GB2094325A - Ethylene-vinyl acetate copolymer packaging films - Google Patents

Ethylene-vinyl acetate copolymer packaging films Download PDF

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Publication number
GB2094325A
GB2094325A GB8107066A GB8107066A GB2094325A GB 2094325 A GB2094325 A GB 2094325A GB 8107066 A GB8107066 A GB 8107066A GB 8107066 A GB8107066 A GB 8107066A GB 2094325 A GB2094325 A GB 2094325A
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United Kingdom
Prior art keywords
vinyl acetate
weight
copolymer
film
ethylene
Prior art date
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Application number
GB8107066A
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TRANSPARENT PAPER Ltd
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TRANSPARENT PAPER Ltd
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Filing date
Publication date
Application filed by TRANSPARENT PAPER Ltd filed Critical TRANSPARENT PAPER Ltd
Priority to GB8107066A priority Critical patent/GB2094325A/en
Publication of GB2094325A publication Critical patent/GB2094325A/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/08—Copolymers of ethene
    • C08L23/0846—Copolymers of ethene with unsaturated hydrocarbons containing other atoms than carbon or hydrogen atoms
    • C08L23/0853—Vinylacetate
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B65—CONVEYING; PACKING; STORING; HANDLING THIN OR FILAMENTARY MATERIAL
    • B65D—CONTAINERS FOR STORAGE OR TRANSPORT OF ARTICLES OR MATERIALS, e.g. BAGS, BARRELS, BOTTLES, BOXES, CANS, CARTONS, CRATES, DRUMS, JARS, TANKS, HOPPERS, FORWARDING CONTAINERS; ACCESSORIES, CLOSURES, OR FITTINGS THEREFOR; PACKAGING ELEMENTS; PACKAGES
    • B65D65/00—Wrappers or flexible covers; Packaging materials of special type or form
    • B65D65/38—Packaging materials of special type or form
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L53/00—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
    • C08L53/02—Compositions of block copolymers containing at least one sequence of a polymer obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers of vinyl-aromatic monomers and conjugated dienes

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Mechanical Engineering (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

Polyolefin film bags are susceptible to failure at low temperatures, as when used to contain frozen foods. Improvement in durability has been obtained by using ethylene/vinyl acetate copolymer film bags, but the film cannot be effectively used in printing and packing machinery if the vinyl acetate content exceeds 7% by weight. It has now been discovered that low temperature durability of such films can be improved by increasing the vinyl acetate content to from above 7% up to 15% by weight while retaining practical machineability, if the melt flow index of the copolymer is selected to be from 0.2 g/10 min to 0.9g/10 min (ASTM D 1238). The copolymer may be blended with a rubbery modifier, such as a copolymer of ethylene and propylene or a copolymer of styrene and butadiene.

