GB2063278A - Composition for Production of Cold Drawn Film - Google Patents

Composition for Production of Cold Drawn Film Download PDF

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Publication number
GB2063278A
GB2063278A GB8100807A GB8100807A GB2063278A GB 2063278 A GB2063278 A GB 2063278A GB 8100807 A GB8100807 A GB 8100807A GB 8100807 A GB8100807 A GB 8100807A GB 2063278 A GB2063278 A GB 2063278A
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Application
Patent type
Prior art keywords
composition
film
ethylene
olefin
copolymer
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
Application number
GB8100807A
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GB2063278B (en )
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Asahi-Dow Ltd
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Asahi-Dow Ltd
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Classifications

    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/04Homopolymers or copolymers of ethene
    • C08L23/08Copolymers of ethene
    • C08L23/0807Copolymers of ethene with unsaturated hydrocarbons only containing more than three carbon atoms
    • C08L23/0815Copolymers of ethene with aliphatic 1-olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/16Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/10Homopolymers or copolymers of propene
    • C08L23/14Copolymers of propene
    • C08L23/142Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • CCHEMISTRY; METALLURGY
    • C08ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08LCOMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02Compositions 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
    • C08L23/18Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms

Abstract

A polymer composition useful for production of a stretched, shrinkable wrapping film by cold-drawing comprises a homogeneous blend of: (b) an ethylene- alpha -olefin copolymer elastomer having a density of not more than 0.91 g/cm<3> and (c) at least one polymer selected from crystalline polypropylene and crystalline polybutene-1, the amounts of the components being such as to satisfy in terms of weight ratio the expression 0.90>/=b/(b+c)>/=0.30.

Description

SPECIFICATION Composition for Production of Cold Drawn Film In our copending patent application no.

39283/78 we describe and claim a cold drawn film having a tensile strength of not less than 5.0 kg/mm2 and a haze of not more than 4.0%, which film comprises a homogeneous blend of components (A), (B) and (C) in the combinations (A)+(B), (B)+(C) or (A)+(B)+(C), wherein (A) is at least one polymer selected from low-density polyethylene and copolymers of ethylene with vinyl ester monomers, unsaturated aliphatic monocarboxylic acids and alkyl esters of said carboxylic acids which are all copolymerizable with ethylene, (B) is an ethylene--olefin copolymer elastomer having a density of not more than 0.91 g/cm3, and (C) is at least one polymer selected from crystalline polypropylene, high-density polyethylene or crystalline polybutene- 1.

The said copending application also describes and claims a method for producing the above cold drawn film. The present invention provides certain compositions which may be used to produce the film which is the subject of patent application no.

39283/78.

The present invention provides a composition comprising a homogeneous blend of components (b) and (c); wherein (b) is an ethylene-a-olefin copolymer elastomer having a density of not more than 0.91 g/cm3 and (c) is at least one polymer selected from crystalline polypropylene and crystalline polybutene-1, the amounts of the components being such as to satisfy in terms of weight ratio the expression 0.90~b/(b+c)~0.30.

The manufacture of a cold drawn film from this composition is described in detail in patent application no. 39283/78.

The thermoplastic elastomer comprising a copolymer of ethylene with at least one -olefin as the component (b) is a non-rigid copolymer of ethylene with at least one ct-olefin selected from ct;-olefins having from 3 to 12 carbon atoms. As dccasion demands, this elastomer may be further copolymerized with a small amount of a hydrocarbon of the polyene structure such as, for example, 1,4-hexadiene, ethylidene norbornene, etc. Examples of the n-olefin suitable for this purpose include propylene, butene-1, hexene-1, heptene-1, 4-methyl-1-pentene, octene-1, etc.Of these n-olefins, preferable are propylene and butene-1. In any of these copolymers, the ethylene content is desired to fall in the range of from 20 to 90 mol %, more desirably from 40 to 90 mol %, preferably from 65 to 88 mol %.

These copolymers are of such nature that the density is not more than 0.91 g/cm3, the Vicat softening point as determined in accordance with ASTM D-1 525 (value under 1 kg of load) is not more than 800 C, preferably not more than 700C and the crystallinity in the rubbery zone generally ranges from substantiai amorphousness to low partial crystallinity of the order of not more than 30% of crystallinity degree determined with Xray.

The component (b) is particularly desired to be a copolymer of ethylene with propylene or butene-1, and this copolymer may, when necessary, incorporate therein a small amount of a compound of the diene structure in the form of a copolymer. It is, therefore, a thermoplastic elastomer in the form of a random copolymer obtained by the polymerization using a catalyst of the system produced with a vanadium compound and an organic aluminum compound. The elastomer possesses a melt index of from 0.1 to 10, preferably from 0.2 to 6.

