GB2076741A - Heat-sealable Multiply Polypropylene Film - Google Patents
Heat-sealable Multiply Polypropylene Film Download PDFInfo
- Publication number
- GB2076741A GB2076741A GB8115820A GB8115820A GB2076741A GB 2076741 A GB2076741 A GB 2076741A GB 8115820 A GB8115820 A GB 8115820A GB 8115820 A GB8115820 A GB 8115820A GB 2076741 A GB2076741 A GB 2076741A
- Authority
- GB
- United Kingdom
- Prior art keywords
- film
- heat
- layer
- sealable
- weight
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
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Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B27/00—Layered products comprising a layer of synthetic resin
- B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
- B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form
- B32B3/26—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer
- B32B3/266—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar form; Layered products having particular features of form characterised by a particular shape of the outline of the cross-section of a continuous layer; characterised by a layer with cavities or internal voids ; characterised by an apertured layer characterised by an apertured layer, the apertures going through the whole thickness of the layer, e.g. expanded metal, perforated layer, slit layer regular cells B32B3/12
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2250/00—Layers arrangement
- B32B2250/24—All layers being polymeric
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2270/00—Resin or rubber layer containing a blend of at least two different polymers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/30—Properties of the layers or laminate having particular thermal properties
- B32B2307/31—Heat sealable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/50—Properties of the layers or laminate having particular mechanical properties
- B32B2307/514—Oriented
- B32B2307/518—Oriented bi-axially
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2307/00—Properties of the layers or laminate
- B32B2307/70—Other properties
- B32B2307/732—Dimensional properties
- B32B2307/734—Dimensional stability
- B32B2307/736—Shrinkable
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2323/00—Polyalkenes
- B32B2323/10—Polypropylene
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B32—LAYERED PRODUCTS
- B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
- B32B2553/00—Packaging equipment or accessories not otherwise provided for
Abstract
A heat-sealable and shrinkable, coextruded, multi-layer packaging film having a propylene homopolymer base layer and a skin layer of either a propylene-ethylene copolymer or of a blend of such a copolymer with up to 50% by weight of a propylene homopolymer, a preferred blend comprising 60% to 80% of the copolymer.
Description
SPECIFICATION
Heat-sealable Multiply Polypropylene Film
This invention relates to thermoplastic, heat-shrinkable packaging films, particularly polypropylene films, having improved heat sealing characteristics. These films can be used to package a wide variety of food and non-food items.
Oriented polypropylene films are useful and widely accepted packaging films because of their good moisture barrier, stiffness, high strength, and optical properties. However, films of polypropylene do not, in general, exhibit good heat-sealing properties which is an important consideration in packaging applications. This is because polypropylene films have very narrow sealing temperature
ranges.
The sealing temperature range for a thermoplastic film can be considered as beginning at that point where upon application of heat and pressure the surfaces of the film will seal or bond together.
As temperature is increased further, a point is reached where the thermoplastic melts and flows so readily that it is difficult to achieve a seal in a specific area. This marks the upper end of the sealing range. Also at the upper end of the sealing range the film may tend to burn and char leaving weak and unsightly seals. For propylene homopolymerfilm, as temperature is increased, the film does not become sealable but rather suddenly flows undesirably as its melting point is approached making it quite difficult to achieve smooth, continuous, satisfactory seals. This type of sealing performance cannot be tolerated on high speed packaging equipment.
In order to get good heat sealability, it has been the practice to apply various types of coatings to the films. Coatings have conventionally been applied in separate coating operations, such as from emulsions, extrusion coating, and so forth, but such operations are costly and require additional handling of the film. Coextrusion has been used successfully to put a heat sealable coating on polypropylene and produce a film of good seal strength, but until the present invention coextruded polypropylene film laminates had a very narrow heat seal range, and were expensive to produce.
Accordingly, the present invention provides a polypropylene film having a wide sealing range. The invention also provides a polypropylene film having acceptable seal strength for shrink packaging applications.
