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WO1996007699A1 - Film de copolymere a capacite de retrait elevee - Google Patents

Film de copolymere a capacite de retrait elevee Download PDF

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Publication number
WO1996007699A1
WO1996007699A1 PCT/US1995/011041 US9511041W WO9607699A1 WO 1996007699 A1 WO1996007699 A1 WO 1996007699A1 US 9511041 W US9511041 W US 9511041W WO 9607699 A1 WO9607699 A1 WO 9607699A1
Authority
WO
WIPO (PCT)
Prior art keywords
film
monomer
polyolefin
range
group
Prior art date
Application number
PCT/US1995/011041
Other languages
English (en)
Inventor
Edward K. Bullock
Original Assignee
Applied Extrusion Technologies, Inc.
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Applied Extrusion Technologies, Inc. filed Critical Applied Extrusion Technologies, Inc.
Priority to EP95931034A priority Critical patent/EP0779911A1/fr
Priority to MX9701781A priority patent/MX9701781A/es
Priority to NZ292443A priority patent/NZ292443A/en
Priority to AU34621/95A priority patent/AU3462195A/en
Priority to BR9508998A priority patent/BR9508998A/pt
Publication of WO1996007699A1 publication Critical patent/WO1996007699A1/fr

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Classifications

    • 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
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/04—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique
    • B29C55/06—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed
    • B29C55/065—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets uniaxial, e.g. oblique parallel with the direction of feed in several stretching steps
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • B29C55/14—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial successively
    • 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
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • 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
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/14—Copolymers of propene
    • C08L23/142—Copolymers of propene at least partially crystalline copolymers of propene with other olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2023/00—Use of polyalkenes or derivatives thereof as moulding material
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
    • B29K2995/0037—Other properties
    • B29K2995/0049—Heat shrinkable
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L57/00—Compositions of unspecified polymers obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C08L57/02—Copolymers of mineral oil hydrocarbons