Description

SPECIFICATION Polyolefin packaging films and manufacture and use thereof This invention relates to polyolefin packaging films, and to a method of manufacturing them.
The invention also relates to bags formed from such packaging films, especially bags containing frozen foodstuffs.
The use of polyolefin film, in the form of bags, to package deep frozen food-stuffs is a popular form of commerical packaging for distribution to the consumer. Deep frozen vegetable such as peas, brussels sprouts and broad beans present a special problem when packaged in polyolefin film bags because of their near spherical shape. This shape confers a much greater mobility on such contents when compared with, say, frozen chipped potatoes and sliced beans which are more irregular in shape. Such mobility combined with typical commercial packaging and cold storage temperatures of the order of 30a C. to --400C. impose considerable stresses on the polyolefin film bag during handling which can lead to the unacceptable splitting of the bag with consequent loss of contents.
Low density polyethylene film bags are particularly susceptible to this type of failure at temperatures below only OOC. Low density polyethylene film modified by incorporating small percentages of "rubbery" block copolymers of styrene and butadiene are known to offer improved impact strength and durability at temperatures down to as low as -200C. Below this temperature, such films, nevertheless, begin to fail at an unacceptable rate.
It is also known that a further improvement in the durability of polyolefin films can be achieved for temperatures below -200C. if film comprising a copolymer of ethylene and vinyl acetate is substituted for polyethylene homopolymer and is similarly modified with a "rubbery" styrene/butadiene block copolymer. These films can exhibit acceptable durability at temperatures in the range -300C. to -400C. This latter improvement is attributed to the presence of the vinyl acetate co-monomer in the ethylene/vinyl acetate copolymer. Impact tests performed upon ethylene/vinyl acetate copolymer films of this type confirm that the impact strength at sub zero temperatures improves as the percentage content of the vinyl acetate comonomer increases.
However, in practice if the vinyl acetate content exceeds about 7% the resulting film, whilst having good impact strength, normally becomes too "rubbery" and elastic to permit effective machineability on printing and packaging machinery. Films with vinyl acetate contents of less than 7% are described in British Patent Specification No. 1,575,846.
We have now found that it is possible further to improve the low temperature durability of such films by increasing above 7% by weight the percentage of the vinyl acetate co-monomer present in the ethylene/vinyl acetate copolymer films while retaining for the films sufficiently nonrubbery or elastic properties to permit practical machineability of the films on conventional printing and packaging machinery, provided that the melt flow index (hereinafter termined"MFí") of the ethylene/vinyl acetate copolymer is selected so as to lie in the range of from 0.2 g./1 0 min. to 0.9 g./I 0 min. (ASTM D 1238).
Accordingly one aspect of the present invention broadly provides a packaging film, comprising an ethylene/vinyl acetate copolymer in which the vinyl acetate content is from above 7% to 1 5% by weight and the MFI of which is from 0.2 g./1 0 min. to 0.9 g./1 0 min. (ASTM D 1238).
According to another aspect of the present invention there is provided a method of manufacturing a packaging film, wherein an ethylene/vinyl acetate copolymer in which the vinyl acetate content is from above 7% to 1 5% by weight and the MFI of which is from 0.2 g./1 0 min. to 0.9 g./1 0 min. is formed into a film.
The ethylene/vinyl acetate copolymer of the packaging film of the present invention may be modified by blending it with a "rubbery" modifier which may be a copolymer of ethylene and propylene, or a copolymer of styrene and butadiene. The modifier may be present in an amount of 5% to 15% by weight, preferably 5% to 10%.
In accordance with the present method, packaging film comprising an ethylene/vinyl acetate copolymer with a vinyl acetate content in the range of 10% to 15% by weight and an MFI in the range of 0.2 to 0.9 g./1 0 min. (ASTM D 1238) and containing an ethylene/propylene copolymer in the range of 5% to 1 5% by weight of the blend has been produced. This film exhibits exceptional durability at temperatures in the range -300C. to 40C C. whilst remaining sufficiently non "rubbery" or elastic to permit practical machineability on conventional printing and packaging machinery.
Preferably the vinyl acetate content of the ethylene/vinyl acetate copolymer is from 1 1% to 13% by weight and the MFI of the copolymer is from 0.30 to 0.40 g./1 0 min. (ASTM D 1238).
The MFI of the ethylene/vinyl acetate copolymer is not necessarily directly related to the higher level of vinyl acetate present although the level of the latter can have a minor affect in some of these copolymers. Indeed increasing the level of vinyl acetate normally increases rather than decreases the value of the MFI where it has an effect at all. The MFI is primarily a function of general polymer structure and is affected more by overall molecular weight and the degree of chain branching on the polymer back bone, neither of these parameters being necessarily deperident themselves on the level of any comonomer (such as vinyl acetate) present.