Typical patents which disclose coatings for polypropylene film are U.S. Patent No. 3,285,756 (which issued on November 1 5, 1 966 to Edward Barkis et al) which discloses a method of extruding a coating containing at least 65% ethylene onto a sheet of polypropylene; U.S. Patent No. 3,671,383 (which issued on June 20, 1 972 to Rikita Sakata et al) which discloses a biaxially oriented polypropylene film laminated to a uniaxially oriented ethylene-propylene copolymer film with at least 75% by weight polypropylene; U.S. Patent No. 4,132,050 (which issued on January 2, 1979 to Roger
N. Young) and which discloses a film having a substrate formed of a blend of 87.5 to 60 parts of polypropylene and 12.5 to 40 parts of ethylene-propylene block copolymer with a heat-sealable layer; and U.S.Patent No. 4,148,972 (which issued on April 10, 1979 to Toshi Hiro Yamane et al) which discloses a polypropylene film laminate made by laminating a polypropylene layer having 1 to 8 weight percent of an ionomer with an ionomer layer.
It has been surprisingly discovered that the seal temperature range of a multi-layer polypropylene film can be increased and that acceptable seal strength for such a film can be provided by a multi-layer film which comprises a base layer of propylene homopolymer and a skin layer affixed to one surface of the base layer wherein the skin layer comprises a blend of 50% to 100% by weight of propyleneethylene copolymer with 50% to 0% by weight of propylene homopolymer. The preferred blend is 60% to 80% copolymer with 40% to 20% homopolymer. In a particularly desirable embodiment, the skin layer has 70% by weight of propylene-ethylene copolymer blended with 30% by weight of propylene homopolymer and the copolymer contains 2 to 6% by weight of ethylene, or even more preferably, 3% to 4% ethylene by weight.In addition, the ratio of the thickness of the skin layer to the thickness of the base layer is preferably 4:1 or greater.
The invention also provides a method of producing a heat-sealable multi-layer film as aforesaid which comprises (a) providing a base layer of propylene homopolymer; (b) laminating a skin layer to at least one side of the propylene homopolymer film, said skin layer comprising a blend of 50 to 100% by weight of the propylene-ethylene copolymer with 50 to 0% by weight of propylene homopolymer; and biaxially stretching the laminated film. The final total film thickness is preferably in the range of 0.25 to 2.5 mils (6.35-63.5 microns). Such a film will usually have a sealing range of at least 200C and should produce a seal strength of greater than 300 gms/inch (11 8 g./cm). A preferred method of producing the laminated film is to coextrude the skin layer and the base layer.
The invention also provides a method of producing a heat-sealed and preferably shrunken package of polypropylene film which comprises overwrapping a product to be wrapped with a heatsealable, and normally heat-shrinkable film as aforesaid, bringing skin layer surfaces into contact with each other at points to be heat-sealed; and applying heat and pressure at the points to be sealed thereby sealing said film at said points, the sealing temperature range of said applied heat being in the range of 135"C to 1 600 C; and then preferably applying heat in the range of 11 00C to 1 350C to said package for time sufficient to shrink the said film aboutthe said product. The film may be perforated.
The preferred embodiment of the present invention is a two-layer film made by blending 70% by weight of propylene-ethylene copolymer having 3.5 to 4.2% by weight of ethylene with 30% by weight of propylene homopolymer for the skin or outside layer. This mixture is blended in a Banbury blender and then fed into the hopper of an extruder which feeds into an annular die for extruding a tube having two layers. The inside or base layer comprises propylene homopolymer which is fed into the hopper of a second extruder which also feeds the annular die to provide the inside layer.
In the annular die the two tubular extrudates are joined to become a multi-layer tubular laminate.
This tubular laminate is rapidly cooled and then collapsed. Afterwards, the tubing is inflated and heated to the orientation temperature range of polypropylene which is in the range of 1 350C to 1 50cC. The heating takes place in an oven, and as the flattened film emerges from the oven, it passes through pinch rolls and is opened to a bubble by the well known trapped bubble technique where it is stretched about five times in both vertical and horizontal directions which reduces the film to a thickness in the range of 0.60 to 0.80 mils (1 5.24 to 20.3 microns). Prior to stretching the typical tubing would have a thickness of about 1 8 mils (457 microns) with the thickness ratio of the polypropylene layer to the blended layer being 5:1. A description of one such bubble technique for biaxially orienting polypropylene is given in U.S.Patent No. 3,260,776 which issued on July 17, 1966 to C. A. Lindstrom et al.
