Laminates of ethylene vinyl acetate polymers and polymers of vinylidene chloride
6 claims: 4 independent, 2 dependent
- 1Patentkrav 1. Varmekrympbart, fleksibelt laminat, eventuelt i form av en slange eller pose for anvendelse ved krympeemballering av frosne matvarer og omfattende et første lag av en orientert kopolymer av etylen som eventuelt kan være fornettet, et andre lag som er et oksygenbarrierelag av en kopolymer av vinylidenklorid med minst én annen etylenisk umettet monomer, fortrinnsvis vinylklorid, hvilken kopolymer inneholder minst 50 vekt-% vinylidenkloridavledede enheter, og hvor barrierelaget eventuelt også inneholder en mindre mengde av en ytterligere harpiks såsom en epoksyharpiks og et tredje lag av en termoplastisk poly15 mer, karakterisert ved at det første lag er en kopolymer av etylen og vinylacetat inneholdende 5-20 vekt% vinylacetatavledede enheter og at det tredje lag består av (i) en kopolymer av etylen og vinylacetat som ovenfor angitt eller (ii) en blanding på basis av isotaktisk poly- propylen inneholdende ataktisk polypropylen og polybuten-1.
- 2Laminat ifølge krav 1, karakterisert ved at det tredje lag omfatter en orientert kopolymer av etylen og vinylacetat inneholdende 5-20 vekt-%, fortrinnsvis 8-12 vekt-% vinylacetatavledede enheter.
- 3. Laminat ifølge krav 1 eller 2, karakteri- sert ved at den orienterte etylenpolymeren til sjiktet (1) er orientert, fornettet kopolymer av etylen og vinylacetat, som inneholder 5-20 vekt-%, fortrinnsvis 8-12 vekt-% derivatenheter av vinylacetat.
- 4Laminat ifølge krav 1-3, karakterisert ved at sperresjiktet også inneholder 2-10 vekt-%, fortrinnsvis 4-6 vekt-% av en epoksyharpiks.
- 5Laminat ifølge kravene 1-5, karakterisert ved at minst 5 vekt-% vinylidenkloridpolymer i sperresjiktet er av en væskeovertrekks-kvalitet. 150503 —. _ Ί 19 1 ί
- 6Fremgangsmåte ved fremstilling av et varmekrympbart laminat ifølge krav 1 - 5, hvor et etylenkopolymerlag ekstruderes som et rørformet substrat, som eventuelt er fornettet, og belegges på den ytre overflate ved hjelp av smelteekstrudering, til å gi et oksygenbarrierelag av en kopolymer av vinylidenklorid og minst én annen etylenisk umettet monomer, fortrinnsvis vinylklorid, og hvor kopolymeren inneholder minst 50 vekt-% polymeriserte vinylidenkloridavledede enheter, og hvor et tredje lag av en termoplastisk syntetisk polymer belegges på den ytre overflate av oksygenbarrierelaget, hvoretter det erholdte laminat oppvarmes, fortrinnsvis i et vannbad, og strekkes biaksialt ved boblemetoden for å gjøre det varmekrympbart og for å tilveiebringe orientering av i det minste etylenpolymeren i det første lag, karakterisert vee d at for det første lag ekstruderes en kopolymer av etylen og vinylacetat inneholdende 5-20 vekt-% vinylacetatavledede enheter og for det tredje lag ekstruderes enten (i) en kopolymer av etylen med vinylacetat inneholdende 5-20 vekt-% enheter avledet fra vinylacetat, eller (ii) en blanding på basis av isotaktisk polypropylen inneholdende ataktisk’ polypropylen og polybuten-1. 150503 . Eig-Å
Independent claims6
143 paragraphs in 13 sections, as filed
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[B] (11) EXPRESSION WRITING
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M 150503
> NORWAY (51) Inf Cl? B 29 D 9/08, B 32 B 27/08 [NO]
GOVERNMENT OF THE INDUSTRIAL JUSTICE
<td>(21) Patent application no.</td><td> 1104/72</td>
<td>(22) Filed</td><td> 29.03.72</td>
<td>(24) Race day</td><td> 29.03.72</td>
(41) Widely available from 03.10.72 (44) Application submitted, Explanation of expenditure 23.07.84 (30) Priority requested
30.03.71, USA, No. 129501 (54) Designation of the Invention (71) (73) Applicant / Patent Owner
Heat shrinkable, flexible laminate and process for making it.