The polymer (c) is at least one selected from crystalline PP (polypropylene) and high molecular PB-1 (polybutene-1) which each possess relatively high rigidity and relatively high degree of crystallinity. The polymer has relatively high rigidity and desirably a Vicat softening point of not less than 1 000C.

The crystalline PP which is one of the members of the group from which the component (c) of the composition of this invention is selected is a crystalline PP with high isotacticity usually available on the market. It is desired to be a homopolymer of propylene or any of the copolymers of propylene with not more than 10 mol % of ethylene, 1-butene or some other r'.- olefin. It may be a mixture of these copolymers.

The polybutene-1 is desired to be a crystalline homopolymer of more than 90 mol % of butene-1 with other monomer. Unlike a liquid-to-waxy low molecular polymer, these polymers are desired to possess a melt index in the range of from 0.2 to 10 for the same reason as mentioned above. Of the possible members of the aforementioned group, it is desirable to use chiefly the crystalline polypropylene.

The composition of the present invention comprises a combination of components (b)+(c).

The mixing ratio of these components in terms of weight ratio is such as to satisfy 0.30 < c/(b+c) < 0.90 and more desirably to satisfy: 0.40 < c/(b+c) < 0.87 and preferably to satisfy: 0.50~c/(b+c) < 0.85 If the amount of the non-rigid component (b) is less than the allowable lower limit indicated above, the blend fails to manifest the expected synergistic effect and, therefore, suffers from inferior processibility, lowered film strength and impaired optical properties and low-temperature shrinkability.If the amount is more than the allowable upper limit, a tubular sheet produced from the blend is degraded in film-forming property and stretchability and becomes so soft as to entail the phenomenon of film-to-film blocking and the produced film exhibits insufficient heat resistance, sealability, strength dnd optical properties. The component (c) serves to improve not only modulus but also seal properties such as, for example, thermal properties including heat resistance particularly in the higher portion of the allowable temperature range.

As described above, this invention permits the quenched tubular sheet which has been produced from the composition obtained by using the specific comporveats iatheis sespectiMe specE & c %%t\\\ amounts to be cold stretched with ample stability in the manner to be described hereinafter. If the tubular sheet is further treated with a specific high-energy ray so as to have the gel content (insolubles in boiling xylene) or the melt index brought into a specific range, the components in the composition produce a synergistic effect such as to manifest the desired cold stretchability (at temperatures in the range of from 20 to 1 000C) under specific stretching conditions, giving rise to a film of outstanding properties.

Now, the composition produced by using the components in the preferred mixing ratio will be described Generally, the crystalline PP component (c) is hardly crosslinked even when it is subjected to treatment with high-energy radiation. The elastomer of the copolymer of a-- olefin (b) exhibits rather high compatibility with polypropylene and induces the reaction of crosslinking readily. Consequently, the synergistic effect brought about from the proper dispersion of the components in the composition is coupled with the synergistic effect which issues from the action of the high-energy radiation. The combination of these synergistic effects is believed to result in the production of a film wherein there is formed a specific, molecularly heterogeneous crosslinked matrix.The treatment with high-energy radiation, accordingly, improves notably the stable cold stretchability of the tubular sheet and the film's heat resistance and heat seal strength, enhances the thermal shrinkability and strength of the film at low temperatures, represses possible degradation in optical properties and physical properties after thermal shrinkage (such as optical properties, seal strength and mechanical strength) and expands the range of packaging temperatures. Thus, the properties possessed by the film which is produced from the crosslinked tubular sheet far excel those possessed by the plasticized PVC film and PP film which have heretofore been rated to be the best films.

The composition of this invention may also be effectively used when it is mixed with some other composition insofar as the amount of the additive composition does not impair the stretchability and various other properties of a film which is produced from the composition.

The compositions of this invention are illustrated in the following Examples.

Example 1 80 parts by weight of an ethylene-a-olefin copolymer elastomer (melt index: 0.25, Vicat softening point: less than 50dC, density 0.88 g/cm3, a-olefin: butene-1, a-olefin unit content 20 mol %) were mixed with 20 parts by weight of crystalline polypropylene (melt index: 0.8, ethylene unit content: 6% by weight). The composition was extruded, at the maximum temperature of the cylinder part of 2500C, from an annular die 150 mm in diameter having a slit of 1.5 mm provided with a mixing head type scew 65 di2nQttx Th\\ \\) o\ .

The extruded film was quenched with water about 10 cm from the lip of the die. A raw tubular film 200 u in thickness and with a deviation in thickness of +2.0% was obtained.