After the film has been expanded into the bubble and the bubble cooled, it is collapsed, slit, and wound up.
In some instances it is desirable to perforate the film so that an array of perforations or small holes are made in the film. Depending on the desired application, the number of holes may be from eight to ten per square inch of film up to several hundred holes per square inch and the holes may run anywhere from 2 to 20 mils (50 to 500 microns) in diameter. A typical apparatus for perforating the film employs a cooled grid over which the film is passed while it is exposed to a jet of hot gas which will melt the film in the uncooled areas. Such an apparatus and method are described in U.S. Patent No.3,038,198 which issued on June 12, 1962 to C. H. Schaar.
To determine the sealing range and seal strength of the preferred film two sheets of the film were superposed with the skin layer surfaces in contact. An electrical resistance heated flat sealing bar 5 mm. wide was used to press the sheets together against a backing surface with a pressure of 1 kg./s-q.cm. for 0.5 second and the temperature of the sealing bar was recorded. After the sealing had been completed a one inch (25 mm.) strip was cut perpendicular to and across the seal made by the bar, and the ends of the respective strips were placed in the jaws of an Instron testing machine with the seal located at approximately the mid point between the gripping jaws. Force was applied by driving the jaws apart until the seal either peeled or broke.Seals having a minimum strength of approximately 300 gms/inch (118 g./cm.), the minimum considered sufficient for packaging applications, were achieved by the preferred embodiment at a seal bar temperature as low as 1 35 OC and satisfactory seals continued to be made as temperature increased up to about 1 600C for a sealing range of approximately 250C. (Hereinbelow, field tests indicate that the operable range is 300C.). A maximum seal strength of about 1,400 gms/inch (551 g./cm.) was achieved.
As stated previously, a monolayer polypropylene film has an essentially "zero" width sealing range. Because seal bars are cooled by contact with film, in packaging machinery it is the necessary practice with polypropylene to set the temperature of the seal bars somewhat above the melting point so that a sealed package can be obtained but seals made in this way have a poor appearance and burned zones. With a film such as that of the present invention, setting the seal bars and temperatures near the top of the sealing range does not run the risk of melting the film or burning it plus at high speeds where the film tends to cool the seal bars, the seal bars will still maintain sufficient heat to seal the film and not be cooled below the sealing range.
A number of products can be packaged in the film of the present invention and the various
machines use different techniques. In some instances, the product is placed on one sheet of film and then a second sheet is laid over the product and a complete perimeter seal is then made; and, in some instances the sealing operation also severs the excess film to trim the package. After sealing, the product passes through a heat tunnel which may have a temperature as low as 11 00C but is usually set in the range in which the film was stretched. In the tunnel the heat causes the stretch tensions to release and the film to shrink around the product. In other packaging processes the product may be placed between the folds of a center folded film and a seal on the remaining three unsealed sides is made. Many methods of over-wrapping a product in shrink film are understood by those skilled in theart.
Products such as bread, soft bakery products including rolls, pizzas, and the like may be packaged
with the film of the present invention. Also food products requiring breathing through the film such as fruits and vegetables may be packaged using the perforated film.
Examples
In order to solve the probiem presented by the virtually non-existent heat sealing range of polypropylene, a number of blended sealing layer compositions were tried. Listed below in Table 1 are the two-layer films having a polypropylene homopolymer base or substrate layer which has been coextruded with the specifically designated sealing layer composition. Only those compositions which could be successfully processed by the trapped bubble technique into film are shown in Table 1. The footnotes immediately below the table explain the abbreviations for the polymers, and sealing range and seal strength were determined as explained above.Haze is the percentage of transmitted light which in passing through the specimen deviates from the incident beam more than 2.50 on the average and which is determined by ASTM Method Dl 003. The measurement of thickness reported is of the total film laminate.