WR GRACE & CO.,
Hanover Square, New York, NY 10004, USA.
<td>(72) Inventor</td><td>HARRY 30UNA BRAX, Spartanburg, SC, JOSEPH FREDERICK PORINCHAK, Spartanburg, SC, ALAN STUART WEINBERG, Greenville, SC, USA.</td>
<td>(74) Agent</td><td>A / S Oslo Patent Office Dr.ing. KO Berg, Oslo.</td>
<td>(56) Cited publications</td><td>Norwegian (NO) Patent No. 106611, British (GB) Patent No. 1222398, U.S. Patent No. 3549389, Modern Plastics for March 1958, pp. 125, 126, 128, 130 and 133, Modern Packaging, September 1966, pp. 155-161, Encyclopedia of Polymer Science and Technology vol. 6 (1967), pp. 409-410.</td>
150503 I 'I 1!
! The present invention relates to a laminate of the kind set forth in the preamble of claim 1, and to a method of the kind set forth in the preamble of claim 6.
For many purposes, high-wrapping materials are required. resilience to withstand harsh external stress during transport and handling of packages. When the goods inside the package are not soft or elastic, the hard stress can also come from within the package during transport and handling. Examples of items that are particularly subject to severe stress from within are meat with bone in, ie a piece of meat containing bone. Penetration of the wrapping material can take place on the relatively hard bone, and this will of course have a detrimental effect on the meat. Many other consumer goods require packaging in a high-resistance material.
Polymers of the first layer are copolymers of ethylene and vinyl acetate, which contain 5 to 20% by weight units derived from vinyl acetate. The ethylene / vinyl acetate copolymer ref, referred to herein, contains (consists wholly or only partially) of polymerized ethylene and vinyl acetate units. Thus, other ingredients may be present, and the polymer may be a terpolymer or any polymer other than copolymer as long as the major portion is ethylene and vinyl acetate. To orient such polymers, they are preferably cross-linked. Methods for carrying out such cross-linking are known per se, e.g. by irradiation.
The laminates of the present invention have many and varied applications, e.g. by wrapping etc. and can be made by melt-extruding a backing film, cooling to solidify the film, melt-extruding a barrier layer over it, solidifying the barrier layer, and melt-extruding a film that is resistant to harsh stresses, over the laminate, thereby forming a biaxially stretched laminate.
The second layer is an oxygen barrier layer and consists of a copolymer of vinylidene chloride with at least one other ethylene-containing unsaturated monomer, whereby the copolymer contains at least 50% by weight units of vinylidene chloride. Such copolymers are hereinafter referred to as vinylidene chloride polyires. It is desirable that this be a copolymer of vinylidene chloride with vinyl chloride.
It may contain e.g. 70 - 85 wt% vinylidene chloride units and 30 - 15 wt% vinyl chloride units.
Laminates containing a barrier layer of vinylidene chloride polymer are known from US Pat. 3,549,389, Canadian Patent No. 743,021, U.S. Patent No. 3,031,332; 2,968,576 and 2,955,869. In the case of such laminates, it has usually been necessary to use breakthrough protective agents, such as disclosed in U.S. Patent No. 2,891,870. In addition, it is noted that prior art laminates require additional layers to obtain the necessary resistance to a lamina, the necessary adhesion properties of further other lamina, or various special treatments to obtain suitable adhesion properties between the layers. Moreover, ethylene copolymers down mainly vinyl acetate content have not been considered to be satisfactory for an outer or inner lamina or coating which must be resistant to harsh stresses. Generally, only such ethylene-vinyl acetate copolymers with vinyl acetate content below 5% have been considered suitable for such use. The above drawbacks are some of the drawbacks attached to known laminates.
Accordingly, there is a need for a simple, laminate structure, and provides all the necessary properties required for wrapping, especially for wrapping cuts of meat with bone in, and then without the use of special wrapping aids. Laminates according to the present invention satisfy this need. The laminate is characterized by that of the characterizing part of claim 1 and manufactured according to the characterizing part of claim 6.
The vinylidene polymer for the barrier layer in the laminates of the invention is preferably a mixture of 5 - 40% by weight polymer suspension and 60 - 95% by weight polymer emulsion, preferably with an epoxy resin admixed in an amount ratio of 2 - 10% by weight. based on polymer
-i;
in
The preferred polymeric material for the first layer of the laminate is a copolymer of ethylene with vinyl acetate, which consists of 5-20% by weight, preferably 8-12% by weight, vinyl acetate units.
