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    • 专利摘要:
    Summary The invention relates to methods for lowering the melt viscosity and thereby improving the heat sealability of a polyester. The invention also relates to a process for producing a heat-sealed container or packaging of fiber-based, polyester-coated packaging material, and to a process for heat-sealing polyester. The solution according to the invention is to subject polyester to electron beam (EB) straining. The reduced melt viscosity allows a lower heat sealing temperature and allows the sealing of polyester against an uncoated fiber surface. The preferred polyester for the invention is polylactide, as such or blended with another polyester.
    公开号:SE1400034A1
    申请号:SE1400034
    申请日:2014-01-24
    公开日:2015-07-25
    发明作者:Kimmo Nevalainen；Ville Ribu；Jari Räsänen；Outi Kylliäinen；Ari Rosling；Mohammad Bagher Khajeheian；Jurkka Kuusipalo；Sami Kotkamo；Mikko Tuominen
    申请人:Stora Enso Oyj；
    IPC主号:
    专利说明:

    FIELD OF THE INVENTION The invention relates to methods for lowering the heat viscosity of a polyester and thereby improving the heat sealability of a polyester. The invention also relates to a process for the manufacture of a heat-sealed container or package of fiber-based, polyester-coated packaging material. The invention further relates to a process for heat sealing polylactide or other polyester.
    Technical background In packaging technology, heat sealing is a common method of making or sealing containers or packages made of polymer film or polymer-coated packaging material, such as paper, cardboard or cardboard. Layer density polyethylene (LDPE) is a material commonly used in packaging due to its easy heat sealability. In addition, many other polymers are used in packaging, e.g. polyesters, which unlike LDPE are biodegradable, or have better barrier properties for water vapor and / or oxygen than LDPE. However, these other polymers are usually more heat-sealed than LDPE, which is the reason why they are not placed as a surface layer, but rather as an inner layer of a multilayer packaging material.
    Polyethylene terephthalate (PET) is a polyester that is often used in packaging and containers, has good barrier properties and is very heat-resistant, which is the shell even if it is suitable for coating, for example, oven-shaped food containers or packaging, or for baking cardboard. One disadvantage is that PET is the answer to heat sealing. In addition, ordinary PET is not biodegradable.
    Polylactide (PLA) is a biodegradable polymer commonly used in biodegradable packages consisting of polymer film or polymer coated paper or polymer coated paperboard. Polylactide has relatively good 2 barrier properties for water vapor and gas, but has problems with d 'Mg adhesion to a fibrous substrate and a high melting temperature which results in poor heat sealability.
    To further improve the heat sealability of polylactide, US 2002-0065345 A1 discloses a mixture of polylactide with a biodegradable aliphatic polyester prepared from a diol and a dicarboxylic acid, for example polycaprolactone (PLC) or polybutylene succinate adipate (Pb %.
    According to US 2005-0192410 A1, the processability of polylactide is improved by mixing polycaprolactone and mineral particles therein. US 20070259195 A1 further discloses polylactide-based films and polymer coatings which are extruded onto a fibrous substrate and in which polybutylene adipate terephthalate (PBAT) is mixed with polylactide to improve its heat resistance.
    WO 2011/110750 describes a polylactide-based double layer coating, which is extruded on a fibrous substrate and where the outer layer has a larger proportion of biodegradable polyester (other than polylactide) mixed with the same as the inner layer, with a goal of optimizing the adhesion between the polylactide and the fiber sealing substrate. .
    When the heat sealability of polylactide is treated with another polyester or similar additives mixed with it, there is the disadvantage that these additives are more expensive than polylactide. The mixing of polymers is also an extra step in the complicated process.
    Another approach juice is represented by WO 2011/135182, which advocates ultraviolet (UV) coating of a polyester layer to further improve its heat sealability. According to research, the heat sealing temperature dropped, but no explanation is given as to why this is happening. The% retailer even as if the beneficial effect is quite limited to polylactide only.
    WO 98/04461 advocates the use of electron beam (EB) radiation to improve heat seals of polyolefins, such as 16 Density Polyethylene (LDPE), on cardboard substrates. EB is said to induce crosslinking of the polymer and therefore the molecular weight must be the same. The melt index of the polyolefin 3 drops markedly and causes an increase in melt viscosity and melting point. Such an increase in fact reduces the latency of heat sealing by raising the required heat sealing temperature, although the strength of the seal can be improved, which is ground for these prior art clays.
