle and breaks more prematurely.
    [074] The present invention will be illustrated through the following example:
    [075] A series of test bars having a thickness ranging from 5 to 7 mm were injection molded from a number of polyethylene resins.
    [076] A number of test bars were subjected to 0, 6, 10, 14 and 18 MR of electron beam radiation.
    [077] Then, irradiated and non-irradiated test bars were tested for bending cycles before a radius of 90° ± 20° in the automated joint tester of Figure 3.
    [078] Figure 3 consists of a drawing of a device (100) for determining the flexibility durability of a cover or a thinned or fluted region in a molded polyethylene part comprised in a cooperative arrangement with: a) a plate (101) comprising of a trailing edge (102, not shown), two parallel sides (103), a body (104) containing a rounded leading edge (105), said body containing one or more mechanisms for the attachment of said part to the body (106), typically incorporating a series of holes or threaded claws with even spacing that enable the polyethylene part to be attached to the body (104) so that the tapered or fluted region of the polyethylene part becomes present in line with the rounded leading edge (105), a top bar (107) grounded between the rotational disk adjacent the rounded leading edge (105) to retain the thinned region of the thinned portion in contact close with rounded edge 105; b) two rotational discs (108 and 109) in parallel cooperating arrangement fixed on each side of the plate close to the rounded edge connected to each other, through a central bar (not shown) below and close to said rounded edge (105 ) next to the central holes (not shown) in their foci around which the discs rotate; c) two parallel contact bars (110 and 110) attached to each end through holes spaced 2 to 10 mm from the perimeter of each disc (108 and 109) with said contact bars being rotatable above and below said rounded edge (105) so as to engage the test object in a manner that enables curvature of the tapered or fluted region around said rounded edge (105) during rotation; d) a pair of pneumatic cylinders (112 and 113 (not shown)), although other types of cylinders (liquid driven) of transmission mechanisms, such as an electric motor, can be used attached to the legs (114 and 115 ( not shown)) along the opposite sides of the plate (101) and also connected through holes displaced by 1 to 5 cm from the respective center hole next to each disc (108 and 109); e) a pair of cam pins (116 and 117 (not shown)) that project, respectively, from the outer trim of each disc (108 and 109), located in a position that is within the same radius, but offset at an angle to each other; f) a pair of sequence valves (118 and 119 (not shown)), respectively, adjacent to each of the legs 114 and 115; g) a steering valve (120) controlling the flow of air to the pneumatic cylinders, which reverses the flow of air to the pneumatic cylinders when a sequence valve (one of 118 or 119) is connected with a pin cam (one between 116 and 117); and h) a counter (121 (not shown)) for counting the number of bending cycles the part has completed, typically cooperating with one of the cam pins (116 or 117).
    [079] When in operation, the angular displacement between the two cam pins controls the degree of rotation of the articulation discs. The sample is installed close to the plate so that the tapered section is at or near the rounded edge. The portion of the sample that extends beyond the rounded edge fits between the parallel contact bars. Air is provided to the pneumatic cylinders and the rotational discs rotate until a cam pin hits a sequence valve that reverses the air flow with the pneumatic cylinders causing the discs to rotate in the opposite direction until the cam pin closes together. the other disc hits the sequence valve on the other leg causing air to flow into the cylinders to be reversed causing the disc to rotate in the opposite direction. This cycle repeats until the part breaks. A counter keeps track of the number of cycles until the part breaks. A technician monitors the samples and shuts down the machine when a part breaks, and records the number of cycles.
    [080] A series of 10 samples of the same polymer for each level of irradiation comes to be tested at the same time and the number of cycles for each bar to break is recorded together with the range of cycles for all samples to break.
    [081] Irradiation control 0 consists of the control for each sample.
    [082] The data is fitted in Table 1 below together with the density, and the MI of the resin or mixture tested.


    [083] A graph of average cycle failure acting as a function of radiation treatment is set out in Figure 4.
    [084] Additionally, samples were analyzed for gel levels.
    [085] For SCLAIR® 2714 an average life cycle of around 10000 came to result from a product presenting around 25% in gel and with 35% in gel the product seems to have become brittle. For the SCLAIR® IG454-A, an average life cycle of around 10,000 was observed at a gel level of 15% and an average life cycle of 30,000 was observed for a gel level of around 35%. At 50%, the product gel seemed to become brittle.
    [086] Since the test took place near a simple thinned area, the data indicate a relative improvement in the bar. The data is indicative of a cover, however the bar does not present the internal tension of a pressure cap so the data value may be higher than in the case for a pressure top cap. Some of the irradiated bar samples were able to withstand a life cycle greater than 8000 open and close cycles. Industrial Applicability
    [087] Toppings prepared in accordance with the present invention can be used in a number of applications where "pressure top" lids are generally employed in condiment containers, such as for oils, salad dressings, ketchup, mustard and condiment containers.
    权利要求:
    Claims (22)
    [0001]
    1. Cover, CHARACTERIZED by the fact that it comprises a frame, a panel having an opening therethrough and a cover in cooperation fixed to the frame by a joint comprising one or more webs of injection-molded or compression-molded polyethylene, in which the polyethylene is chosen from high pressure polyethylene, Ziegler Natter catalyst polyethylene, chromium catalyst polyethylene, single site catalyst polyethylene and mixture thereof, each of said one or more webs having a thickness of 0.1 to 1 mm and having been irradiated crosslinked and having a gel level not exceeding 35% by weight, wherein the number of opening and closing cycles to rupture at a radial curvature of 90° ± 20° at a joint temperature of 25°C is increased by not less than 30% in relation to the number of opening and closing cycles for rupture at a radial curvature of 90° ± 20° at a temperature of 25°C of a joint of the same polyethylene and of the month model that has not been crosslinked by irradiation.