Embodiments of the invention will now be described with reference to the accompanying drawings, in which:
FIG. 1 is a schematic representation of apparatus suitable for the manufacture of a laminate according to the invention:
FIG. 2 is a cross-sectional view of a nozzle head forming part of this apparatus; FIG. 3 is a sectional view taken along line 3-3 of FIG. 2;
FIG. 4 is a cross-sectional view of a laminate of the present invention;
Percentages are given in% by weight unless otherwise stated.
Referring to FIG. 1 extruded tube 10 downward from the nozzle head 11 fed from extruder 9. The extruded tube is
250 - 750 µm thick, preferably 375 - 625 µm. After cooling or abrupt cooling by water spray from cabling 12, the helm is squeezed by means of clamping rollers 13, and fed through an irradiation vault 14 surrounded by protective shield 15, where it is irradiated with electrons from an iron core transformer accelerator 16. Other accelerators, such as Van der Graff or resonant transformer may be used. The radiation is not limited to electrons from an accelerator, and any ionizing radiation can be used. The irradiation unit used in the present application is RAD, which is defined as the amount of irradiation whereby 100 erg energy (measured as absorbed energy) is consumed per day. grams
irradiated material. MRI is a million (10) RAD.
In special cases, it may be desirable to crosslink the polymer by other means, such as by chemical crosslinking agents. However, in the preferred method, irradiation is used, and preferably as described above. The irradiation time of ethylene / vinyl acetate copolymer rudder 10 is not critical, but only needs to be sufficient to provide the desired degree of crosslinking. According to this embodiment, 10 is preferably irradiated at a dose of 2-15 MR or more, preferably a dose of 2-10 MR.
Pipe 10 is passed through irradiation vault 14 by means of the drums 17. After irradiation, rudder 10 passes through clamping drums 18, 1θ followed by a gentle inflation by means of a gas bubbling through water trap 20. The pipe is not noticeably extended longitudinally to the inflation, as the drums 18 operated with approx. the same speed as the previous rollers 13. The rudder is inflated only sufficiently to provide a substantially round rudder without appreciable transverse orientation.
The gently inflated and irradiated rudder 10 passes through vacuum caromer 21 to a laminating or coating nozzle 22, which is placed under chamber 21. A second tubular film 20 23 is melt extruded from coating nozzle 22 to provide a coating and a coating. direct attachment to the irradiated tube 10, thereby forming a two-layer tubular laminate 24. The second tubular film 23 is the latch film.
It consists of a vinylidene polymer having at least 50% by weight <3 E <sup>ζυ</sup> units of vinylidene monomer, and most preferably a composition consisting of copolymers of vinylidene chloride and vinyl chloride having 5 to 40% units of vinyl chloride, preferably 15 to 30%. This composition is preferably 5 - 40% suspension polymer and 60 - 95% emulsion polymer, preferably 5 - 15% suspension polymer and 85 - 95% emulsion polymer. The preferred barrier layer also consists of 2 - 10% by weight, preferably 4-6% by weight. of a layer of epoxy resin. Accordingly, the preferred barrier layer is based on a copolymer of vinylidene chloride with vinyl chloride having 5 to 40% vinyl chloride units mixed with
QE
- 10% epoxy resin, the copolymer itself being a mixture of from 5 to 40% suspension polymer and 60 to 95% emulsion polymer. The most preferred barrier layer consists of (a) a vinylidene chloride / vinyl chloride copolymer having 15-30% vinyl chloride units, and (b) 4-6% epoxy resin, the copolymer being a mixture of 5-15% suspension polymer and 85 95%. emulsion polymer.
The epoxy resin means a high viscosity epoxy-containing curable resin and should not be confused with epoxidized oils which are common epoxy plasticizers and which are usually made of much less viscous epoxidized natural oil.
It has been found that when the suspension polymer content in the polymer mixture exceeds 20%, the orientation of the film becomes difficult. Only with very careful handling is it possible to use a mixture containing up to 40% suspension polymer. The reason for the difficulty of orientation is due to the fact that crystals are formed more quickly in a suspension polymer film. Accordingly, the suspension polymer acts as a contaminant in the emulsion polymer in the sense that the suspension polymer crystallizes too quickly with respect to sufficient extraction (reduction of film thickness) during the orientation step.
We have found it possible to dress with extrusion temperatures between normal process conditions for emulsion and suspension polymerized polymers, i.e. usually from 138 to 171 ° C for the most preferred compositions. It was not expected that the mixed materials would be suitable in the molten polymer state due to the different melting rates of the two polymers.