    From the publications CN 101824211 A, CN 101735409 A and CN 101225221 A it is possible to improve the heat resistance of polylactide by exposing it to electron beam (EB) radiation, which provides crosslinking while preserving the biodegradability of the material. Crosslinking is accomplished by the addition of a catalyst such as triallyl isocyanurate (TAIC). The prior art clays refer to molded articles or granules, but not coatings on a fibrous substrate, where adhesion to the substrate and heat sealability are required. Since crosslinking increases the molecular weight and the melt viscosity, the polymer has this advantage all of which has a negative effect on heat sealability.
    Summary of the Invention There is still a need for an alternative reading to improve the heat sealability of polyesters, especially with respect to the heat seal temperature. There is also a need to provide an improved process for making heat sealed containers or packages using heat sealable polyester as a coating on the packaging material.
    The solution according to the invention is in general terms of exposed polyester for electron beam (EB) radiation. In this way a new method is provided for lowering the melt viscosity of the polyester, as well as a new method for improving the heat sealability of a polyester, which [Ada can be characterized by the above-mentioned features.
    There is further provided a new method of making a heat sealed container or package, in which (i) a fibrous substrate is provided with a polymeric coating comprising polyester, (ii) the coating is subjected to EB-straining, and (iii) the container or package is sealed by heat sealing. the coating polymer. In addition, a novel method of sealing polyester is provided, in which (i) EB radiation is directed to a surface comprising polyester, and (ii) the irradiated surface is then heat sealed to a counter surface. According to the invention, it has surprisingly been found that EB radiation (beta rays) directed at a film or coating layer containing polyester, such as polylactide, alone or mixed with other polyesters, significantly improves the heat sealability of the polyester by reducing the melt viscosity and shrinkage viscosity. thereby the required heat sealing temperature. The result is the opposite of what happens with polyolefins, ie. an increase in the melt viscosity as described in WO 98/04461. The result is also an indication that aft EB radiation, in contrast to free * polyolefins, does not crosslink polyesters but rather breaks down their polymer chains and thereby makes narrow polyester less viscous and easier to heat seal. This is important in view of the usually high melting temperatures of polyesters and the similarity with heat sealing which becomes foolish.
    In order to ensure reduced melt viscosity and a lower heat sealing temperature, it is essential to avoid any catalyst or other component of the polyester which could promote crosslinking thereof in the EB treatment.
    Another result of the invention is the adhesion of an extruded single layer of polyester, such as PLA, to a fibrous substrate is improved by directing EB radiation towards the polyester. The poor adhesion of PLA has previously been solved by adding a separate adhesion layer between the PLA layer and the substrate. Through improved adhesion, the weight of the polyester layer on the fibrous substrate can be reduced, resulting in cost savings.
    EB radiation has a penetrating and ionizing effect on the polymer coating layer, while it is absorbed and gradually weakened by the polymer. In contrast to UV radiation, which only works by heating the surface of the polymer layer without penetrating into the layer to a greater depth, it is possible to regulate the effect of EB radiation by extending to the whole by affecting the effective acceleration voltage. the depth of the polymer layer, while avoiding burning or discoloration of the underlying paper or board substrate of fiber-based packaging materials. The acceleration voltage is suitably kept relatively low, at 100 keV or lower.
    The material may be a polymer-based packaging film with one or more layers, or packaging paper, cardboard or cardboard, wherein a polymer coating with one or more layers is applied to the fibrous substrate by lamination or extrusion, its top layer containing polyester being EB-irradiated. An appropriate absorbed dose of EB radiation is at least 20 kGy, preferably in the range of 20 - 200 kGy.
    A suitable polyester for use in the invention is polylactide (PLA). When the PLA release coating polymer contains the fiber-based packaging material, such as paper or board, it can be extruded directly onto the cardboard / board base without the need for an intermediate polymer adhesive layer. PLA can be used as such, or mixed with the other biodegradable polyesters, for example polybutylene succinate (PBS). Alternatively, an inner adhesive layer may be coextruded with an outer heat seal layer of PLA, or a mixture thereof, which allows the outer heat seal layer which comes from EB-irradiated to be tailored solely for optimal heat sealability. The invention allows heat sealing of PLA or other polyester against an uncoated fibrous substrate, which is generally more similar to ordinary polymer-to-polymer sealing.
    Other polyesters useful in the invention include polyethylene terephthalate (PET) and polybutylene adipate terephthalate (P BAT).
    The containers and packages which, according to the invention, can be heat sealed from the fiber-based polymer-coated packaging material prepared and EB-irradiated as described above, include cardboard cups, such as disposable drinking cups, as well as cardboard and cartonboard or cardboard packages, such as confectionery, biscuits, groats, cosmetics and bottle packaging, as well as juice cartons. The drinking cups can be polymer coated on the inside and uncoated on the outside, the vertical joint of the cup in the invention being created by sealing the coating of the inner surface against the uncoated cardboard of the outer surface. In cartons instead, the outer surface of the package may be polymer coated and the inner surface uncoated, the coating of the outer surface being heat sealed against the uncoated cardboard surface of the inside of the package at sealing. In mugs, such as drinking cups, as well as in cardboard packaging, however, the cardboard / carton is often polymer coated on ram sides, whereby, according to the invention, the coating on one or both sides can be EB irradiated and the coating layers sealed to each other by heat sealing. Also in this case, the EB radiation according to the invention improves the heat sealability of polyester.
