GB2033838A - Heat sealable polypropylene films - Google Patents

Heat sealable polypropylene films Download PDF

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Publication number
GB2033838A
GB2033838A GB7928896A GB7928896A GB2033838A GB 2033838 A GB2033838 A GB 2033838A GB 7928896 A GB7928896 A GB 7928896A GB 7928896 A GB7928896 A GB 7928896A GB 2033838 A GB2033838 A GB 2033838A
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GB
United Kingdom
Prior art keywords
copolymer
ethylene
polypropylene film
alpha olefin
film
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Granted
Application number
GB7928896A
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GB2033838B (en
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British Cellophane Ltd
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British Cellophane Ltd
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Filing date
Publication date
Priority claimed from GB7835846A external-priority patent/GB2029317A/en
Application filed by British Cellophane Ltd filed Critical British Cellophane Ltd
Priority to GB7928896A priority Critical patent/GB2033838B/en
Publication of GB2033838A publication Critical patent/GB2033838A/en
Application granted granted Critical
Publication of GB2033838B publication Critical patent/GB2033838B/en
Expired legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/048—Forming gas barrier coatings
    • 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
    • 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
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/322—Layered products comprising a layer of synthetic resin comprising polyolefins comprising halogenated polyolefins, e.g. PTFE
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/0427—Coating with only one layer of a composition containing a polymer binder
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/043—Improving the adhesiveness of the coatings per se, e.g. forming primers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J7/00—Chemical treatment or coating of shaped articles made of macromolecular substances
    • C08J7/04—Coating
    • C08J7/052—Forming heat-sealable coatings
    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09J—ADHESIVES; NON-MECHANICAL ASPECTS OF ADHESIVE PROCESSES IN GENERAL; ADHESIVE PROCESSES NOT PROVIDED FOR ELSEWHERE; USE OF MATERIALS AS ADHESIVES
    • C09J123/00—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers
    • C09J123/02—Adhesives based on homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Adhesives based on derivatives of such polymers not modified by chemical after-treatment
    • C09J123/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • 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
    • B32B2272/00—Resin or rubber layer comprising scrap, waste or recycling material
    • 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
    • B32B2323/00—Polyalkenes
    • B32B2323/04—Polyethylene
    • 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
    • B32B2439/00—Containers; Receptacles
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2423/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
    • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
    • C08L2666/04—Macromolecular compounds according to groups C08L7/00 - C08L49/00, or C08L55/00 - C08L57/00; Derivatives thereof

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Laminated Bodies (AREA)

Abstract

A heat-sealable oriented polypropylene film comprising a base oriented polypropylene film having on one surface a layer of a random propylene/ ethylene copolymer (ethylene content 2-6% by weight) and on the other surface a predominantly linear random copolymer of ethylene and a further alpha olefin having at least three carbon atoms per molecule (for example propylene and butene-1) the further alpha olefin content being 6-40% by weight. The film is particularly useful for packaging merchandise on horizontal form-fill-seal packaging machines.