Definitions

  • a unique feature of a shrink film is its capacity, upon exposure to heat, to shrink or, if restrained, to create shrink tension within the film.
  • shrink film When such a shrink film is used in a process to label or wrap a container, and then it is subjected to a heat history, this process causes the film to shrink around the product, producing a tight, transparent or opaque, wrapping that conforms to the contour of the article and provides useful functions required of label or packaging materials.
  • the ability of a film to shrink upon exposure to some level of heat arises from the orientation of the film during manufacture.
  • the films are usually heated to their orientation temperature range, which varies with the different polymers used for the films, but is usually above room temperature and below the melting temperature of the polymer.
  • the film is then stretched in the cross or transverse direction (TD) and in the longitudinal or machine direction (MD) to orient it. After being stretched, the film is rapidly cooled to quench it, thus freezing the film in its oriented state.
  • TD cross or transverse direction
  • MD longitudinal or machine direction
  • Polyolefin shrink films having a higher shrinkage in the machine direction than in the transverse direction are disclosed or suggested in the prior art.
  • European Publication No. 0 498 249 which was published on August 12, 1992, corresponding to United States Application Serial No. 08/144,629, the entire disclosure of which is incorporated by reference herein, and which is assigned to the same assignee as the present invention, generally describes a single or multilayer biaxially oriented polyolefin film with the predominant orientation in the MD direction and having an MD shrinkage capacity of 4% to 40% in the temperature range of 100*C to 140'C, and a TD shrinkage capacity in the range of -15% to 15% between 100*C and 140*C.
  • the most preferred film is formed of a polypropylene homopoly er.
  • the biaxially oriented polyolefin MD shrink films may be monolayer films, multilayer films, coextruded films, extrusion coated films or coated films.
  • the shrink films of this invention can also exhibit a variety of surface behavior or characteristics common to typical biaxially oriented packaging films as is known to the art.
  • any conventional lamination process may be used inasmuch as the novel polymer shrink film of the present invention has been observed to be capable of being suitably laminated using known technology, e.g., selected from the group consisting of wet bonding, dry bonding, hot melt or wax laminating, extrusion lamination, and thermal or heat laminating; however, dry bonding and thermal or heat laminating are preferred.
  • Dry bonding involves applying adhesive to one of the films or webs.
  • the solvent is evaporated from the adhesive and the adhesive-coated web is combined with the other web material by heat and pressure or by pressure only.
  • Thermal laminating brings together coated substrates under heat and pressure.
  • the webs are heated to the softening point of the coating; however, improved results, e.g., in clarity are obtained when using preheat rolls and a steam box.
  • labels are normally printed and the printing is expected to be permanent. If the exposed printed surface is abraded, then the printing can be removed or scuffed. If, however, the printing is on the inside surface of a clear film and this clear film is laminated to another film, the printing is protected by the clear film. Alternatively, the printing can be on the inside surface of the clear or opaque web which is then laminated to the clear protective overweb. In addition, the outermost surface of the laminate can be made matte, glossy, of low coefficient of friction, different in surface functionality or composition, independent from the nature of the surface required to accept inks. Printing can also be applied to a clear film layer and either a clear or opaque film, or a metallized version of either type of film, can be laminated to the printed web.
  • Flexographic printing procedures typically employ presses selected from the group consisting of stack, central- impression, and in-line presses. Flexographic printing which employs a central impression or common impression plate is preferred.
  • shrinkable films with different shrinkage properties can be laminated to a common printed shrinkable film to give laminates with different shrinkage properties tailored to the particular container or the requirements of the application.
  • shrinkable films of different shrinkage properties can also be laminated together to give a laminate whose shrinkage properties might be difficult to achieve using only a single film.
  • the manufacturing apparatus used in the sequential blown film process as shown in Fig. 1 consists of an extruding system 1, a tubular die 2, a water bath quench system 3, a nip roll assembly 4, reheating oven 5, a single stage bubble blowing section 6 (where MD and TD draw occur) , a convergence section 7, including convergence rolls 7a, 7b and 7c, and draw rolls 8, a heating oven 9 for altering shrinkage properties, draw rolls 10 and a mill roll winder 11.
  • the extrusion system 1 consists of an extruder with output capabilities of 400 lb/hr.
  • the terminal end of the extruder has an annular die 2 which forms the melted polymer into a hollow polymer tube (six inches in diameter) .
  • the extrusion system 21 is composed of one main extruder (60 kg/hr maximum output) and three satellite extruders (two with 12 kg/hr maximum output and one with a 6 kg/hr maximum output) (not shown) .
  • the casting unit of one of the one/two stage MD draw section 22 is composed of an air knife (not shown) , a chrome casting roll 26, a water bath (not shown) , and a dewatering air knife (not shown) .
  • the melt is laid on a chill roll (not shown) , which brings one side of the casting into contact with a cold mirror chrome surface. Seconds later, the other side of the casting is introduced to the water bath.
  • the casting drum or roll 26 is oil heated and cooled, allowing for rapid temperature change.
  • the manufacturing apparatus shown in Fig. 3 consists of an unwind stand 31, 15 driven film rolls 32 (each with a variable speed and heating control) , including a driven chill roll, and a winding stand 33.
  • Biaxially oriented film to be converted into shrinkable film is loaded into the unwind stand 31.
  • This film can be produced by any process; however, biaxially oriented films made by a tentering or a bubble process are generally used.
  • This film can be clear or opaque and single layer or multilayer.
