WO1994006849A1 - Film similaire a du papier et procede et compositions pour le fabriquer - Google Patents

Film similaire a du papier et procede et compositions pour le fabriquer Download PDF

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Publication number
WO1994006849A1
WO1994006849A1 PCT/CA1993/000385 CA9300385W WO9406849A1 WO 1994006849 A1 WO1994006849 A1 WO 1994006849A1 CA 9300385 W CA9300385 W CA 9300385W WO 9406849 A1 WO9406849 A1 WO 9406849A1
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WIPO (PCT)
Prior art keywords
film
filler
density polyethylene
high density
melt index
Prior art date
Application number
PCT/CA1993/000385
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English (en)
Inventor
Kevin Bergevin
Dean Scott Gray
Original Assignee
Dupont Canada 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 Dupont Canada Inc. filed Critical Dupont Canada Inc.
Priority to AU48124/93A priority Critical patent/AU4812493A/en
Publication of WO1994006849A1 publication Critical patent/WO1994006849A1/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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/34—Silicon-containing compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • 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
    • C08J2323/04—Homopolymers or copolymers of ethene
    • C08J2323/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/016—Additives defined by their aspect ratio

Definitions

  • the present invention relates to the production of a paper-like thermoplastic film and more particularly to the production of such paper-like films from polyethylene containing inorganic fillers.
  • Such films may be useful for envelopes, posters, packages, books, maps, films for graphic arts applications, labels, in-mould labels and the like.
  • Paper-like thermoplastic films are known.
  • U.S.Patent 4 082 880 which issued 1978 April 4 to V.G. Zboril discloses paper-like thermoplastic films made from 70-98 wt.% of a polyethylene having a melt index of up to 5 dg/min and 2-30 wt.% of an inorganic lamellar filler, using a blown film process.
  • Canadian Patent 1 043 931 which issued 1978 December 5 to T.M. Tuszynski discloses paper-like thermoplastic butter and margarine wrap made from high density polyethylene having a density in the range of 0.945-0.970 g/cm 3 and containing aluminium pigment and, • optionally, mica particles.
  • Patent 3 154 461 discloses film made from a selection of polymers and from 1 to 25% filler. The film is biaxially oriented 2.5 to 3.5 times in the transverse and machine directions.
  • U.S. Patent 3 738 904 assigned to E.I. du Pont de Nemours and Company, discloses paper-like films made from blends of homopolymers, copolymers or blends of C 2 -C ⁇ 0 ct-olefins having a crystallinity of at least 60%, containing from 26 to
  • the films had been biaxially oriented at least two times in the machine and transverse directions. It is known in the art that microvoided films can be produced by stretching certain filled polymer compositions. Such film possess certain paper-like qualites, e.g. opacity, whiteness and printability. However, such films suffer from low flexural stiffness. Microscopic evaluation of the internal structure of such films generally reveals a large number of filler particles which are no longer well bonded to the polymer matrix and therefore the particles are not able to provide the flexural stiffness.
  • One method of providing flexural stiffness involves
  • SUBSTITUTESHEET coating the film with clay.
  • the clay also makes the films more acceptable for writing or printing thereon.
  • coating with clay adds to the expense of the film and makes such films difficult to recycle.
  • the present invention seeks to provide a film which possesses flexural stiffness and may be written or printed on, without the necessity of coating with clay.
  • the invention provides a micro-voided film having a thickness of from 8 to 200 ⁇ m, made from a composition comprising i) a polyolefin resin component comprising polyethylene or a blend of polyethylenes, and ii) a filler component consisting of from 5 to 25 wt.% of at least one lamellar filler and from 15 to 50 wt.% of at least one filler having a low aspect ratio, and the total filler component being in an amount of from 30 to 60 wt.%, said filler percentages being based on the total composition, said film having a structure with voids surrounding or adjacent to the low aspect ratio filler particles, in the interior of the film.
  • the film thickness is from 25 to 200 ⁇ m, and especially from 50 to 150 ⁇ m.
  • the polyolefin resin component comprises high density polyethylene or a blend of polyethylenes, at least one of which is a high density polyethylene.
  • the polyolefin resin component comprises one or more polyethylenes, at least one of which is a high density polyethylene having a melt index of less than 0.5 dg/min.