Description

SPECIFICATION Heat-sealable polypropylene films This invention relates to heat-sealable polypropy- lene films.
Polypropylene film is well known for use as a packaging material lt has high clarity, excellent barrier properties in respect of water vapour and excellent strenggh particularly when its molecular structure has been oriented by stretching in one or preferably two directions at right angles to each otherwhile subjected to to a temperature in the range between 2 C below the crystalline melting point of - the polypropylene and its second order transition: temperature.
Although polypropylene film is inherently heat sealable ta itself an.d: is capable of fo-rrning heat seals of adequate strength at temperatures of about 160 C, at such temperatures and down to about 140 C oriented polypropylene film will shrink and produce undesirable buckling in the region of the heat-sea.r..
It is known to overcome this distortion problem by forming on one or both surfaces of the oriented polypropylene film a layer of a heat-sealable polym er or copolymer capable offorming heat-seals of adequate strength at temperatures below the tem perature at which heat distortion occurs to any significant extent in the base oriented polypropylene film One such known heat-sealable copolymer applied to one or both surfaces of an oriented base polyp ropylene film is a propylene/ethylene copolymer in which the ethylene content lies in the range between 2%- and 6% by weight as described in British Patent' Specification No. 1145199.Another such known heat-sealable copolymer is a predominantly linear random copolymer of ethylene with at least one further alpha olefin having at least three carbon atoms per molecule, present up to about 12 mole per cent in the copolymer,. such as described in our British Patent Specification No. 1440317.
Heat-sealable oriented polypropylene fi:l:rns having heat-sealable outer layers of these heat-sealable copolymers are used extensively upon high speed packaging: machines known as "form-fill-seal" machines, in which m-erchandise is packed into individual sealed bags formed from the films in one continuous operation. In a so-called horizontal "form-fill-seal" machine (such as the "Versoflow" machine marketed by Auto Wrappers of Norwich, England) merchandise, for example, individual trays of confectionery is forward to an input end o the machine at predetermined intervals and is covered by a continuous length of film.The film is folded over the merchandise and the edges of the film are brought together beneath the merchandise between a pair of nip rollers which serve to pull the film from its supply roll. The edges ofthe fil:m then pass between one or more heated rollers which further provide traction upon the film and seal the edge margins together to form- a longitudinal fin seal' thus enclosing the merchandise in a tube of film.Trans- verse seals are then formed across the tube between each unit of merchandise by crimp heat-sealiing jaws and individual sealed bags each containing a unit of merchandise are separated by severing through the body of each transverse seal.
Usually the film is pre-printed at bag length intervals together with a series of datum marks which are "read" with an electric "eye" to check that the printing lies in register with the transverse sealing operation. If through gradual mouvement of the film from register the "eye" fails to detect a datum mark the feed of film is temporarily speeded up or slowed down (depending upon the make of the machine) to bring the film back into register. If, however, the movement of the film from register exceds about 5 millimetres, for example through excessive slip on the nip roller applying traction to the film, the register control is lost and excessive speding up or slowing down (as the case may be) of the film feed results in the heat-seal jaws operating actoss the merchandise causing considerable damage and loss of production.
During the transverse sealing operation, the longitudinal fin seal is so placed that it is turned and flattened against the body of the tube and is tack-sealed by virtue of the outer heat-sealable copolymer layer to each transverse seal.
The speed of the film through the horizontal form-fill-seal machine depends upon the speed at which heat-seals of adequate strength, particularly the transverse heat-seals, can be made. The strength of the heat-seal is measured by cutting a superposed pair of strips from a formed bag, 38 millimetre wide, with the heat-seal towards one end of the pair. The force in grams required to peel the strips apart at the seal is measured and is termed the heat-seal strength.For most purposes, the minimum acceptable heat-seal strength is 450 grams/38 millimetres When the film used on the horizontal form-fill-seal machine is a base oriented polypropylene film having on each surface a layer of a random propylene/ethylene copolymer (ethylene content being between 2% and 6% by weight), the packaging operation is satisfactory at relatively low speeds, but at higher speeds, the heat-seal strength of the transverse heat-seals fall below the acceptable limit.
This is due to the dwell time of the heat-seal jaws being insufficient to raise the temperature of the film portions being sealed to the temperature required to give effective sealing.
Higher speeds with acceptable heat-seals may be attained by employing a base oriented polypropylene film having on each surface a layer of a predominantly linear random copolymer of ethylene with at least one further alpha olefin having at least three carbon atoms per molecule present in the range betwen 6% and 40% by weight, since these copolymers are capable of providing heat-seals of ade4quate strength at lower heat-seal temperatures than the propylene/ethylene copolymers. However, such heat-sealable polypropylene film tends to slip excessively when passing through the nip rollers and heated rollers and as a result the register adjusting mechanism loses control, the length of bags produced on the machine varies widely and considerable damage is caused by the heat-seal jaws closing over the merchandise.
The present invention is concerned with an improved heat-sealable polypropylene.tilm partIcularly for use on horizontal form-fill-seal machines.
According to the present invention a heatrsealable oriented polypropylene film. having on one surface an layer of a random propylene/ethylene copolymer in which the ethylene content lies in the range betwen 2% and 6% by weight, and on the other surface a predominantly linear random copolymer of ethylene and between 6% and 40% by weight of the random copolymer of at least one further alpha olefin having at least three carbon atoms per molecule.