  • the film is usually in the thickness range of 50 to 200 gauge, most preferably 60 to 140 nominal gauge.
  • the film After unwinding, the film passes from a feed section (three powered rollers - i.e., nos. 1-3), into a preheat section.
  • the film is then passed through a draw zone of five driven rolls, i.e., nos. 7-11, followed by a corona treatment zone with two drive ceramic rolls, i.e., nos. 12 and 13, then over a large diameter chill roll no. 14 which reduces the film temperature before windup, and finally, through an output nip (no. 15) before windup.
  • MD Mechanical Draw is the ratio of output roll speed to input roll speed.
  • the preferred method of and means for heating the film may be by use of heated rolls, a hot air oven or an infrared oven.
  • the more preferred method of heating the film is by the use of heated rolls and infrared ovens, with the most preferred method being heated rolls.
  • the preferred number of draw gaps is between 1 and 12 with the more preferred number being between 1 and 6.
  • the film thickness at SI has a preferred range of 40 to 200 gauge with a more preferred gauge in clear film within the range of 60 to 110 gauge and in opaque film within the range of 90 to 140 gauge.
  • the most preferred gauge in clear film is within the range of 70 to 90 gauge and within the range of 120 to 140 gauge in opaque film.
  • the type of film anchorage during draw includes electrostatic pinning and nip rolls with both types being preferred.
  • the film tension during draw has a preferred range of 2000 psi to 10,000 psi.
  • thermosetting urethane adhesive Morton Adcoat 333
  • methyl ethyl ketone is diluted with methyl ethyl ketone until a #2 Zahn cup viscosity of 17.5 is achieved.
  • This adhesive solution 42 is placed into a reservoir 47 in contact with a 130 quad pattern gravure cylinder 48, chosen to deliver an adhesive coating weight of 0.7 to 1.5 lb/ream to the film at 2000 ft/. in.
  • Solvent is evaporated from the film coated with adhesive in a drying tunnel 43 maintained at 170"C to 180*C during a 3.5 second residence period.
  • the tension in this film web is maintained at 0.75 lb/linear inch.
  • a second roll 44 of 20 inch wide shrinkable label film is mounted in a secondary unwind stand. It can be either a clear or opaque, coated or metallized shrinkable label film. The tension of this film web is maintained at from about 1 to 1.25 lb./linear inch.
  • the coated surface of the primary film is then brought in contact with one side of the second shrinkable label film roll under pressure in a combining nip 45. If the second film is caused to be opaque by containing voids, it is preferred that the side to be brought in contact with the adhesive coated side consist of a thin, non-voided skin.
  • the resulting laminated roll 46 is wound up on a winding stand.
  • novel polymer shrink films in accordance with the present invention are capable of being heat shrunk onto an article, such as a beverage can, the upper and bottom parts of which are tapered inwardly.
  • the novel shrink films and laminates of novel shrink films of the present invention are particularly advantageous in labeling more modern beverage cans which taper inwardly at the upper and lower extremities so that a label must either avoid extending to these extremities or must conform closely to the shapes thereof; for example, in accordance with the procedures disclosed in U.S. Patent No. 4,844,957, the entire disclosure of which is incorporated by reference herein.
  • incoming packages are spaced by an infeed worm and transferred, via the infeed star, to a central rotary carousel.
  • a base platform and overhead centering bell they are caused to rotate about their own axis.
  • the film label is withdrawn laterally from the magazine, it receives hot melt adhesives to provide the overlap bond, although other previously described methods of adhesion may also be utilized in accordance with the present invention, e.g., providing a heat seal layer.
  • Continued rotation of the package past a short brushing section ensures a positive overlap seal.
  • the fully labelled packages are then transferred, via the discharge star-wheel, to the down-stream conveyor.
  • the labeller is particularly useful for applying wrap ⁇ around film labels made from shrinkable plastic film in which case, the overlap bond is achieved by the previously mentioned hot melt adhesive technique.
  • the adhesive used is dependent upon the type of plastic film used.
  • the plastic film label is applied in the previously described otherwise conventional way by the labeller using the hot melt adhesive, and the size of the film label is such that it extends (top and bottom) beyond the cylindrical portion of the bottle or can.
  • bottles or cans are passed through a heating section to ensure the upper and lower film label areas shrink tightly and uniformly to the bottle contours.
  • hot air preferably be directed towards the top and bottom of the film label or other specific area of the labelled container where a non-uniform contour is located to allow preferential shrinkage of the heat shrink film labels in these areas.
  • none of the conventional non-shrink film labels have been observed to be as suitable for labeling of irregularly shaped beverage containers, and other irregularly shaped articles, as contemplated in accordance with the present invention.
  • conventional non-shrink film labels have been observed to distort during the process of applying the same to irregular shaped articles, for example by heat shrinking.
  • such conventional non-shrink film labels, and particularly laminated non-shrink film labels do not readily conform to the irregular shape of the article, for example, especially at the tapered extremes of beverage containers such as cans.
  • an irregularly shaped article such as a beverage container, which includes a cylindrical wall of metal, glass or plastic, and a top and a bottom on the wall, wherein the wall tapers inwardly adjacent to the top/bottom to form top and bottom tapered portion(s) is provided with a heat shrinkable film, or lamination of novel shrink films produced in accordance with the present invention, to encircle the wall and conform to the tapered portions, for example, as disclosed in U.S. Patent Nos. 4,704,172 and 4,844,957, the disclosures of which are incorporated by reference herein.
  • the shrink film label comprises first and second films as a lamination.
  • the polymers which may be used to produce this new MD shrink film include:
  • the first monomer being selected from the group consisting of ethylene, propylene, butylene and mixtures thereof; and (ii) the second monomer being selected from the group consisting of alpha olefin monomers having two to ten carbon atoms and mixtures thereof; wherein the first monomer is present in the copolymer in an amount in the range of 99.5% to 75% by weight and the second monomer is present in the copolymer in an amount in the range of 0.5% to 25% by weight in either a random or non-random sequence within the copolymer; wherein the terpolymer is comprised of a primary, secondary and tertiary monomer: (i) the primary monomer being selected from the group consisting of ethylene, propylene, butylene and mixtures thereof; (ii) the secondary monomer being selected from the group consisting of alpha olefin monomers having two to ten carbon atoms and mixtures thereof; and (iii) the tertiary monomer being selected from
  • homopolymer is selected from the group consisting of polyethylene, polypropylene and polybutylene; and wherein the MD and TD shrinkage capacities are as follows:
  • the examples of this invention are presented as a demonstration of the object of this invention where the level of MD shrinkage is a function of the composition of the polymer employed when prepared under similar MD orientation process conditions.
  • MD orientation conditions primarily the degree of MD orientation, and to a lesser degree the temperature of MD orientation, also have a significant relation to the level of MD shrinkage in the resultant MD shrink films.
  • polyolefin polymer compositions including polypropylene, polypropylene with a seven (7) percent hydrogenated hydrocarbon resin additive, propylene/ethylene copolymers at about 1.4%, about 2.2%, and about 4.5% ethylene, a blend of polypropylene and an approximately 2.2% propylene/ethylene copolymer, and an approximately 8% propylene/butylene copolymer.
  • the level of MD shrinkage is a function of the polymer composition.
  • the standard polypropylene polymer composition of example 1 results in the lowest level of MD shrinkage at 140*C.
  • the level of MD shrinkage can be increased by other polymer additives, such as a hydrogenated hydrocarbon resin as detailed in example 2, but the object of this invention is to achieve this improved MD shrink performance by modification of the base polymer by the addition of a co-monomer or co-monomers to the polyolefin polymer. This results in a reduction in melting point and overall crystallinity and under equivalent MD shrink films processing conditions, as described in this invention, a higher level of MD shrinkage, especially at higher temperatures up to 140 C C.
  • These new polymer shrink films are advantageous over the prior art as they achieve a higher level of maximum MD shrinkage and achieve a given level of MD shrinkage at a lower temperature. These aspects are useful in achieving a MD shrink film which has a higher level of MD shrinkage, which is useful in shrinking to the non-uniform contour of an articles or container with a higher percentage of dimensional change. These aspects are also useful in achieving a MD shrink film which has a given MD shrinkage at a lower temperature which is advantageous for certain labeling or packaging processes or is beneficial to minimize the temperature exposure of the labeled or package article or container.
  • the approach of this invention by modifying the polyolefin polymer composition to achieve higher levels of MD shrinkage, is preferred over other approaches as described in the prior art such as employing a higher level of MD orientation in the manufacturing process, which results in increased manufacturing difficulties, or by adding non-polyolefin polymer additives to the polymer composition, such as a hydrogenated hydrocarbon resin, which is typically more complex, more expensive and may have other detrimental side effects as a consequence of the non-polyolefin additives such as plate out on production, labeling or packaging equipment.
  • non-polyolefin polymer additives such as a hydrogenated hydrocarbon resin
  • An out of line MD orientation process was used to prepare polyolefin shrink films. This process is similar to the out of line process described in the detailed description. All samples were first prepared as biaxially oriented films by a standard tubular polypropylene oriented film forming process. Overall biaxial film orientation was approximately 7 times in the MD and TD direction.
  • the out of line process is approximately described as in Fig. 3, and consists of an unwind stand, a series of fifteen driven and heated rolls (variable speed and temperature) , a chill roll, a treatment section, and a winding or take-up section.
  • the minimum roll speed for the out of line MD orientation process was 1000 ft/ in. and this was the first roll after the unwind section.
  • the maximum roll speed was 1050 ft./min. and this was the tenth roll in this series of rolls.
  • the roll surface temperatures varied from 100*C to 125'C. Prpcess 2
  • the minimum roll speed for the out of line MD orientation process was 1000 ft./min. and this was the first roll after the unwind section.
  • the maximum roll speed was 1234 ft./min. and this was the tenth roll in this series of rolls.
  • the roll surface temperatures varied from 100"C to 125*C.
  • the minimum roll speed for the out of line MD orientation process was 1000 ft./min. and this was the first roll after the unwind section.
  • the maximum roll speed was 1300 ft./min. and this was the tenth roll in this series of rolls.
  • the roll surface temperatures varied from 100"C to 125*C.
  • Example 2
  • This example also contains minor amounts of other additives such as an amide slip agent (0.12 eight percent Kemamide B, Witco Chemical), clay antiblock (0.36 weight percent of equal parts of Kaophile 2, Georgia Kaolin and Kaopolite SFO, from Antor, Inc.), and an antioxidant (0.10 weight percent Ethanox 330, Ethyl Chemical) and an antacid (0.10 weight percent calcium stearate) .
  • the polymer composition of example 3 is a propylene/ethylene copolymer, Exxon Escorene PP 9122 (about 2.2 percent ethylene) .
  • Example 4 is a propylene/ethylene copolymer, Exxon Escorene PP 9122 (about 2.2 percent ethylene) .
  • the polymer composition of example 4 is a propylene/ethylene copolymer, Exxon Escorene PLTD 994 (about 1.4 percent ethylene) .
  • Example 5 is a propylene/ethylene copolymer, Exxon Escorene PLTD 994 (about 1.4 percent ethylene) .
  • the polymer composition of example 5 is a propylene/ethylene copolymer Fina 8573 (about 4.5 percent ethylene) .
  • the polymer composition of example 6 is a 50/50 blend of a polypropylene, Exxon Escorene PD 4222 El and a propylene/ethylene copolymer, Exxon Escorene PP 9122 (about 2.2 percent ethylene) .
  • Example 7
  • the polymer composition of example 7 is a propylene/butylene copolymer, Shell Cefor SRD4-12 (about 8 percent butylene) .