Table I
Min. Seal Temp. Max. Seal
Sealing Thickness Sealing (0C) to Have Strength
layer {mils/ Range 300 Flinch (Gflnch or Haze
composition microns) (0C) (118 G./CM.) G./CM.) 100% PP 0.70/17.8 ZERO - 500 or 197 1.0 90/10 PP/PB 0.71/18.0 5 155 850Or335 1.1 80/20 PP/PB 0.69/17.5 10(15-20) 150 500 or 197 1.3 75/25 PP/EVA 0.79/20.1 5 155 300Or118 2.8 50/50 PP/EVA 0.77/19.6 5 1 55 300 or 118 2.9 90/10 PP/SURLYN 0.80/20.3 5 155 350 or 138 1.5 80/20 PP/SURLYN 0.72/18.3 5 155 400 or 157 1.9 50/40/10PP/P-E/ 0.75/19.1 10 150 1200Or472 1.1
SURLYN 50/50PP/P-E 0.73/18.6 10 150 1400Or551 0.31 40/60PP/P-E 0.74/18.8 20to25 140 1550Or610 0.70 30/70PP/P-E 0.73/18.6 25to30 135 1400Or551 2.0 100 P-E 0.70/17.8 30 130 1200 or 472 2.4
PP=Propylene homopolymer (Film grade resin, predominately isotactic polymer)
PB=Polybutylene P-E=Prnpylene-ethylene copolymer (Approx. 4% Ethylene) SURLYN1Type 1601 from Du Pont
EVA=Ethylene-vinyl acetate copolymer having approx. 10% vinyl acetate.
Examples 3, 10, and 11 are expressed as ranges because these samples were run on actual equipment in the field as well as having their sealing range measurement in the laboratory and, in the field, about a 50C increase in sealing temperature range was observed thus increasing the upper seal temperature to about 165bC. These three samples were run as perforated films packaging rolls and crusty bread. Each of these films had good machinability, i.e. they were stiff enough to perform well in standard packaging equipment.
The film according to Example 11 also performed well in the field for packaging crescent rolls and pizzas with non-perforated film.
Looking at Table 1 it is evident that Examples 10, 11, and 12 have desirably wide sealing ranges and each of these films has good machinability and the haze is not objectionable. However, above approximately 80% propylene-ethylene copolymer in the blend processability problems in the trapped bubble process become pronounced as the sealing layer tends to flow and distort at the high temperature needed to stretch and orient the polypropylene base layer. In other words, the propylene-ethylene copolymer is beginning to melt at the orientation temperature of the propylene homopolymer and the sealing layer, being on the outside of the tubing, tends to stick to pinch rolls after being heated but prior to being blown into a bubble.Thus, the preferred range for the propyleneethylene copolymer in the sealing layer blend is from 60 to 80% by weight and this gives a sealing temperature range of from 200C to 300 C. The composition of Example 11 is the best all around combination of seal temperature range, seal strength, processability on present state of the art film manufacturing equipment, and machinability. On commercial packaging machinery 50 to 80 packages per minute can be made and the indications are that these rates can be successfully exceeded.
By coextruding the base layer and skin as a flat sheet from a slot die, rapidly cooling the sheet, and using a tenterframe to stretch the flat sheet when heated to orientation temperature continuous manufacture of a film in which the skin layer blend is greater than 80% could be achieved but trim wastage and other factors make the tenterframe method less attractive. In any event, it should be recognized that the widening of the heat seal range begins noticeably with a skin layer blend of at least 50% copolymer and continues up to 100% copolymer.
The propylene homopolymer used in the present invention is predominately isotactic polypropylene of film grade available from a number ofwell known resin suppliers. Likewise, the propylene-ethylene copolymer is a random copolymer of film grade also available from well known resin producers and the ethylene weight percentage is in the range of 2% to 6% which will perform satisfactorily. With a higher percentage of ethylene in the copolymer it is to be expected that the percentage of the copolymer in the blend may be increased.
The layer thickness ratios of the multi-layer film of this invention are those which give the optimum combination of machinability, sealability and processability. If the sealing layer thickness is increased much beyond the 4:1 ratio processing problems are incurred at the orientation temperature of polypropylene as explained above. Thus, the base layer to sealing layer ratio should be greater than 4:1 and as noted above, a 5:1 ratio gives quite satisfactory performance. In addition, a total film thickness in the range of 0.25 to 2.5 mil (6.3 to 63 microns) produces the most satisfactory combination of film characteristics.