By way of illustrating further the effect which the low MFI value has on the impact strength of ethylene/vinyl acetate copolymers of similar vinyl acetate content, a 50 micron thick film made from an ethylene/vinyl acetate copolymer having a vinyl acetate content of 12% by weight and an MFI of 0.35 g./1 0 min. and containing no additional "rubbery" modifier, has an impact strength of 788 g. at room temperature while a similar film made from a copolymer with a vinyl acetate content of 10% by weight but an MFI of 1.3 g./1 0 min, has an impact strength of only 343 g. at room temperature. These values would naturally be lower at -25 to -270C. but the advantageous difference of the copolymer having the lower MFI would be retained.
The invention also includes a packaging film in accordance with the invention when formed into a bag and when the bag so formed contains frozen food-stuffs.
The invention will now be more specifically illustrated by way of the following Example: Example A film (a) was produced by blending together 90% by weight of an ethylene/vinyl acetate copolymer in which the vinyl acetate content was 12% by weight and the MFI was 0.35 g./1 0 min.
(ASTM D 1238) with 10% by weight of the blend of an ethylene/propylene copolymer (marketed by Esso Chemical Company as "Vistaflex" VM6).
A film (b) was produced by blending together 90% by weight of an ethylene/vinyl acetate copolymer in which the vinyl acetate content was 12% by weight and the MFI was 0.35 g./1 0 min.
(ASTM D 1238) with 10% by weight of the blend of a styrene/butadiene copolymer (marketed by Shell Chemicals U.K. Limited as "Cariflex" TR 1102).
A further film (c) was produced, by way of comparison, according to known prior art (for example British Patent Specification No.
1,575,846) by blending together an ethylene/vinyl acetate copolymer in which the vinyl acetate content was only 4% by weight with 10% by weight of the blend of a styrene/butadiene copolymer (Shell "Cariflex" TR 1102).
All three films were produced by conventional tubular blown film extrusion to a thickness of approximately 63 microns. The chosen die gap was nominally 1 mm. and the blow-up-ratio was 2:1 in each case.
The films so obtained were subsequently subjected to impact testing at a temperature of -270C. using a falling dart method similar to that described in British Standard No. 2782 Method 306F. The impact strength was determined in the number of grams weight of the falling dart, falling through a vertical height of 400 mm. and capable of rupturing 50% of the specimens of the particular sample under test. The results correlate to the likelihood of the film, in bag form, bursting under stress.
Impact Strength Film Sample at --27 OC. (grams) (a) 778 (b) 875 (c) 500 Despite the higher vinyl acetate content present in films (a) and (b) the subsequent machineability of the films on printing and packaging machinery was satisfactory when compared with film (c).
Claims (filed on 22 February 1982) 1. A packaging film, wherein the film comprises an ethylene/vinyl acetate copolymer in which the vinyl acetate content is from above 7% to 1 5% by weight and of which the MFI (as hereinbefore defined) is from 0.2 g./1 0 min. to 0.9 g./10 min.
2. A packaging film as claimed in Claim 1, wherein the copolymer has been modified by blending it with a rubbery modifier.
3. A packaging film as claimed in Claim 2, wherein the rubbery modifier is a copolymer of ethylene and propylene or a copolymer of styrene and butadiene.
4. A packaging film as claimed in Claim 2 or 3, wherein the rubbery modifier is present in an amount of 5% to 15% by weight.
5. A packaging film as claimed in any one of Claims 2 to 4, wherein the rubbery modifier is present in an amount of 5% to 10% by weight.
6. A packaging film as claimed in any one of Claims 1 to 5, wherein the vinyl acetate content .of the ethylene/vinyl acetate copolymer is from 1 1%two 13% by weight.
7. A packaging film as claimed in any one of Claims 1 to 6, wherein the MFI of the ethylene/viny! acetate copolymer is 0.30 to 0.40 g./10 min.
8. A packaging film substantially as hereinbefore described in Example (a) or (b) of the foregoing Examples.
9. A packaging film as claimed in any one of Claims 1 to 8 when formed into a bag.
10. A packaging film as claimed in Claim 9 when the bag contains frozen food-stuffs.
11. A method of manufacturing a packaging film, wherein an ethylene/vinyl acetate copolymer in which the vinyl acetate content is from above 7% to 15% by weight and of which the MFI (as hereinbefore defined) is from 0.2 g./1 0 min. to 0.9 g./1 0 min. is formed into a film.
12. A method as claimed in Claim 11, wherein the copolymer has been modified by blending it with a rubbery modifier.
13. A method as claimed in Claim 12, wherein the rubbery modifier is a copolymer of ethylene and propylene or a copolymer of styrene and butadiene.
14. A method as claimed in Claim 12 or 13, wherein the rubbery modifier is present in an amount of 5% to 15% by weight.
1 5. A method as claimed in any one of Claims 12 to 14, wherein the rubbery modifier is present in an amount of 5% to 10% by weight.
1 6. A method as claimed in any one of Claims 11 to 14, wherein the vinyl acetate content of the ethylene/vinyl acetate copolymer is from 11% to 13% by weight.
17. A method as claimed in any one of Claims
**WARNING** end of DESC field may overlap start of CLMS **.