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Health & Medical Sciences (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Materials Engineering (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Laminated Bodies (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un film polymère rétrécissable à orientation biaxiale, présentant une capacité de retrait dans la direction machine (DM) supérieure à la capacité de retrait dans la direction transversale (DT), de sorte que DT soit inférieur ou égal à DM/2 dans la plage de températures allant de 100 °C à 140 °C. Ce film comprend au moins un des constituants suivants: (a) un copolymère polyoléfinique; (b) un terpolymère polyoléfinique; (c) des mélanges de copolymères et d'homopolymères polyoléfiniques; (d) des mélanges de copolymères et de terpolymères polyoléfiniques; (e) des mélanges de terpolymères et d'homopolymères polyoléfiniques; et (f) des mélanges de copolymères, d'homopolymères et de terpolymères polyoléfiniques. Le copolymère en question comprend un premier et un second monomère. Le premier monomère est choisi dans le groupe constitué par l'éthylène, le propylène, le butylène et leurs mélanges. Le second monomère est choisi dans le groupe constitué par les monomères alpha-oléfiniques ayant de deux à dix atomes de carbone et leurs mélanges. Le premier monomère est présent à raison de 99,5 % à 75 % en poids et le second monomère est présent à raison de 0,5 % à 25 % en poids. Le terpolymère comprend: (i) un monomère primaire éthylène, propylène, butylène et leurs mélanges; (ii) un monomère secondaire alpha-oléfinique ayant de deux à dix atomes de carbone et des mélanges de tels monomères; et (iii) un monomère tertiaire alpha-oléfinique ayant de deux à dix atomes de carbone et leurs mélanges, le monomère primaire étant présent à raison de 50 % à 99 % en poids et les monomères secondaire et tertiaire à raison de 0,5 % à 49,5 % en poids. L'homopolymère est le polyéthylène, le polypropylène et le polybutylène.
PCT/US1995/011041 1994-09-07 1995-08-29 Film de copolymere a capacite de retrait elevee WO1996007699A1 (fr)