  • the film is an opaque micro- voided film in which the polyolefin component comprises a blend of a first high density polyethylene having a melt index of less than 0.2 dg/min and a second high density polyethylene having a melt index of at least 30 dg/min, the weight ratio of first high density polyethylene to second high density polyethylene being from 20:80 to 80:20, said blend optionally containing from 0 to 20 wt.%, based on the
  • SUBSTITUTESHEET total polyolefin component weight of low density polyethylene having a melt index of from 0.4 to 3.0 dg/min, and in which the polyolefin component is blended with a filler component of from 5 to 25 wt.% of at least one lamellar filler and from 15 to 50 wt.% of at least one filler having a low aspect ratio, and the total filler component being in an amount of from 30 to 60 wt.%, said filler percentages being based on the total composition.
  • the opaque micro-voided film contains up to about 2 wt.% at least one C ⁇ 0 -C M organic acid based on the total composition.
  • the lamellar filler is present in a concentration of from 10 to 20 wt.%
  • the lamellar filler is talc.
  • the low aspect ratio filler is present in a concentration of from 25 to 40 wt.%.
  • a preferred low aspect ratio filler is calcium carbonate.
  • the first high density polyethylene has a melt index of from 0.03 to 0.10 dg/min.
  • the second high density polyethylene has a melt index of from 50 to 100 dg/min.
  • the low density polyethylene is a linear low density polyethylene having a melt index of from 0.5 to 1.5 dg/min.
  • the film of the present invention is preferably 50 to 150 ⁇ m in thickness.
  • melt index is measured by the procedures of A.S.T.M. D-1238-90b
  • density of polyethylene is measured by the procedures of A.S.T.M. D- 1505-85.
  • polyethylene as used herein, means ethylene homopolymers or copolymers made of ethylene and at least one other olefin monomer.
  • High density polyethylene means a polyethylene having a density of at least 0.940 g/cm 3 and low density polyethylene means a polyethylene having a density of 0.925 g/cm 3 or less.
  • SHEET aspect ratio is the average value determined for a representative number of particles by examination through a microscope.
  • the length is the longest dimension, measured through the centre of mass of the particle. Once the length is known, it is possible to measure the dimensions of the particle in two other directions which are mutually perpendicular to each other and perpendicular to the length. These two dimensions are referred to as the width and thickness of the particle, with the thickness being the smaller of the two, when they are unequal.
  • Fillers with low aspect ratio, i.e. tending to a ratio of 1.0, although irregular, are most often described as spherical, round, cubic.
  • Fillers of high aspect ratio are most often described as lamellar (i.e. plate-like) , fibrous, needle- like.
  • Lamellar fillers are those whose particle lengths and widths are considerably larger than their thicknesses.
  • the present invention also provides a process for making a film, comprising: a) extruding into film or sheet form of thickness 100 to 2500 ⁇ m a composition comprising i) a polyolefin resin component comprising polyethylene or a blend of polyethylenes, and ii) a filler component consisting of from 5 to 25 wt.% of at least one lamellar filler and from 15 to 50 wt.% of at least one filler having a low aspect ratio, and the total filler component being in an amount of from 30 to 60 wt.%, said filler percentages being based on the total composition; and b) orienting said film or sheet at a stretch ratio of at least 4 in at least one direction, said orientation being conducted at a film temperature between the line drawing temperature and the melting temperature of the composition, the resulting film having a thickness of from 8 to 200 ⁇ m.
  • the resulting film has a thickness of from 25 to 200 ⁇ m, and especially from 50 to 150 ⁇ m.
  • the polyolefin resin component comprises high density polyethylene or a blend of polyethylenes, at least one of which is a high density polyethyl
  • the polyolefin resin component comprises one or more polyethylenes, at least one of which is a high density polyethylene having a melt index of less than 0.5 dg/min.
  • the sheet in step a) is extruded to a thickness of from 1000 to 2500 ⁇ m.
  • the extruded sheet is biaxially oriented, sequentially, first in the machine direction and then in the transverse direction, in a tenter frame.
  • the invention provides a process for making a film, comprising: a) extruding into film or sheet form of thickness 100 to 2500 ⁇ m a composition comprising i) a polyethylene component of a first high density polyethylene having a melt index of less than 0.2 dg/min and a second high density polyethylene having a melt index of at least 30 dg/min, the weight ratio of first high density polyethylene to second high density polyethylene being from 20:80 to 80:20, said blend optionally containing from 0 to 20 wt.%, based on the total polyethylene component weight, of low density polyethylene having a melt index of from 0.4 to 3.0 dg/min, and ii) a filler component of from 5 to 25 wt.% of a lamellar filler and from 15 to 50 wt.%
  • the composition includes up to about 2 wt.% of at least one C I0 -C 24 organic acid based on the total composition.
  • the sheet is oriented biaxially, at a stretch ratio of at least 4 in each
  • SUBSTITUTESHEET direction Preferably the biaxial orientation is in the transverse and machine directions.