Also within the scope of this invention are three layer films where the central layer is the propylene homopolymer layer which is oriented and the sealing layers are on both sides of the oriented homopolymer layer to give it balance. This is to prevent curl which can occur in structurally unbalanced, multi-layer films.
Claims (17)
1. A heat-sealable, multi-layer film for packaging comprising:
a) a base layer comprising propylene homopolymer;
b) a skin layer affixed to one surface of said base layer, said skin layer comprising a blend of 50% to 100% by weight of propylene-ethylene copolymer with 50% to 0% by weight of propylene homopolymer.
2. A heat-sealable film according to claim 1 wherein the said copolymer comprises 2% to 6% by weight of ethylene.
3. A heat-sealable film according to claim 1 or 2 wherein the said film is heat-shrinkable, the ratio of the thickness of the base layer to the thickness of the skin layer is at least 4:1, and the said blend comprises 60% to 80% by weight of propylene-ethylene copolymer with 40% to 20% by weight of propylene homopolymer.
4. A heat-sealable film according to any of claims 1 to 3 wherein the said film has a sealing range of at least 200C.
5. A heat-sealable film according to any of claims 1 to 4 having a skin layer affixed to both sides of the base layer to structurally balance said film.
6. A heat-sealable film according to any of claims 1 to 5 wherein said film is perforated.
7. A heat-sealable film according to any of claims 1 to 6 which will produce a seal strength of at least 300 gms/inch (118 g./cm.) at a temperature as low as 1 35 or.
8. A heat-sealable film according to any of claims 1 to 7 having a total thickness in the range 0.25 mil to 2.5 mil (6.3 to 63 microns).
9. A method of producing a heat-sealable multi-layer film as claimed in any of claims 1 to 8 which comprises:
a) providing a base layer comprising propylene homopolymer;
b) laminating a skin layer to at least one side of the said propylene homopolymer film, said skin layer comprising a blend of 50% to 100% by weight of propylene-ethylene copolymer with 50% to 0% by weight of propylene homopolymer; and,
c) biaxially stretching said laminated film thereby producing a heat-sealable, heat shrinkable propylene homopolymer film.
10. A method according to claim 9 wherein equal thickness skin layers are laminated to both sides of the said base layer to balance the final film.
11. A method according to claim 9 or 10 wherein the ratio of the thickness of the base layer to the thickness of the skin layer is at least 4:1 and the skin layer comprises a blend of 60% to 80% by weight of propylene-ethylene copolymer with 40% to 20% by weight of propylene homopolymer.
12. A method according to any of claims 9 to 11 wherein the said laminating step is achieved by coextruding the skin layer or layers and the base layer.
1 3. A method according to any of claims 9 to 12 wherein the biaxially stretched film is perforated.
14. A method according to claim 9 substantially as described in Example 10, 11 or 12.
15. A heat-sealable multi-layer film when produced by the process of any of claims 9 to 14.
1 6. A method of producing a heat-sealed package of polypropylene film which comprises overwrapping a product to be wrapped with a heat-sealable film as claimed in any of claims 1 to 8 or 1 5, bringing skin layer surfaces into contact with each other at points to be heat sealed, and applying heat and pressure at the points to be sealed thereby sealing said film at said points, the temperature range of said applied heat being 1 350C to 1 650C.