The production of a stretched film is described in Example 4 (Run No. 22) of GB 2007685.

Example 2 80 parts by weight of ethylene--olefin copolymer elastomer (cr-olefin: propylene, a- olefin unit content: 20 mol %, melt index: 0.25, density: 0.88 g/cm3, Vicat softening point: less than 400C) were mixed with 20 parts by weight of crystalline polypropylene (ethylene unit content: 5% by weight, melt index: 0.6, Vicat softening point: 1200 C, density: 0.87 g/cm3).

The composition was plasticized and kneaded, at the maximum temperature of the cylinder part of 2600C, by a mixing head type screw 45 mm in diameter (VD=44), and pelletized. The composition was extruded through an extruded 45 mm in diameter (L/D=37) fitted with a T-type die which had a slit 1 mm in thickness and 40 cm in width. While extruding a liquid additive was injected into the rear part of the cylinder under pressure. The melted polymer composition extruded from the die was introduced into water to form a raw tubular film 100 St in thickness.

The production of a stretched film is described in Example 10 (Run No. 29) of GB 2007685.

Claims (12)

Claims
1. A composition comprising a homogeneous blend of components (b)+(c); wherein (b) is an ethylene-a-olefln copolymer elastomer having a density of not more than 0.91 g/cm3 and (c) is at least one polymer selected from t crystalline polypropylene and crystalline polybutene-1, the amounts of the components being such as to satisfy in terms of weight ratio the expression 0.90 > b/(b+c) > 0.30
2. A composition according to Claim 1, wherein the ethylene-a-olefin copolymer as the component (b) has an ethylene unit content of not more than 90 mol % and not less than 20 mol %.
3. A composition according to Claim 1, wherein the ethylene-a-olefin copolymer as the component (b) has an ethylene unit content of not more than 90 mol % and not less than 40 mol %.
4. A composition according to any one of Claims 1 to 3, wherein the elastomer as the component (b) is a non-rigid copolymer having a Vicat softening point of not more than 800C and a degree of crystallization of not more than 30%, wherein the a-olefin component contained therein is at least one a-olefin having from 3 to 1 2 carbon atoms.
5. A composition according to any one of Claims 1 to 4, wherein the elastomer as the component (b) is a random copolymer wherein the a-olefin component is propylene or butene-1.
6. A composition according to any one of Claims 1 to 5, wherein the ethylene-a-olefin copolymer as the component (b) has copolymerized polyene units in addition to the main components derived from ethylene and aolefin.
7. A composition according to Claim 6, wherein the polyene contains not more than 5 mol % of a non-conjugate diene selected from hexadiene and norbornene derivatives.
8. A composition according to any one of Claims 1 to 7, wherein the component (c) is a rigid polymer having a Vicat softening point of not less than 1000C.
9. A composition according to any one of Claims 1 to 8, wherein the component (c) is a crystalline polypropylene or a crystalline copolymer of propylene with ethylene in an amount of not more than 10 mol % or a mixture thereof.
10. A composition according to any one of Claims 1 to 9, wherein the components are in amounts such as to satisfy the expression 0.87 ~b/(b+c)~0.40 in terms of weight ratio.
11. A composition according to Claim 1 substantially as described in any one of the Examples.
12. A composition according to Claim 1 in the form of an unstretched film.
GB8100807A 1978-10-04 1978-10-04 Composition for production of cold drawn film Expired GB2063278B (en)

Priority Applications (1)

Application Number Priority Date Filing Date Title
GB8100807A GB2063278B (en) 1978-10-04 1978-10-04 Composition for production of cold drawn film

Applications Claiming Priority (1)

Application Number Priority Date Filing Date Title
GB8100807A GB2063278B (en) 1978-10-04 1978-10-04 Composition for production of cold drawn film

Publications (2)

Publication Number Publication Date
GB2063278A true true GB2063278A (en) 1981-06-03
GB2063278B GB2063278B (en) 1983-01-12