    [0002]
    2. Cover, according to claim 1, CHARACTERIZED by the fact that the joint has an increase in the number of opening and closing cycles for rupture at a radial curvature of 90° ± 20° at a temperature of not less than 25°C at 100%, in relation to the number of opening and closing cycles to rupture at a radial bend of 90° ± 20° at a temperature of 25°C of a joint of the same polyethylene and of the model that has not been crosslinked by irradiation.
    [0003]
    3. Covering, according to claim 2, CHARACTERIZED by the fact that the joint has a number of opening and closing cycles for rupture in a radial curvature of 90° ± 20° at a temperature of 25°C not less than 250 cycles.
    [0004]
    4. Coverage, according to claim 3, CHARACTERIZED by the fact that one or more of said frames has been irradiated from 20 to 140 kGy(6-14 Mrads (MR)) of electronic beam radiation.
    [0005]
    5. Coverage, according to claim 3, CHARACTERIZED by the fact that the articulation comprises a simple weft.
    [0006]
    6. Cover, according to claim 5, CHARACTERIZED by the fact that the cover is in the form of a parallelogram.
    [0007]
    7. Coverage, according to claim 5, CHARACTERIZED by the fact that the coverage is circular.
    [0008]
    8. Cover, according to claim 5, CHARACTERIZED by the fact that the cover further comprises a continuous ring extending downwards.
    [0009]
    9. Coverage, according to claim 8, CHARACTERIZED by the fact that the articulation comprises two frames.
    [0010]
    10. Covering, according to claim 9, CHARACTERIZED by the fact that the outer edges of said two wefts imply an angle from the center of the panel of 20° to 75°.
    [0011]
    11. Covering according to claim 10, CHARACTERIZED by the fact that the outer edges of said two wefts imply an angle from the center of the panel of 50° to 75°.
    [0012]
    12. Cover, according to claim 5, CHARACTERIZED by the fact that the opening through the panel comprises a gargoyle extending upwards.
    [0013]
    13. Cover according to claim 12, CHARACTERIZED in that the cover comprises a plug extending downwardly along its lower surface which cooperates with said gargoyle to form a seal in closing.
    [0014]
    14. Cover, according to claim 5, CHARACTERIZED by the fact that, during opening, the cover pivots together with said wefts through a region of greater tension to "instantly secure" the open cover and retains the cover so that the cover is in an open position.
    [0015]
    15. Cover, according to claim 14, CHARACTERIZED by the fact that, during closing, the cover pivots together with said wefts through a region of greater tension to "instantly fasten" the closed cover and retains the cover so that the cover is in a closed position.
    [0016]
    16. Cover according to claim 15, CHARACTERIZED by the fact that additional elements are provided next to the cover rim that engage the cover rim when the cover is in a closed position.
    [0017]
    17. Covering according to claim 1, CHARACTERIZED by the fact that the polyethylene has a density of 0.920 g/cm3 to 0.970 g/cm3 and comprises one or more ethylene polymers comprising from 100% by weight to 80% by weight of ethylene and from 0 to 200% by weight of one or more C4-8 alpha olefin monomers.
    [0018]
    18. Covering, according to claim 17, CHARACTERIZED by the fact that the polyethylene, before being cross-linked by irradiation, has a melt index (MI) (ASTM D 1238 - 2.16 kg and 190°C) of 5 to 80 g/10 min.
    [0019]
    19. Cover, according to claim 18, CHARACTERIZED by the fact that the joint is injection molded.
    [0020]
    20. Covering, according to claim 17, CHARACTERIZED by the fact that the polyethylene, before being cross-linked by irradiation, has a melt index (ASTM D 1238 - 2.16 kg and 190°C) of 0.25 to 50 g/min.
    [0021]
    21. Cover, according to claim 20, CHARACTERIZED by the fact that the joint is molded by compression.
    [0022]
    22. Coverage, according to claim 1, CHARACTERIZED by the fact that it is in cooperation with a compressible container.
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    同族专利:
    公开号 | 公开日
    CA2844886A1|2015-09-06|
    KR20160130291A|2016-11-10|
    JP6444428B2|2018-12-26|
    CN106458386B|2019-05-28|
    CA2844886C|2020-09-01|
    MX2016011019A|2017-02-27|
    US20170107365A1|2017-04-20|
    ES2880747T3|2021-11-25|
    CN106458386A|2017-02-22|
    US10377536B2|2019-08-13|
    EP3113922A1|2017-01-11|
    JP2017513777A|2017-06-01|
    US20190337685A1|2019-11-07|
    EP3113922B1|2021-06-30|
    WO2015132680A1|2015-09-11|
    BR112016020055A2|2017-08-15|
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    法律状态:
    2020-01-07| B06U| Preliminary requirement: requests with searches performed by other patent offices: procedure suspended [chapter 6.21 patent gazette]|
    2021-06-15| B09A| Decision: intention to grant [chapter 9.1 patent gazette]|
    2021-07-06| B16A| Patent or certificate of addition of invention granted [chapter 16.1 patent gazette]|Free format text: PRAZO DE VALIDADE: 20 (VINTE) ANOS CONTADOS A PARTIR DE 29/01/2015, OBSERVADAS AS CONDICOES LEGAIS. |
    优先权:
    申请号 | 申请日 | 专利标题
    CA2844886|2014-03-06|
    CA2844886A|CA2844886C|2014-03-06|2014-03-06|Radiation crosslinked polyethylene hinge|
    PCT/IB2015/050664|WO2015132680A1|2014-03-06|2015-01-29|Radiation crosslinked polyethylene hinge|
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