Accordingly, extruder 25 is preferably operated at a drum temperature at 43 DEG-16 DEG C., preferably at 121 DEG-149 DEG C., and the extrusion nozzle is preferably operated at a temperature of 138 DEG-171 DEG C., preferably 146 DEG-157 DEG C. The extruded rudder is 25 - 125 µm thick, preferably 50 - 100 µm.
Extruder 25 is conventional, e.g. a standard 8.2 cm extruder.
The details of the nozzle 22 will be better illustrated with reference to FIG. 2 and 3. The nozzle 22 is a circular crosshead 150503 nozzle with a spacer 26 attached thereto which provides in a preferred shape an 8.9 cm aperture 27 for the gentle inflation of rudder 10. Aperture 27 through which the inflated substrate passes has been formed by means of mandrels attached to the nozzle housing 29. The flow path of the molten coating material 23 is indicated by arrows in FIG. 2 and 3. Vacuum chamber 21 causes a smaller vacuum, e.g.
in the region of 0 to 6.4 cm of water column, in the nozzle 22, thereby obtaining an attraction or suction force on the extruded film
23, while still molten, and against the inflated rudder 10 so as to avoid formation of enclosed blisters in laminate
24. Vacuum chamber 22 may simply consist of a cylindrical housing whose inner diameter fully adapts to the outer diameter of the inflated tube. A vacuum can be provided by outlet opening 30 and by conventional vacuum producing devices (not shown).
An alternative preferred material for the barrier layer is a coating material of the type used to deposit a vinylidene polymer coating from a solution or emulsion. In the past, it has normally been applied as a solution in a solvent, at room temperature, and the bed has thereby been dried. The liquid coating polymer can replace the suspension polymerized polymer previously described and which is preferred as a barrier composition. It is believed that this liquid-coating vinylidene polymeric material acts in the exact opposite manner as compared to the suspension polymer, and has a lower melt viscosity and hence the flow properties of the barrier layer composition will be analog rubber. Liquid-coating vinylidene polymers are not intended to be melt-extrudable. In other cases, it has been found possible to replace all the vinylidene polymer in the composition with the liquid-coating vinylidene polymer, as well as mold the barrier layer with melt extrusion. It is surprising that it is possible to shape a good film in this way. Liquid coating vinylidene polymers are also usually emulsion polymerized. Preferably, this vinylidene polymer contains from 5 to 15% by weight of vinyl chloride units.
. 'i
The two-layer film 24 passes the coating or lamination nozzle 32, preferably while still warm. In a discontinuous process, it will be possible to dress or rip off the rudder 24 before it passes the secondary coating nozzle 32, but this will usually also necessitate a re-inflation, as well as a reheat of the rudder to obtain the best possible bond between the second layer. and the first layer. By looking at the rudder from the outside, the first layer will be both an outer layer and the outer layer of the rudder.
A third layer is melt extruded from coating nozzle 32, and is coated on and directly attached to the two-layer and tubular laminate 24, thereby forming a three-layer tubular laminate 34, The tubular laminate 33 is preferably of a composition selected from the compositions which . is cited in connection with the above description of the tubular film 10. Although it does not need to have the same composition as the tubular film 10, it is easiest to be of the same composition. The coating process at nozzle 32 is the same as at nozzle 22. The vacuum chamber 36 serves the same function as vacuum chamber 21 and is operated in the same manner, whereby the vacuum is produced through outlet conduit 37. The tubular film or layer 33 is 75 to 375 microns thick, preferably 100 - 300 microns.
The three-layer tubular laminate 34 is cooled or abruptly cooled using water spray from cabling 39. The water is normally approx. 7 ° C. The clamping rollers 40 press the pond into the three-layer tubular film and the film is wound up on winding drum 41. In a continuous process, alternatively, the film will not be wound up on winding drum 41, but will be delivered directly to the next step of the subsequent process (stretching).
As shown in FIG. 1, a dispensing drum 42, formerly a winding drum 41, is developed via guide drum 43. Laminate 34 is substantially unstretched and non-oriented as it passes over guide drum 43. The film passes from guide drum 43 to a hot bath 44 containing water 45.
The preferred reheat temperature or hot water temperature is 70-100 ° C, and preferably 82-96 ° C. The compressed three-layer, tubular film is immersed in warm water for at least approx. 5 seconds. This time is usually required to bring the film's temperature up to that required for orientation stretching. A typical retention time in the water bath is approx. 20 seconds. The guide drums 46 and 47 guide the compressed rudder through water bath 45.