  • the film or sheet is oriented at a stretch ratio of at least 4 in the machine direction and at least 5 in the transverse direction.
  • the first high density polyethylene has a melt index of from 0.03 to 0.10 dg/min.
  • the second high density polyethylene has a melt index of from 50 to 100 dg/min.
  • the low density polyethylene is a linear low density polyethylene having a melt index of from 0.5 to 1.5 dg/min.
  • the lamellar filler is present in a concentration of from 10 to 20 wt.% In a further embodiment the lamellar filler is talc.
  • the low aspect ratio filler is present in a concentration of from 25 to 40 wt.%.
  • a preferred low aspect ratio filler is calcium carbonate.
  • the resulting film of the present process is preferably from 25 to 200 ⁇ m, and especially from 50 to 150 ⁇ m in thickness.
  • the invention also provides a film made by the above process.
  • line drawing temperature refers to the temperature above which uniform orientation is obtained, as is known in the art.
  • the line drawing temperature and melting temperature can be determined experimentally.
  • a significant fact related to line-drawing is that the line-drawing temperature can change.
  • a film has a given line drawing temperature before stretching.
  • the line-drawing temperature of the film in the direction perpendicular to the direction of stretch, e.g the transverse direction is higher than the given temperature. This fact should be taken into consideration in order to provide biaxial stretching at the proper stretching temperature.
  • the melting temperature can be experimentally determined by differential scanning calorimetry.
  • stretch ratio is the ratio of a length of a sample of the film in the orientation direction, after stretching, compared to the original length of the film in the orientation direction, before stretching.
  • any of the low aspect ratio particles become detached from the surrounding polymer matrix and small spaces or voids are created around or adjacent to the filler particles. In some cases these voids can remain isolated. In other cases, especially when large numbers of voids are created, these voids can partially merge and become interconnected. Voids which form near the surface of the film may open onto the surface, thereby providing an uneven surface.
  • microvoid relates to the small size of the voids, because they are smaller than the film thickness and are generally not visible to the
  • SUBSTITUTESHEET unaided eye. These microvoids can be observed by fracturing a film specimen and examining the exposed surface or cross- section under an optical or electron microscope.
  • microvoids appear to manifest itself as an increase in opacity and whiteness of the film compared to films without microvoids. There is also a noticeable reduction in density which results from the fact that the film is no longer a uniform solid structure. This reduction in density cah create difficulties when comparing film samples of differing degrees of microvoiding. This may be further complicated by films which do not have smooth surfaces. For these reasons, some additional measurements are used for evaluating the films.
  • the density of a film sample is determined by measuring the length, width and average thickness of the sample and determining its mass. Care must be taken not to overly compress the sample when measuring the thickness. It is desirable to use a micrometer which applies only light force.
  • the (compounded) resin density can be determined by using, for example, a density column or other suitable method. "Void fraction" for the film sample is then calculated from the following formula:
  • Void Fraction 1 - (Film density/Resin density) It should be noted that the void fraction calculated in this way takes into account internal voids and the effects of surface roughness.
  • Equivalent thickness Thickness x (1 - Void fraction)
  • the equivalent thickness is intended to be a measure of the thickness that the film would have had if compressed into a smooth, uniform, solid layer. Except where explicitly stated as “equivalent thickness”, the term thickness refers to the measured thickness of the film and not the equivalent thickness.
  • the invention also provides a composition
  • a composition comprising i) a polyolefin resin component comprising polyethylene or a
  • the polyolefin resin component comprises high density polyethylene or a blend of polyethylenes, at least one of which is a high density polyethylene.
  • the polyolefin resin component comprises one or more polyethylenes, at least one of which is a high density polyethylene having a melt index of less than 0.5 dg/min.
  • the composition comprises i) a polyethylene component of a first high density polyethylene having a melt index of less than 0.2 dg/min and a second high density polyethylene having a melt index of at least 30 dg/min, the weight ratio of first high density polyethylene to second high density polyethylene being from 20:80 to 80:20, said blend optionally containing from 0 to 20 wt.%, based on the total polyethylene component weight, of low density polyethylene having a melt index of from 0.4 to 3.0 dg/min, and ii) a filler component of from 5 to 25 wt.% of a lamellar filler and from 15 to 50 wt.% of a filler having a low aspect ratio, and the total filler component being in an amount of from 30 to 60 wt.%, said filler percentages being based on the total composition
  • the composition includes up to about 2 wt.% at least one C ⁇ 0 -C 24 organic acid based on the total composition.
  • the lamellar fillers useful in the present invention have an aspect ratio of at least about 5. Examples of suitable lamellar fillers which may have the
  • SUBSTITUTESHEET above characteristics are talc, mica and kaolin clay.