Claims (17)

**WARNING** start of CLMS field may overlap end of DESC **. vinyl acetate content of 12% by weight and an MFI of 0.35 g./1 0 min. and containing no additional "rubbery" modifier, has an impact strength of 788 g. at room temperature while a similar film made from a copolymer with a vinyl acetate content of 10% by weight but an MFI of 1.3 g./1 0 min, has an impact strength of only 343 g. at room temperature. These values would naturally be lower at -25 to -270C. but the advantageous difference of the copolymer having the lower MFI would be retained. The invention also includes a packaging film in accordance with the invention when formed into a bag and when the bag so formed contains frozen food-stuffs. The invention will now be more specifically illustrated by way of the following Example: Example A film (a) was produced by blending together 90% by weight of an ethylene/vinyl acetate copolymer in which the vinyl acetate content was 12% by weight and the MFI was 0.35 g./1 0 min. (ASTM D 1238) with 10% by weight of the blend of an ethylene/propylene copolymer (marketed by Esso Chemical Company as "Vistaflex" VM6). A film (b) was produced by blending together 90% by weight of an ethylene/vinyl acetate copolymer in which the vinyl acetate content was 12% by weight and the MFI was 0.35 g./1 0 min. (ASTM D 1238) with 10% by weight of the blend of a styrene/butadiene copolymer (marketed by Shell Chemicals U.K. Limited as "Cariflex" TR 1102). A further film (c) was produced, by way of comparison, according to known prior art (for example British Patent Specification No. 1,575,846) by blending together an ethylene/vinyl acetate copolymer in which the vinyl acetate content was only 4% by weight with 10% by weight of the blend of a styrene/butadiene copolymer (Shell "Cariflex" TR 1102). All three films were produced by conventional tubular blown film extrusion to a thickness of approximately 63 microns. The chosen die gap was nominally 1 mm. and the blow-up-ratio was 2:1 in each case. The films so obtained were subsequently subjected to impact testing at a temperature of -270C. using a falling dart method similar to that described in British Standard No. 2782 Method 306F. The impact strength was determined in the number of grams weight of the falling dart, falling through a vertical height of 400 mm. and capable of rupturing 50% of the specimens of the particular sample under test. The results correlate to the likelihood of the film, in bag form, bursting under stress. Impact Strength Film Sample at --27 OC. (grams) (a) 778 (b) 875 (c) 500 Despite the higher vinyl acetate content present in films (a) and (b) the subsequent machineability of the films on printing and packaging machinery was satisfactory when compared with film (c). Claims (filed on 22 February 1982)
1. A packaging film, wherein the film comprises an ethylene/vinyl acetate copolymer in which the vinyl acetate content is from above 7% to 1 5% by weight and of which the MFI (as hereinbefore defined) is from 0.2 g./1 0 min. to 0.9 g./10 min.
2. A packaging film as claimed in Claim 1, wherein the copolymer has been modified by blending it with a rubbery modifier.
3. A packaging film as claimed in Claim 2, wherein the rubbery modifier is a copolymer of ethylene and propylene or a copolymer of styrene and butadiene.
4. A packaging film as claimed in Claim 2 or 3, wherein the rubbery modifier is present in an amount of 5% to 15% by weight.
5. A packaging film as claimed in any one of Claims 2 to 4, wherein the rubbery modifier is present in an amount of 5% to 10% by weight.
6. A packaging film as claimed in any one of Claims 1 to 5, wherein the vinyl acetate content .of the ethylene/vinyl acetate copolymer is from 1 1%two 13% by weight.
7. A packaging film as claimed in any one of Claims 1 to 6, wherein the MFI of the ethylene/viny! acetate copolymer is 0.30 to 0.40 g./10 min.
8. A packaging film substantially as hereinbefore described in Example (a) or (b) of the foregoing Examples.
9. A packaging film as claimed in any one of Claims 1 to 8 when formed into a bag.
10. A packaging film as claimed in Claim 9 when the bag contains frozen food-stuffs.
11. A method of manufacturing a packaging film, wherein an ethylene/vinyl acetate copolymer in which the vinyl acetate content is from above 7% to 15% by weight and of which the MFI (as hereinbefore defined) is from 0.2 g./1 0 min. to 0.9 g./1 0 min. is formed into a film.
12. A method as claimed in Claim 11, wherein the copolymer has been modified by blending it with a rubbery modifier.
13. A method as claimed in Claim 12, wherein the rubbery modifier is a copolymer of ethylene and propylene or a copolymer of styrene and butadiene.
14. A method as claimed in Claim 12 or 13, wherein the rubbery modifier is present in an amount of 5% to 15% by weight.
1 5. A method as claimed in any one of Claims 12 to 14, wherein the rubbery modifier is present in an amount of 5% to 10% by weight.
1 6. A method as claimed in any one of Claims 11 to 14, wherein the vinyl acetate content of the ethylene/vinyl acetate copolymer is from 11% to 13% by weight.
17. A method as claimed in any one of Claims
11 to 1 5, wherein the MFI of the ethylene/vinyl acetate copolymer is 0.30 to 0.40 g./1 0 min.
1 8. A method as claimed in any one of Claims 11 to 17, wherein the film is formed by a tubular blown film extrusion technique.
1 9. A method of manufacturing a packaging film substantially as hereinbefore described in Example (a) or (b) of the foregoing Examples.
GB8107066A 1981-03-06 1981-03-06 Ethylene-vinyl acetate copolymer packaging films Withdrawn GB2094325A (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB8107066A GB2094325A (en) 1981-03-06 1981-03-06 Ethylene-vinyl acetate copolymer packaging films