After reaching an appropriate orientation temperature, bubble 54 is blown into the film which is outside the water, and the film is stretched in both transverse and longitudinal directions in a preferred proportion of 1: 1.5 - 1: 6, preferably. 1: 2 - 1: 4, respectively, which corresponds to a biaxial orientation of respectively. 1: 2.25 - 1: 3.60 and 1: 4 - 1:16. The thickness of the layers is reduced substantially in the same ratio. The bubble 54 is maintained between the press rollers 48 and 49. The rudder breaks at the drums 50 and the laminate, which passes through the press rollers 49, passes the guide drum 51 and under the guide roller 53, and is wound on the drum 52.
In FIG. 4 is a cross-sectional view of the oriented laminate '34.
The first applied layer, which is the inner layer of the rudder, is layer 10 having a preferred thickness of 12 - 125 µm, preferably 25 - 50 microns. The barrier layer is indicated at 23, and has a preferred thickness of 1.25 - 50 µm, preferably 2.5 - 6 microns. The third layer 33, which is the outer protective layer of the rudder, is preferably 2.5 - 100 µm, and preferably 6-25 µm thick. The laminate jmj; θη shrinkage voltage of usually 14 - 35 kp / cm, preferably 14 - 28 kp / cm<sup>2</sup>and a free shrinkage of at least 40%, preferably at least 50% at 96 ° C, and a free shrinkage of at least 20%, preferably at least 30%, at 85 ° C.
According to another preferred method of preparing the laminate, the second and third layers can be co-extruded on the preformed tube from a co-extrusion nozzle. This will give the same laminate as the final product with a somewhat more difficult method.
» <sup>9 ;</sup> in
The rudder-shaped film made from the rudder of the invention provides an excellent protective bag whereby the bed 10 self-binds at temperatures between 93 and 177 ° C without deformation which is obtained mainly by heat sealing by a thermal impulse seal.
The layer 10 also provides excellent strength against piercing the bag. The thin barrier layer provides the necessary barrier properties with minimal thickness and cost. The outer layer of unirradiated copolymer provides high resistance at low temperatures and improved tear strength.
An advantageous method of using bags made of rudder according to the present invention is described in Applicant's US Patent No. 3,552,090. After the bags are evacuated, it is convenient to seal them by compression as shown in applicant's U.S. Patent No. 3,383,746. A suitable evacuation device is disclosed in Applicant's U.S. Patent Application No. 844,884, filed July 25, 1969.
While it is obvious that the above laminate can be used for many purposes, the laminate was specially made as packing material for packages containing cut fresh red meat with bone in. For this application, a three-layer laminate made from the above-described preferred materials should be used. A laminate with a different and inferior barrier layer can be used, but this will be at the expense of the process's ability to produce high quality laminate. The laminate is non-toxic and usually suitable for food packaging. It is clear that when a bag is used for wrapping a piece of fresh red meat, which is not frozen and which should not be frozen, but should be packed and stored at lower temperatures, e.g.
Θ - 7 ° C, the laminate will enclose the cut meat with bones in and the bones will with some force work against the inner layer of the bag.
In addition to losing resistance to stress at heat shrinkage temperatures, heat sealing will result in delamination when the vinyl acetate content substantially exceeds 18% in this particular laminate. If the vinyl acetate5 content is less than 5%, then the elasticity will decrease at low temperature, and the modulus of elasticity increases to such an extent that the bag no longer meets the requirements for an efficient packaging operation.
The preferred three-layer laminate has many high desirable properties, the typical being good shrinkage at a moderately high temperature, an elongation of at least 50%, preferably 100 125%, an oxygen permeability ratio of not more than 7 cm / (1 m / 24 h). / 1 atm) at 22.8 ° C and 0% relative humidity (ASTM
D 1434); and usually not more than 25 cm / (1 m / 24 h / l).
15 o at 22.8 c and 0% relative humidity (ASTM D 1434).
In a preferred form, the film has a ball burst impact resistance of at least 25 cm-kg, painted with a Ball Burst Tester No. 13-8 using a 2Q standard hemispherical head.