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Cited By (13)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2529563A1 (en) * 1982-06-30 1984-01-06 Charbonnages Ste Chimique polypropylene compositions and ethylene / a-olefin and their application in the manufacture of mono-oriented son
EP0191990A2 (en) * 1984-12-27 1986-08-27 Nippon Oil Co. Ltd. Crosslinked resin compositions
EP0235930A2 (en) * 1986-01-31 1987-09-09 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive tape
EP0294770A2 (en) * 1987-06-08 1988-12-14 Union Carbide Corporation Impact polypropylene
US4904253A (en) * 1986-01-31 1990-02-27 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive tape
EP0397517A2 (en) * 1989-05-11 1990-11-14 Nippon Petrochemicals Company, Limited Polypropylene film
US4981231A (en) * 1988-04-15 1991-01-01 W. R. Grace & Co.-Conn. Container closure caps and compositions for forming gaskets for them
GB2245572A (en) * 1990-06-26 1992-01-08 Du Pont Canada A stretch wrap film
WO1992014784A2 (en) * 1991-02-22 1992-09-03 Exxon Chemical Patents Inc. Heat sealable blend of very low density polyethylene or plastomer with polypropylene based polymers and heat sealable film and articles made thereof
US5530065A (en) * 1992-01-07 1996-06-25 Exxon Chemical Patents Inc. Heat sealable films and articles made therefrom
EP0870603A4 (en) * 1995-06-30 1998-10-14
US6689436B2 (en) * 1995-12-18 2004-02-10 Basell Technology Company Bv LLDPE-based thermoshrinkable films
CN100551675C (en) 1999-09-01 2009-10-21 埃克森化学专利公司 Cold stretching film

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE69333773T2 (en) 1992-11-13 2006-04-06 Cryovac, Inc. Heat-shrinkable, produced by single-site catalysis copolymers containing films.

Cited By (23)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2529563A1 (en) * 1982-06-30 1984-01-06 Charbonnages Ste Chimique polypropylene compositions and ethylene / a-olefin and their application in the manufacture of mono-oriented son
EP0102857A1 (en) * 1982-06-30 1984-03-14 Ecp Enichem Polymeres France Compositions of polypropylene and ethylene/alpha-olefin copolymers and their use in the manufacture of stretched filaments
EP0191990A2 (en) * 1984-12-27 1986-08-27 Nippon Oil Co. Ltd. Crosslinked resin compositions
EP0191990A3 (en) * 1984-12-27 1989-06-07 Nippon Oil Co. Ltd. Crosslinked resin compositions
EP0235930A2 (en) * 1986-01-31 1987-09-09 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive tape
EP0235930A3 (en) * 1986-01-31 1989-05-03 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive tape
US4904253A (en) * 1986-01-31 1990-02-27 Minnesota Mining And Manufacturing Company Pressure-sensitive adhesive tape
EP0294770A2 (en) * 1987-06-08 1988-12-14 Union Carbide Corporation Impact polypropylene
EP0294770A3 (en) * 1987-06-08 1989-03-22 Union Carbide Corporation Impact polypropylene
US5104710A (en) * 1988-04-15 1992-04-14 W. R. Grace Co.-Conn. Container closure caps and compositions for forming gaskets for them
US4981231A (en) * 1988-04-15 1991-01-01 W. R. Grace & Co.-Conn. Container closure caps and compositions for forming gaskets for them
EP0397517A2 (en) * 1989-05-11 1990-11-14 Nippon Petrochemicals Company, Limited Polypropylene film
EP0397517A3 (en) * 1989-05-11 1992-04-08 Nippon Petrochemicals Company, Limited Polypropylene film
GB2245572A (en) * 1990-06-26 1992-01-08 Du Pont Canada A stretch wrap film
WO1992014784A2 (en) * 1991-02-22 1992-09-03 Exxon Chemical Patents Inc. Heat sealable blend of very low density polyethylene or plastomer with polypropylene based polymers and heat sealable film and articles made thereof
WO1992014784A3 (en) * 1991-02-22 1992-10-15 Exxon Chemical Patents Inc Heat sealable blend of very low density polyethylene or plastomer with polypropylene based polymers and heat sealable film and articles made thereof
US5358792A (en) * 1991-02-22 1994-10-25 Exxon Chemical Patents Inc. Heat sealable blend of very low density polyethylene or plastomer with polypropylene based polymers and heat sealable film and articles made thereof
US5530065A (en) * 1992-01-07 1996-06-25 Exxon Chemical Patents Inc. Heat sealable films and articles made therefrom
EP0870603A4 (en) * 1995-06-30 1998-10-14
EP0870603A1 (en) * 1995-06-30 1998-10-14 Sumitomo Bakelite Company Limited Laminate
US5976651A (en) * 1995-06-30 1999-11-02 Sumitomo Bakelite Company Limited Propylene packaging laminate comprising methylpentene resin blend layer
US6689436B2 (en) * 1995-12-18 2004-02-10 Basell Technology Company Bv LLDPE-based thermoshrinkable films
CN100551675C (en) 1999-09-01 2009-10-21 埃克森化学专利公司 Cold stretching film

Also Published As

Publication number Publication date Type
GB2063278B (en) 1983-01-12 grant

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732 Registration of transactions, instruments or events in the register (sect. 32/1977)
PE20 Patent expired after termination of 20 years

Effective date: 19981003