17. A method according to claim 16 in which the film is also heat-shrinkable and heat in the range of 11 00C to 1 350C is applied to the said package for a time sufficient to shrink the said film about the said product.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US15297080A | 1980-05-23 | 1980-05-23 |
Publications (2)
Publication Number | Publication Date |
---|---|
GB2076741A true GB2076741A (en) | 1981-12-09 |
GB2076741B GB2076741B (en) | 1984-04-18 |
Family
ID=22545224
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
GB8115820A Expired GB2076741B (en) | 1980-05-23 | 1981-05-22 | Heat-sealable multiply polypropylene film |
Country Status (22)
Country | Link |
---|---|
JP (1) | JPS578156A (en) |
AR (1) | AR225081A1 (en) |
AU (1) | AU536917B2 (en) |
BE (1) | BE888914A (en) |
BR (1) | BR8102322A (en) |
CA (1) | CA1149122A (en) |
CH (1) | CH656349A5 (en) |
DE (1) | DE3111269A1 (en) |
DK (1) | DK164093C (en) |
ES (1) | ES8203697A1 (en) |
FI (1) | FI75526C (en) |
FR (1) | FR2482900B1 (en) |
GB (1) | GB2076741B (en) |
IE (1) | IE51291B1 (en) |
IL (1) | IL62940A (en) |
IT (1) | IT1136935B (en) |
MX (1) | MX156235A (en) |
NL (1) | NL188022C (en) |
NZ (1) | NZ196286A (en) |
PT (1) | PT72887B (en) |
SE (1) | SE451692B (en) |
ZA (1) | ZA811494B (en) |
Cited By (11)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8300616A (en) * | 1982-02-19 | 1983-09-16 | Grace W R & Co | LINEAR POLYETHENE SHRINKLING FOILS. |
EP0114311A2 (en) * | 1982-12-24 | 1984-08-01 | Hoechst Aktiengesellschaft | Sealable polyolefinic multilayer film |
EP0114312A2 (en) * | 1982-12-24 | 1984-08-01 | Hoechst Aktiengesellschaft | Sealable transparent polyolefinic multilayer film |
EP0207719A3 (en) * | 1985-06-28 | 1987-12-02 | W.R. Grace & Co.-Conn. | Oxygen barrier oriented film |
FR2635312A1 (en) * | 1988-08-11 | 1990-02-16 | Okura Industrial Co Ltd | THERMORETRACTABLE COMPOSITE FILM AND METHOD FOR PACKAGING AN OBJECT |
US4986496A (en) * | 1985-05-31 | 1991-01-22 | Minnesota Mining And Manufacturing | Drag reduction article |
US5133516A (en) * | 1985-05-31 | 1992-07-28 | Minnesota Mining And Manufacturing Co. | Drag reduction article |
CH686178A5 (en) * | 1993-10-01 | 1996-01-31 | Alusuisse Lonza Services Ag | Sealable wrapper for solid foods stuffs |
EP0698486A1 (en) * | 1994-07-13 | 1996-02-28 | Sumitomo Chemical Company, Limited | Self-tacky packaging film |
US6420625B1 (en) | 1997-09-12 | 2002-07-16 | Kimberly-Clark Worldwide, Inc. | Breathable, liquid-impermeable, apertured film/nonwoven laminate and process for making same |
US20120240511A1 (en) * | 2009-12-11 | 2012-09-27 | Huhtamaki Forchheim Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co. Kg | Multi-Layer Film Having a High Puncture Resistance and Resistance to Further Tearing |
Family Cites Families (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US3285766A (en) * | 1963-03-28 | 1966-11-15 | Avisun Corp | Biaxially oriented ethylene polymer coated polypropylene sheet and method for makingsame |
GB1145199A (en) * | 1966-06-13 | 1969-03-12 | Nat Distillers Chem Corp | Heat-sealable oriented polypropylene film laminate |
DE1769028A1 (en) * | 1968-03-22 | 1972-02-03 | Kalle Ag | Biaxially oriented polypropylene film |
JPS4914343A (en) * | 1972-05-22 | 1974-02-07 | ||
US3983258A (en) * | 1975-02-07 | 1976-09-28 | Continental Can Company, Inc. | Process of packaging edible products containing exposed bones |
GB2029317A (en) * | 1978-09-06 | 1980-03-19 | British Cellophane Ltd | Heat-sealable polypropylene films |
-
1981
- 1981-02-17 NZ NZ196286A patent/NZ196286A/en unknown
- 1981-03-05 ZA ZA00811494A patent/ZA811494B/en unknown
- 1981-03-16 IT IT20364/81A patent/IT1136935B/en active
- 1981-03-16 MX MX186391A patent/MX156235A/en unknown