It will be readily appreciated by one skilled in the art that the term "base oriented polypropylene film" includes an oriented film of propylene homopolym-.
er, a copolymer of propylene with a minor amount (e.g. up to 15%) of a further olefin such as ethylene or a blend of such a homopolymer or copolymer with,a small proportion of a compatible polyolefin which does not significantly affect the physical characteristics of lye film.
The term "predominantly linear random copolymer of ethylene with at least one further alpha olefin" means a copolymer. formed by reacting the monomers under conditions which favour the formation of linear chains of ethylene units with little branching and with random distribution of the comonomer or comonomers along the chains. Such conditions are attained by low pressure catalytic procedures employing, for example, a co-ordination or organometallic catalyst such as a-so-called Zeigler catalyst.
Preferably the-amount of further alpha olefin in the random copolymer of ethylene lies in the range between 10% and 35% by weight of the random copolymer and is either propylene or,butene-l.- The heat-sealable oriented polypropylene film in accordance with the invention is particularly. useful for running on horizontal form-fill-seal machines with the layer of the predominantly linear random copolymer of ethylene/further alpha olefin facing the merchandise, since at relatively high machine speeds, heat-seals of adequate strength are achieved together with the minimum of slip past the nip rollers apply the traction.
The heat-sealable layers may be applied to the base propropylene film by any one of the known methods. For example preformed films of the propylene/ethylene copolymer and the ethylene/alpha olefin copolymer may be laminated to a base oriented propylene film by a-suitable adhesive or by stretching the preformed films while in intimate contact when the combination com.bines to form a unitary film Alternatively, the propylene/ethylene copolymer and the ethylene/alpha olefin copolymer may. separately be melt extruded on to each side of a base polypropylene film followed by stretching the combination under stretch-orienta ble conditions.Preferably, however, the heat-sealabl.e po.lypropylene film is formed by co,-extruding the base polypropylene film with the propylenelethylene copolymer and the ethylene/alpha olefin copolymer-op either sie through a slot or annular orifice die followed by quenching and then stretching. under stretchorientable conditions.- The invention further includes a method for the manufacture of a heat-sealable oriented polypropylene film comprising.,applying to one surface of a base polypropylene film a layer of a random propylene/ethylene copolymer in which the ethylene content lies in the range between 2% and 6% by weight and to the other surface a predominantly linear random copolymer of ethylene and between 6% and 40% by weight of the copolymer of at least one further alpha olefin having at least three carbon atoms per molecule, bringing the combination tQ a stretch orientatabie condition and stretching in at least one direction.
Since the propylenelethylene copolymer and the ethylene/alpha olefin copolymer are compatible with polypropylene, waste heat-sealable oriented polypropylene film, for example, edge trim, may be fed back in small quantities to the polypropylene feed to the extruder for the base polypropylene film, without significantly affecting the physicai characteristics of the base film.
The invention will now be more specifically described with reference to the following Example.
Example A polypropylene melt was co-extruded through a slot die at 2 metres/minute between one outer layer of a melt of a random propylene/ethylene copolymer having an ethylene content of 3.5% by weight and a second outer layer of a melt of a predominantly linear random copolymer of ethylene and butene-1 in which the hutene-1 content was 20% by weight, thus forming a three layered molten film approximately 1,100 microns in thickness. The polypropylene constituted 92% of the thickness and each copolymer layer 4% of the thickness. The molten film was quenched on a chill roll and was then heated to a temperaure of above 80"C and stretched 5:1 in the machine direction between sets of nip rollers in which the rollers at the output end were rotated at a greater peripheral speed than the rollers at the input end.The uni-axially stretched film was then led into a stenterwhere.itwas heated to a temperature of about 1 55,C and stretched transversely to 9 times its original width. The film, now biaxially oriented, was cooled, trimmed at the edges and wound into a roll.
The resulting film had high clarity and was approximately 25 microns in thickness.
A supply roll of the film was fitted to a "Verseflow" horizontal form-fill-seal packaging machine and was used to pack unit trays of confectionary into separately fo.rmed sealed bags with the ethylene/butene1 outer layer next to the trays. The transverse heat-seals were made between crimp heat-seal jaws heated to 1450C. It was found that at speeds up to 46 metres per minute the heat-seal strength of the transverse heat-seals exceeded 450 grams/38 millimetres width. At a speed of 37 metres per minute the average pack length of the bags was measured and found to be 258 millimetres with a pack length variation, measured over 30 bags, of + 2 millimetres.
By way of.control, the procedure was repeated except that both outer layers of the co-extruded melt consisted of a random propylene/ethylene copolymer having an ethylene content of 3.5% by weight. On running the heat-sealable polypropylene film, so produced on the "Versoflow" packaging machine, it was found that at running speeds exceeding 22 metres per minute the heat-seal strength of the transverse heat-seals fell below the acceptable level of 450 grams/38 millimetres width. The average pack length of the bag at a speed of 20 metres per minute was measured and found to be 258 millimetres with a pack length variation, measured over 30 bags, of f 2 millimetres.
The procedure was again repeated except that both outer layers of the co-extruded melt consisted of a predominantly linear random ethylene/butene-1 copolymer in which the butene-1 content was 20% by weight. When the film was run on the "Versoflow" packaging machine, it was found that at running speeds up to 46 metres per minute the heat-seal strength of the transverse heat-seals were above the acceptable level of 450 grams/38 millimetres width. At a speed of 37 metres per minute the average pack length of the bags was measured and found to be only 240 millimetres with a bag length variation measured over 30 bags of + 7 millimetres.