Priority Applications (5)

Application Number Priority Date Filing Date Title
EP95931034A EP0779911A1 (fr) 1994-09-07 1995-08-29 Film de copolymere a capacite de retrait elevee
MX9701781A MX9701781A (es) 1994-09-07 1995-08-29 Pelicula de copolimero de alto encogimiento.
NZ292443A NZ292443A (en) 1994-09-07 1995-08-29 Biaxially oriented copolymer shrink film with high shrinkage in machine direction compared to transverse direction
AU34621/95A AU3462195A (en) 1994-09-07 1995-08-29 High shrinkage copolymer film
BR9508998A BR9508998A (pt) 1994-09-07 1995-08-29 Filme de copolímero de alta contração

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
US30150394A 1994-09-07 1994-09-07
US08/301,503 1994-09-07

Publications (1)

Publication Number Publication Date
WO1996007699A1 true WO1996007699A1 (fr) 1996-03-14

Family

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PCT/US1995/011041 WO1996007699A1 (fr) 1994-09-07 1995-08-29 Film de copolymere a capacite de retrait elevee

Country Status (7)

Country Link
EP (1) EP0779911A1 (fr)
AU (1) AU3462195A (fr)
BR (1) BR9508998A (fr)
CA (1) CA2199465A1 (fr)
MX (1) MX9701781A (fr)
NZ (1) NZ292443A (fr)
WO (1) WO1996007699A1 (fr)

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO1997011115A1 (fr) * 1995-09-18 1997-03-27 Exxon Chemical Patents Inc. Films thermoretractables a base de polymeres de propylene
DE19823142A1 (de) * 1998-05-23 1999-11-25 Inst Polymerforschung Dresden Elastische Fäden, Folien, textile Flächengebilde und Hybridstrukturen mit hohem Schrumpfvermögen bei niedrigen Temperaturen und hoher Temperaturstabilität, Verfahren zu ihrer Herstellung und Verwendung
EP0831994A4 (fr) * 1995-04-25 2000-02-02 Mobil Oil Corp Feuilles de polypropylene a orientation biaxiale et a retrait uniaxial
WO2001036520A1 (fr) * 1999-11-16 2001-05-25 Applied Extrusion Technologies, Inc. Films polyolefiniques adaptes a des utilisations institutionnelles
US9221573B2 (en) 2010-01-28 2015-12-29 Avery Dennison Corporation Label applicator belt system
WO2017193155A1 (fr) * 2016-05-10 2017-11-16 Trenchard Douglas Michael Film de paillis réactif solaire