    In experiments related to the invention, it has been observed that EB radiation improves the sealability of PLA or a mixture containing PLA 5 in heat sealing which is carried out with hot air.
    In addition to the polyester-coated fiber-based packaging materials, the invention also relates in particular to polyester-based packaging films, the heat-sealability of which improves the EB radiation. According to the invention, the surface layer of the film may contain PLA as such, or as a mixture with another polyester, for example PBS and when it comes to the heat sealability of the film, essentially the same as described above with respect to the polymer-coated packaging papers and cartons comprising PLA.
    According to the invention, it is possible to combine ER and UV irradiations by first exposing polyester film or coating for UV-straining in accordance with the clays according to WO 2011/135182 which are incorporated therein by male reference and then for EB-irradiation as described. An opposite sequence of steps, ie. EB irradiation before UV irradiation is also possible.
    Addition of flame treatment as an additional step has also been found to be beneficial. In particular, when PET is used as the polyester, a flame retardant step decreases even after EB irradiation the heat sealing temperature is significantly reduced.
    Infrared (IR) and plasma treatments are also being considered as possible additions that are expected to improve heat sealability.
    Examples In the following, the invention is described in more detail with the aid of application examples and challenging experiments.
    Examples of the preferred implementations of the invention are that on paper or board, made / made of kraft pulp, CTMP or mechanical pulps and whose weight is 40 - 500 g / m2, co-extrude a multilayer coating, which has an adhesive layer furthest in with a weight of 5 - 20 g / m2 consisting of 7 of biodegradable polyester (other than PLA), such as PBAT or PBS, or a mixture of PLA (40 - 95% by weight) and other biodegradable polyester (5 - 60% by weight) , such as PBAT or PBS, and a heat seal layer at the far end with a weight of 5 - 20 g / m2 consisting of PLA or a mixture of PLA (40 - 80% by weight) and other biodegradable polyester (20-60% by weight ), such as PBAT or PBS. A middle layer of PLA with a weight of 5 - 20 g / m 2 can be placed between the layers of polymer mixture along the in and the outside out. The other side of the paper or cardboard can be left uncoated. The polymer-coated web is transported past an EB radiator, with its coated side towards the device, at a speed of 5 -600 m / min, preferably 200-600 m / min. The EB-irradiated web is cut into frames, which are heat-sealed to containers, such as cardboard cups, or packaging, such as packaging bins or cartons. The sealing can be done with hot air, whereby the air temperature can be approximately 360 - 470 ° C.
    For materials that are irradiated more intensively, ie at a slower web speed, the air temperature required for a complete seal is stored for materials that receive less strain. Instead of hot air, sealing jaws can be used, at which the temperature can be approximately 130 - 160 ° C, even in this case low for materials that are irradiated the most.
    Single layer coatings of PLA, mixtures of PLA and PBS, mixtures of PLA and PBAT, and PET are also preferred. Such single-layer coatings can have a weight of 15 - 60 g / m2, preferably 25 - g / m2.
    Instead of a continuous web, the EB radiation can also be directed towards the sealing lines of a web or a frame which is stationary in relation to the radiator, which lines on such a sail have a larger radiation fraction, while the other parts of the polymer surface are not exposed to radiation. . The supporting frames consisting of PET-coated backing board can be given as an example.
    For the experiments of Figures 1 - 4, single layers of polyester coating were extruded on one side of a paperboard base and subjected to various treatments to establish the abrasion effect on the heat sealing temperature. The treatments were ultraviolet irradiation with 21 kW, electron beam irradiation with a dose of 100 kGy, 35 corona treatment with 3400 W, and flame treatment with the use of a
    权利要求:
    Claims (1)
    [1]
    1. 8 oxygen shots (at a track speed of 150 m / min). In the figures, these have been marked with "UV", "EB", "C" and "F" respectively. Combinations of these treatments were also included in the trial. For conventional test tests, the initial temperature of the heat seal was measured as the temperature of the heat seal air at an electrically heated air nozzle before it hit the surface of the coating layer. At the indicated temperatures, the polymer was narrow enough for perfect sealing with the uncoated back of the carton. The requirement is that a Mrs & to Open the seal results in tearing inside the fiber-based cardboard base.
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    引用文献:
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    法律状态:
    优先权:
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