- 1981-03-19 CA CA000373413A patent/CA1149122A/en not_active Expired
- 1981-03-21 DE DE19813111269 patent/DE3111269A1/en active Granted
- 1981-03-25 NL NLAANVRAGE8101472,A patent/NL188022C/en not_active IP Right Cessation
- 1981-04-15 BR BR8102322A patent/BR8102322A/en unknown
- 1981-04-20 PT PT72887A patent/PT72887B/en unknown
- 1981-04-21 JP JP5932781A patent/JPS578156A/en active Granted
- 1981-05-07 AU AU70240/81A patent/AU536917B2/en not_active Ceased
- 1981-05-13 CH CH3120/81A patent/CH656349A5/en not_active IP Right Cessation
- 1981-05-21 BE BE0/204871A patent/BE888914A/en not_active IP Right Cessation
- 1981-05-21 AR AR285408A patent/AR225081A1/en active
- 1981-05-21 FI FI811569A patent/FI75526C/en not_active IP Right Cessation
- 1981-05-21 IE IE1133/81A patent/IE51291B1/en not_active IP Right Cessation
- 1981-05-22 SE SE8103257A patent/SE451692B/en not_active IP Right Cessation
- 1981-05-22 DK DK227081A patent/DK164093C/en not_active IP Right Cessation
- 1981-05-22 ES ES502438A patent/ES8203697A1/en not_active Expired
- 1981-05-22 IL IL62940A patent/IL62940A/en not_active IP Right Cessation
- 1981-05-22 GB GB8115820A patent/GB2076741B/en not_active Expired
- 1981-05-22 FR FR8110273A patent/FR2482900B1/en not_active Expired
Cited By (16)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
NL8300616A (en) * | 1982-02-19 | 1983-09-16 | Grace W R & Co | LINEAR POLYETHENE SHRINKLING FOILS. |
EP0114311A2 (en) * | 1982-12-24 | 1984-08-01 | Hoechst Aktiengesellschaft | Sealable polyolefinic multilayer film |
EP0114312A2 (en) * | 1982-12-24 | 1984-08-01 | Hoechst Aktiengesellschaft | Sealable transparent polyolefinic multilayer film |
EP0114312A3 (en) * | 1982-12-24 | 1985-08-14 | Hoechst Aktiengesellschaft | Sealable transparent polyolefinic multilayer film |
EP0114311A3 (en) * | 1982-12-24 | 1985-08-21 | Hoechst Aktiengesellschaft | Sealable polyolefinic multilayer film |
US4986496A (en) * | 1985-05-31 | 1991-01-22 | Minnesota Mining And Manufacturing | Drag reduction article |
US5069403A (en) * | 1985-05-31 | 1991-12-03 | Minnesota Mining And Manufacturing Company | Drag reduction article |
US5133516A (en) * | 1985-05-31 | 1992-07-28 | Minnesota Mining And Manufacturing Co. | Drag reduction article |
US4726984A (en) * | 1985-06-28 | 1988-02-23 | W. R. Grace & Co. | Oxygen barrier oriented film |
EP0207719A3 (en) * | 1985-06-28 | 1987-12-02 | W.R. Grace & Co.-Conn. | Oxygen barrier oriented film |
FR2635312A1 (en) * | 1988-08-11 | 1990-02-16 | Okura Industrial Co Ltd | THERMORETRACTABLE COMPOSITE FILM AND METHOD FOR PACKAGING AN OBJECT |
CH686178A5 (en) * | 1993-10-01 | 1996-01-31 | Alusuisse Lonza Services Ag | Sealable wrapper for solid foods stuffs |
EP0698486A1 (en) * | 1994-07-13 | 1996-02-28 | Sumitomo Chemical Company, Limited | Self-tacky packaging film |
US6420625B1 (en) | 1997-09-12 | 2002-07-16 | Kimberly-Clark Worldwide, Inc. | Breathable, liquid-impermeable, apertured film/nonwoven laminate and process for making same |
US20120240511A1 (en) * | 2009-12-11 | 2012-09-27 | Huhtamaki Forchheim Zweigniederlassung Der Huhtamaki Deutschland Gmbh & Co. Kg | Multi-Layer Film Having a High Puncture Resistance and Resistance to Further Tearing |
US9752325B2 (en) * | 2009-12-11 | 2017-09-05 | Infiana Germany Gmbh & Co. Kg | Multi-layer film having a high puncture resistance and resistance to further tearing |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
732 | Registration of transactions, instruments or events in the register (sect. 32/1977) | ||
732E | Amendments to the register in respect of changes of name or changes affecting rights (sect. 32/1977) | ||
PE20 | Patent expired after termination of 20 years |
Effective date: 20010521 |