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US8282754B2 (en) 2007-04-05 2012-10-09 Avery Dennison Corporation Pressure sensitive shrink label
RU2505573C2 (ru) 2007-04-05 2014-01-27 Эвери Деннисон Копэрейшн Самоклеящаяся усадочная этикетка и изделие с этикеткой

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0204843A1 (fr) * 1984-12-13 1986-12-17 Showa Denko Kabushiki Kaisha Film retractible a chaud a faible temperature et procede de production
EP0321964A2 (fr) * 1987-12-22 1989-06-28 Union Carbide Corporation Procédé d'extrusion
EP0498249A2 (fr) * 1991-02-07 1992-08-12 Hercules Incorporated Procédé pour la fabrication de films rétractables et films rétractables et laminés ainsi obtenus

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0204843A1 (fr) * 1984-12-13 1986-12-17 Showa Denko Kabushiki Kaisha Film retractible a chaud a faible temperature et procede de production
EP0321964A2 (fr) * 1987-12-22 1989-06-28 Union Carbide Corporation Procédé d'extrusion
EP0498249A2 (fr) * 1991-02-07 1992-08-12 Hercules Incorporated Procédé pour la fabrication de films rétractables et films rétractables et laminés ainsi obtenus

Cited By (12)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0831994A4 (fr) * 1995-04-25 2000-02-02 Mobil Oil Corp Feuilles de polypropylene a orientation biaxiale et a retrait uniaxial
EP0831994B2 (fr) † 1995-04-25 2012-02-15 ExxonMobil Oil Corporation Fabrication de films de propylène à orientation biaxiale et à retrecissement uniaxial
WO1997011115A1 (fr) * 1995-09-18 1997-03-27 Exxon Chemical Patents Inc. Films thermoretractables a base de polymeres de propylene
US5741563A (en) * 1995-09-18 1998-04-21 Exxon Chemical Patents Inc. Shrink films from propylene polymers
DE19823142A1 (de) * 1998-05-23 1999-11-25 Inst Polymerforschung Dresden Elastische Fäden, Folien, textile Flächengebilde und Hybridstrukturen mit hohem Schrumpfvermögen bei niedrigen Temperaturen und hoher Temperaturstabilität, Verfahren zu ihrer Herstellung und Verwendung
DE19823142C2 (de) * 1998-05-23 2001-02-22 Inst Polymerforschung Dresden Elastische Fäden, Folien, textile Flächengebilde und Hybridstrukturen mit hohem Schrumpfvermögen bei niedrigen Temperaturen und hoher Temperaturstabilität und Verfahren zu ihrer Herstellung
WO2001036520A1 (fr) * 1999-11-16 2001-05-25 Applied Extrusion Technologies, Inc. Films polyolefiniques adaptes a des utilisations institutionnelles
US6410136B1 (en) 1999-11-16 2002-06-25 Applied Extrusion Technologies, Inc. Polyolefin films suitable for institutional applications
US9221573B2 (en) 2010-01-28 2015-12-29 Avery Dennison Corporation Label applicator belt system
US9637264B2 (en) 2010-01-28 2017-05-02 Avery Dennison Corporation Label applicator belt system
WO2017193155A1 (fr) * 2016-05-10 2017-11-16 Trenchard Douglas Michael Film de paillis réactif solaire
US11197433B2 (en) 2016-05-10 2021-12-14 Douglas Michael Trenchard Solar-reactive mulch film

Also Published As

Publication number Publication date
NZ292443A (en) 1998-06-26
EP0779911A1 (fr) 1997-06-25
MX9701781A (es) 1997-06-28
AU3462195A (en) 1996-03-27
CA2199465A1 (fr) 1996-03-14
BR9508998A (pt) 1998-01-13

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