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8107066A GB2094325A (en) 1981-03-06 1981-03-06 Ethylene-vinyl acetate copolymer packaging films

Publications (1)

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GB2094325A true GB2094325A (en) 1982-09-15

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GB8107066A Withdrawn GB2094325A (en) 1981-03-06 1981-03-06 Ethylene-vinyl acetate copolymer packaging films

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2139634A (en) * 1983-05-13 1984-11-14 Grace W R & Co Silent film for ostomy pouches
EP0424724A2 (en) * 1989-10-10 1991-05-02 Viskase Corporation Thermoplastic film incorporating high melt index resins
US5034078A (en) * 1985-05-08 1991-07-23 Exxon Chemical Patents Inc. Method of making an elastomeric film

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2139634A (en) * 1983-05-13 1984-11-14 Grace W R & Co Silent film for ostomy pouches
FR2545828A1 (en) * 1983-05-13 1984-11-16 Grace W R Ltd FORMED FILM OF A POLYMERIC MIXTURE HAVING SILENT AND PLIABILITY CHARACTERISTICS, AND CONTAINERS FORMED THEREFROM
US5034078A (en) * 1985-05-08 1991-07-23 Exxon Chemical Patents Inc. Method of making an elastomeric film
EP0424724A2 (en) * 1989-10-10 1991-05-02 Viskase Corporation Thermoplastic film incorporating high melt index resins
EP0424724A3 (en) * 1989-10-10 1992-03-25 Viskase Corporation Thermoplastic film incorporating high melt index resins
US5635261A (en) * 1989-10-10 1997-06-03 Viskase Corporation Thermoplastic film incorporating high melt index resins

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