  • a preferred lamellar filler is talc.
  • the low aspect ratio fillers useful in the present invention have an aspect ratio of less than about 3, preferably less than about 2.
  • suitable low aspect ratio fillers are calcium carbonate, barium sulphate, calcium sulphate, precipitated silica, glass spheres and glass beads.
  • a preferred filler is calcium carbonate.
  • the particle size of the fillers has an effect on the properties of the film. It is desirable that the fillers do not contain particles of excessively large size, otherwise holes or other defects may be generated during the stretching process.
  • the maximum permissible filler particle size depends on the desired film thickness. A.S.T.M. Procedure D-1210 or sieving may be used to determine the size of the largest particles. When thicker films are to be produced, larger particles can be tolerated. If the average particle size of the low aspect ratio filler is too low, there is a tendency for the resulting films to have lower void fractions.
  • both the low aspect ratio filler and the lamellar filler posses a maximum particle size less than about 50 ⁇ m. It is also desirable for at least 99.9% by weight of the filler particles to pass through a 325 U.S. mesh screen (nominal mesh openings of
  • a desirable range for the mean particle size, based on equivalent spherical diameter, for both the low aspect ratio filler and the lamellar filler, is about from 0.2 to 10 ⁇ m, preferably from 0.5 to 5 ⁇ m.
  • Equivalent spherical diameter (ESD) which is the diameter computed for a hypothetical sphere which would have the came volume as the particle, may be calculated from:
  • ESD (6 x particle volume/ ⁇ ) %
  • the smallest dimension of the low aspect ratio filler affects the formation of voids in the oriented film.
  • Voiding is essential for the film of this invention. If the particle size of this filler is too small, the voids are
  • SUBSTITUTESHEET absent or are too small to give practical paper-like films; if the particle size of this filler is too large, the film tends to have holes therein, thus destroying the integrity of the film. It has been found that the lamellar fillers, in at least some cases, do not substantially contribute to the formation of voids but contribute instead to increased stiffness. Thus, by selecting the appropriate combination of fillers, this invention provides for a micro-voided paper-like film with enhanced stiffness relative to other micro-voided or microporous films.
  • the film may be used without further treatment.
  • the composition of the present invention is usually first compounded by known methods for melt blending thermoplastic polymers.
  • the compounded composition is then melted in a cast film or blown film extruder and formed into film or sheet, as is known in the art.
  • the resulting film or sheet is typically 200 to 2500 ⁇ m thick.
  • This film is then oriented, preferably biaxially, by methods known in the art, e.g. using a tenter frame.
  • the resulting films preferably have a thickness of from 25 to 200 ⁇ m.
  • the optimum temperature for stretching will depend on the particular polyethylene or blend of polyethylenes selected. As indicated, when stretching the films, it is necessary for the film temperature to be below the crystalline melting point and above the line drawing temperature. In practice, the actual sheet or film temperature is not usually measured. Instead, what is
  • SUBSTITUTESHEET measured is, for example, the temperature of the fluid used to heat orienting rolls in a machine direction orienter, or the air temperature in a tenter frame oven.
  • the film may break during the stretching operation, or may orient non- uniformly, especially if the film temperature is below the line drawing temperature.
  • the lamellar filler particles may initiate voiding and become detached from the polymer, and their beneficial effect on the film stiffness would thus be lost.
  • the void fraction decreases. If the film temperature is too high, however, the void fraction may be too low. If the void fraction is too low, a commercially desirable mix of properties may not be achieved.
  • the films of the present invention prefferably have a void fraction in the range of 0.15 to 0.60, preferably in the range of 0.20 to 0.50.
  • While the optimum stretching temperatures will depend on the above mentioned factors, they are typically, for a sequential tenter frame stretching process, in the range of 120-130"C for the machine direction orientation (as measured by the heat transfer fluid temperature) and 125-140 ⁇ C for the air temperature in the tenter oven.
  • Films of the present invention tend to have low extensibility, high flexural stiffness, good die- cuttability, opacity, fold retention (good deadfold) and printability. As such it is useful as a paper substitute. It is particularly useful, after coating with a heat seal layer, for in-mould labels, as it is recyclable with high density polyethylene resins, containers, films and the like.
  • Heat seal layers are polyolefin materials with a lower melting point tha ⁇ n the film of the present invention.
  • Ethylene vinyl acetate (EVA) copolymers are examples of such heat sealing layers.
  • antioxidants may be desirable to include antioxidants, processing aids, UV stabilizers and the like.