In some cases, it is desirable to use a different polymer in the outer layer of the laminate. This is the layer that should be resistant to pushing and tearing. These other polyes should also have relatively narrow molecular weight distribution, and then<sup>25</sup> preferably with an arbitrary molecular weight distribution, preferably with a distribution according to the standard clock curve. Examples of such polymers are polypropylene, polyamides, polyesters, etc., as well as copolymers, terpolymers and other polymers of such materials. Such groups of coating polymers are well known.
Of course, in some cases, the outer (third) layer or even the first (inner) layer must not exhibit the advantages of the present invention, but the second lamina is necessary and thus the present invention preferably comprises packaging material and modifications thereof which contain no. only a portion of the present material in the preferred packaging material.
<sup>11</sup> The film according to the invention and various layers of the laminates according to the invention may comprise useful additives such as stabilizers, pigments, auxiliaries such as wax, deodorants, antistatic agents and anti-blocking agents.
This invention will be further illustrated by the following examples.
EXAMPLE I
Using the method shown schematically in FIG. 1 was an ethylene vinyl acetate copolymer containing 10% vinyl acetate with a melt index of approx. 2<sub>z</sub> sold as
UE 637 of the US Industrial Chemicals Division of National Distillers, fed to the filler funnel of extruder 9. The extruder is an 8.9 cm extruder and is run at the following temperatures: rear zone 121 ° C, center cylinder 132 ° C, front of cylinder 143 ° C, spacer 149 ° C and nozzle 166 ° C. The screw speed is 37 rpm. and the pressure is 267 kg / cm. The nozzle diameter is 8.9 cm and the circumference of the produced tube is 20.3 cm. The water temperature from dressing 12 is 7 ° c. The clamping rollers 13 are run at a speed of 10.7 meters per second. and the thickness of the collapsed rudder is approx. 460 microns.
The collapsed rudder passes through an irradiation unit, which is depicted in FIG. 1, and run at '500 kilo-electron volts,
MA and a speed of 35 feet (10.7 meters) per minute. Four passes are made and the rudder receives a dosage amount of approx.
6 megarad (megarads).
The irradiated substrate film then emerges into a coating nozzle 22, where it is coated with a barrier material. The barrier material contains a gentle, plasticized mixture of copolymers of vinylidene chloride with vinyl chloride. The copolymer mixture consists of 10% suspension polymerized and 90% emulsion polymerized copolymer. The emulsion polymerized copolymer consists of ca. 70% units obtained from vinylidene chloride and 30% units obtained from vinyl chloride, and the suspension polymerized copolymer consists of approx. 80% units obtained from vinylidene chloride and 20% units obtained from vinyl chloride. These materials were purchased from Dow Chemical Company and sold as UP 925 (emulsion polymerized resin) and SP 489 (suspension polymerized resin). Other ingredients in the barrier 35 layer are 5% of an epichlorohydrin / bisphenol A epoxy resin sold as EPON resin 828 by Shell Chemical Company, and approx. 0.5% of a microcrystalline paraffin wax was purchased from
Sun Chemical Company and sold as wax 5512. The three resins were mixed in a Prodex-Henschel mixer of high speed and high intensity type, and the mixture is fed to the filling funnel of extruder 25, the extruder being a 5 cm Prodex extruder. which is run with a crosshead nozzle of the type shown in FIG. 2 and 3. This extruder is run at the following temperatures: rear zone 99 ° C, center cylinder 127 ° C, front of cylinder 149 ° C,. the spacer 141 ° C and the nozzle 16 ° C. The screw speed is 34 rpm. my. and the pressure is 390 kp / cm. The nozzle diameter is 8.9 cm and the circumference of the rudder is 20.3 cm. The top drums 18 are run at a speed of fluff, 7 meters per hour. and the coating thickness is approx. 75 hm.
A third layer was then prepared using the same resin as the first layer. The resin is extruded through extruder 35, which runs in the same manner as extruder 9, except for the following temperatures: rear zone 121 ° C, center of section 132 C, front of cylinder 193 C, intermediate section 227 ° C and nozzle 232 ° C. Coating nozzle 32 is of the same type as coating nozzle 22. Bottom drums 40 are run at a speed of 11.0 meters per second. per minute, and the water from boiler 39 has a temperature of 7 ° C. The thickness of the coating is approx. 150 microns.
The biaxial orientation is done by preheating the rudder in water at approx. 88 ° C, as indicated by 44 in FIG. 1, after which the thus heated tube passes through the clamping rollers, which are run at a speed of 5.8 meters per minute. per minute to the vent drums running at a speed of 21.4 meters per minute. per minute as well as inflating the 10 cm wide tube during the production of a film having a width of approx. 41 cm and a film thickness of approx. 61 microns. This rudder is then rolled onto a bearing roller, which is then converted into bags by sealing the rudder transversely at certain distances to form bottom in the usual manner and separating the rudder into desired bag lengths.