Claims (12)

1. A heat-sealable oriented polypropylene film comprising a bse film of oriented polypropylene film having on one surface a layer of a random propylene/ethylene copolymer in which the ethylene content lies in the range between 2% and 6% by weight and on the other surface a predominantly linear randon copolymer of ethylene and between 6% and 40% by weight of the random copolymer of at least one further alpha olefin having at least three carbon atoms per molecule.
2. A polypropylene film as claimed in claim 1 in which amount of the further alpha olefin in the predominantly linear random copolymer lies in the range between 10% and 35% by weight.
3. A polypropylene film as claimed in claim 1 or claim 2 in which the further alpha olefin is propylene.
4. A polypropylene film as claimed in claim 1 or claim 2 in which the further alpha olefin is butene-1.
5. A polypropylene film as claimed in claim 1 substantially as described in the Example.
6. A method for the manufacture of a heatsealable oriented polypropylene film comprising applying to one surface of a base polypropylene film a layer of a random propylene/ethylene copolymer in which the ethylene content lies in the range between 2% and 6% by weight and to the other surface a predominantly linear random copolymer of ethylene and between 6% and 40% by weight of the random copolymer of at least one further alpha olefin having at least three carbon atoms per molecule, bringing the combination to a stretch orientatable condition and stretching in at least one direction.
7. A method as claimed in claim 6 in which the layer of the propylene/ethylene copolymer and the layer of the copolymer of ethylene and at least one further alpha olefin are supplied to the base polypropylene film during co-extrusion of a melt of the copolymers and the polypropylene through a slot or annular orifice die following by quenching prior to stretching under stretch orientatable conditions.
8. A method as claimed in claim 6 or claim 7 in which the amount of the further alpha olefin in the predominantly linear copolymer lies in the range between 10% and 35% by weight of the copolymer.
9. A method as claimed in any one of claims 6 to 8 in which the further alpha olefin is propylene
10. A method as claimed in any one of claims 6 to 8 in which the further alpha olefin is butene-1.
11. A method as claimed in claim 6 substantially as hereinbefore described in the Example.
12. A heat-sealable oriented polypropylene film when manufactured by a method as claimed in any one of claims 6 to 11.
GB7928896A 1978-09-06 1979-08-20 Heat sealable polypropylene films Expired GB2033838B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB7928896A GB2033838B (en) 1978-09-06 1979-08-20 Heat sealable polypropylene films

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
GB7835846A GB2029317A (en) 1978-09-06 1978-09-06 Heat-sealable polypropylene films
GB7928896A GB2033838B (en) 1978-09-06 1979-08-20 Heat sealable polypropylene films

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Publication Number Publication Date
GB2033838A true GB2033838A (en) 1980-05-29
GB2033838B GB2033838B (en) 1982-10-20

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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4439478A (en) * 1980-05-23 1984-03-27 W. R. Grace & Co., Cryovac Division Heat sealable, multi-ply polypropylene film
EP0246369A1 (en) * 1986-05-21 1987-11-25 Shell Oil Company Butylene copolymer blend for form-and-fill film packaging
US4981231A (en) * 1988-04-15 1991-01-01 W. R. Grace & Co.-Conn. Container closure caps and compositions for forming gaskets for them
CN1860034B (en) * 2003-06-18 2010-09-15 阿尔若威金斯安全公司 Security elements

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4390385A (en) 1980-05-23 1983-06-28 W. R. Grace & Co., Cryovac Div. Heat sealable, multi-ply polypropylene film

Cited By (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4439478A (en) * 1980-05-23 1984-03-27 W. R. Grace & Co., Cryovac Division Heat sealable, multi-ply polypropylene film
EP0246369A1 (en) * 1986-05-21 1987-11-25 Shell Oil Company Butylene copolymer blend for form-and-fill film packaging
US4981231A (en) * 1988-04-15 1991-01-01 W. R. Grace & Co.-Conn. Container closure caps and compositions for forming gaskets for them
US5104710A (en) * 1988-04-15 1992-04-14 W. R. Grace Co.-Conn. Container closure caps and compositions for forming gaskets for them
CN1860034B (en) * 2003-06-18 2010-09-15 阿尔若威金斯安全公司 Security elements

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GB2033838B (en) 1982-10-20

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