EXAMPLE II
The above procedure was repeated except for the barrier layer which was varied by the addition of 2% 2-ethylhexyl150503 diphenylphosphate plasticizer sold by Monsanto under the name
Santicizer'141, and by reducing the epoxy resin content to 3%.
EXAMPLE III
The procedure of Example I was repeated except that the barrier layer composition was 66% vinylidene chloride / vinyl chloride copolymer resin UP 925%, 30% of a liquid coating of vinylidene chloride polymer resin sold by Dow Chemical Company as QX 2168, 2% Epon resin 828 and 2% Santicizer 141.
EXAMPLE IV
The procedure of Example III was repeated except that all of the saran in the barrier layer composition was QX 2168.
EXAMPLES V & VI
The procedures of Examples III and IV were repeated except that the liquid coated vinylidene chloride polymer sold by WR Grace & Co. like Daran CR 6795-H, replaced QX 2168.
EXAMPLE VII
The procedure of Example I was repeated except that 5% of an epoxidized soybean oil (not to be confused with epoxy resin) sold by Swift & Co. such as Epoxol 7-4. '! replaced 5% epoxy resin.
EXAMPLE VIII
The procedure of Example I was repeated except that 4% of 1-ethylhexyldiphenyl phosphate plasticizer and 1% of magnesium oxide replaced 5% of epoxy resin.
EXAMPLE IX
The procedure of Example I was repeated except that a mixture of 53.3% by weight isotacticity-showing polypropylene (Novamont FOO7, which is a trademark of Novamont Corp), 33.3% polybutene-1 (Mobile PB 103, which is a trademark for Mobil Oil Co.) and · 13.3% of a.activity exhibiting polypropylene (Novamont Lot 2030) was used to form the third layer. The atactivity-exhibiting and isotactic-exhibiting polypropylene is first added in equal amount to a Banbury mixer and melt-blended for approx.
minutes at 20 ° C, then extrude to a plate which is divided into pellets. These pellets are joined to pellets consisting of polybutene-1 in a rotating cylinder, and this mixture is added to the filling funnel of extruder 35. Extruder 35 is run at the following temperatures: rear zone (196 ° C, middle zone 204 ° C, forward zone 232 ° C, intermediate 204 ° C and the nozzle 218 ° C.
EXAMPLE X
The composition used in Example II to form the barrier layer was used except for the 4% epoxy resin used and the UP 925 resin content is reduced by 1%, after which a self-supporting single layer film was extruded under extrusion conditions as set forth in Example
II. A propylene glycol coating was applied to the interior of the rudder to prevent adhesion when the rudder was broken for the biaxial orientation. The process was continuous and bubble 54 was formed after the rudder was broken, but without the rudder being rolled up. Also, the water bath was kept at approx. 38 ° C. The thickness of the extruded film was approx. 125 microns and the thickness of the biaxially oriented film approx. 19 micron, after a total biaxial orientation-stretch ratio of approx. 12: 1. The film was found to have unexpected hby tear and perforation resistance compared to commonly known oriented films of vinylidene chloride / vinyl chloride copolymers.
PACKAGE-RESISTANCE TESTS
The following test procedure was used. All the sample bags were codified and conditioned 24 hours at 7-10 ° C. Randomly selected bags were used to pack cut ribbed bones with legs, and weighing 11.3 - 13.6 kg. The bags were 41 cm wide and 76 or 81 cm deep. The seals were evacuated and the bags squeezed, shrunk sealed and dried in air stream. The packages were then packed in boxes in wax-coated corrugated containers, three in one container. . The containers were then closed with nylon monofilament tape.
During the fall test, each container will fall from a height of 0.91 meters from a moving device. In the transport test, the containers were stored at 3 ° C for 24 hours and then shaken 7.5 minutes at 1 g on a LAB Vibration tester to simulate a 200 km road transport.
In both tests, the gaskets were pumped with air and submerged under water to determine. leak. A package of leaks was classified as incorrect.
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Contents13
13 sheets
Sheet 1 Sheet 2 Sheet 3 Sheet 4 Sheet 5 Sheet 6 Sheet 7 Sheet 8 Sheet 9 Sheet 10 Sheet 11 Sheet 12 Sheet 13
61 members in 19 offices
Priority claims4
| Document | Office | Kind | Date |
|---|---|---|---|
| 12950171 | United States of America | A | |
| 12950171 | United States of America | A | |
| 129501 | – | – | – |
| US19710129501 | – | – | – |
Members61
| Document | Office | Kind | |
|---|---|---|---|
| BE781425A | Belgium | A | |
| NL7204390A | Netherlands (Kingdom of the) | A | |
| NO833780L | Norway | L | |
| DE2213850A1 | Germany | A1 | |
| FR2132212A1 | France | A1 | |
| ZA722139B | South Africa | B | |
| AR193252A1 | Argentina | A1 | |
| AR193253A1 | Argentina | A1 | |
| BR7201862D0 | Brazil | D0 | |
| BR7201864D0 | Brazil | D0 | |
| IT950888B | Italy | B | |
| US3741253A | United States of America | A | |
| AU4065372A | Australia | A | |
| AU469975B2 | Australia | B2 | |
| ES401294A1 | Spain | A1 | |
| ES401295A1 | Spain | A1 | |
| ES401296A1 | Spain | A1 | |
| GB1392334A | United Kingdom | A | |
| GB1392335A | United Kingdom | A | |
| SE7509006A | Sweden | A | |
| CA975280A | Canada | A | |
| AU478964B2 | Australia | B2 | |
| AU8488275A | Australia | A | |
| FR2283172A1 | France | A1 | |
| US3953557A | United States of America | A | |
| FR2132212B1 | France | B1 | |
| CA1009399A | Canada | A | |
| US4031162A | United States of America | A | |
| CH595256A5 | Switzerland | A5 | |
| FI780578A | Finland | A | |
| CA1028814A | Canada | A | |
| US4082829A | United States of America | A | |
| NO138337B | Norway | B | |
| CH602849A5 | Switzerland | A5 | |
| NO138337C | Norway | C | |
| SE403731B | Sweden | B | |
| FR2283172B1 | France | B1 | |
| SE410195B | Sweden | B | |
| JPS54148046A | Japan | A | |
| FI56975B | Finland | B | |
| FI56975C | Finland | C | |
| JPS5547056B2 | Japan | B2 | |
| DE2213850C2 | Germany | C2 | |
| FI62121B | Finland | B | |
| FI62121C | Finland | C | |
| JPS5843024B1 | Japan | B1 | |
| DK465683A | Denmark | A | |
| DK465683D0 | Denmark | D0 | |
| DK147358B | Denmark | B | |
| NO150503BThis record | Norway | B | |
| NO150503C | Norway | C | |
| DK147358C | Denmark | C | |
| DK147976B | Denmark | B | |
| DK147976C | Denmark | C | |
| DE2265689C2 | Germany | C2 | |
| NL180732B | Netherlands (Kingdom of the) | B | |
| NL180732C | Netherlands (Kingdom of the) | C | |
| NO161210B | Norway | B | |
| NO161210C | Norway | C | |
| DK163806B | Denmark | B | |
| DK163806C | Denmark | C |
Numbers
- Publication, DOCDB
- 150503
- Publication, EPODOC
- NO150503B
- Application
- 110472
- Application, DOCDB
- 110472
- Application, EPODOC
- NO19720001104
Titles2
- Norwegian
- VARMEKRYMPBART, FLEKSIBELT LAMINAT OG FREMGANGSMAATE FOR FREMSTILLING DERAV
- English
- HEATABLE, FLEXIBLE LAMINATE AND PROCEDURE FOR PRODUCING THEREOF
Classification
- CPC, 27
- C08J7/048
- B32B27/00
- C08J2323/08
- C08L27/08
- C08J7/042
- C08J2427/08
- B29C48/09
- B29C48/10
- B29C48/0016
- B29C48/21
- Y10T428/24967
- Y10T428/31928
- C08J7/043
- B32B2439/70
- B32B2307/514
- B32B27/306
- B32B27/08
- B32B27/32
- B32B27/30
- B32B2307/7244
- B32B2270/00
- B32B2310/0875
- B32B2597/00
- B32B2305/72
- B32B2038/0028
- B32B2307/736
- B32B27/304
- IPC, 10
- B29C48 09
- B29C48 10
- B29C48 21
- B32B27 00
- C08J5 18
- C08J7 043
- C08J7 048
- C08L1 00
- C08L27 00
- C08L27 08