  • PE-1 was a high density polyethylene with melt index of 65 and density of 0.959 g/cm 3 .
  • PE-2 was a high density polyethylene with melt index of 0.055 and density of 0.950 g/cm 3 .
  • CaC0 3 -l was a calcium carbonate with mean particle size of 3 ⁇ m and typical particle aspect ratio of about 1.5.
  • the talc was a platy talc with a median ESD (equivalent spherical diameter) of 2.2 ⁇ m and a typical particle aspect ratio of about 10.
  • the clay was a treated kaolin clay with mean particle size of 0.45 ⁇ m, a platelet shape and a typical particle aspect ratio of about 14.
  • the stearic acid blend consisted of 50% C ⁇ 8 (stearic) acid, 42% C l ⁇ (palmitic) acid, 3% C, 4 acid, 2% C i7 acid, 2% C ls (unsaturated acid) and 1% C 15 acid.
  • the compounded resins were extruded in a blown film process to form film having a thickness of 200 ⁇ m.
  • Samples of the blown film were placed in the clips of a film stretcher and stretched at a ratio of 4X in the machine direction at a temperature of 133°C.
  • the flexural stiffness was measured in the machine direction using a Teledyne Taber (trade mark) stiffness tester. The thickness of each sample was determined.
  • SUBSTITUTE SHEET void fraction for each group of samples was estimated by weighing a known area of film of measured thickness and comparing the film density to the resin density. For each sample tested, an equivalent thickness was calculated according to the definition given previously.
  • compositions in % by weight
  • key process parameters which were employed to produce such films.
  • the compositions were prepared by first compounding the raw materials in a Banbury (trade mark) mixer, casting a thick sheet and orienting the sheet sequentially: first in the machine direction and then in the transverse direction.
  • PE-1 was a high density polyethylene with melt index of 65 and density of 1 0.959 g/cm 3 .
  • PE-2 was a high density polyethylene with melt index of 0.055 and density of 0.950 g/cm 3 .
  • PE-3 was a linear low density polyethylene with melt index of 0.75 and density of 0.919 g/cm 3 .
  • CaC0 3 -l was a
  • CaC0 3 -2 was a calcium carbonate with a mean particle size of 1 ⁇ m and a typical particle aspect ratio of about 1.5.
  • the talc was a platy talc with median equivalent spherical diameter of 2.2 ⁇ m and typical particle aspect ratio of about 10.
  • Acid blend-1 consisted of 50% C w (stearic) acid, 42% C l ⁇ (palmitic) acid 3% C 14 acid, 2% C ⁇ r acid, 2% C lt (unsaturated) acid and 1% C I5 acid.
  • Acid blend-2 consisted of 52% C l ⁇ acid, 44% Ci ⁇ acid, 2.5% C ⁇ 7 acid, 1% C I4 acid and 0.5% C 15 acid.
  • the void fractions were determined by measuring the density of the film samples.
  • the flexural stiffness in the machine direction was measured using a Teledyne Taber (trade mark) stiffness tester.
  • the films of example 2 were easy to print and could be written on with pencil or ink. They had excellent fold retention, whiteness, and opacity.
  • Examples 2a, 2b and 2d had excellent tear resistance, strength and stiffness.
  • EXAMPLE 3 Filled polymeric compositions were compounded on a Banbury (trade mark) mixer. The compositions (in % by weight) are listed in the following table:
  • PE-4 was a high density polyethylene with melt index of 0.4 and density of 0.945 g/cm 3 .
  • PE-5 was a medium density polyethylene with melt index of 1.85 and density of 0.935
  • PE-6 was a high density polyethylene with melt index of 1.0 and density of 0.956 g/cm 3*
  • the talc was a platy talc with median equivalent spherical diameter of 2.2 ⁇ m and typical particle aspect ratio of about 1.5.
  • the stearic acid blend consisted of 50% C, 8 (stearic) acid, 42% C l ⁇
  • compositions 3a and 3b were easier to stretch without developing holes or tears and this is attributed to the lower melt index of the polyethylene component. It is for this reason that the inclusion of a low melt index polyethylene is preferred.
  • compositions of examples 3a and 3g of Example 3 were pressed into sheets of 250 ⁇ m thickness and stretched 4.3X at the temperatures indicated, to produce films with the following properties:
  • PE-l was a high density polyethylene with melt index of 65 and density of 0.959 g/cm 3 .
  • PE-2 was a high density polyethylene with melt index of 0.055 and density of 0.950 g/cm 3 .
  • the talc was a platy talc with median ESD (equivalent spherical diameter) of 2.2 ⁇ m and a typical particle aspect ratio of about 10.
  • CaC0 3 -2 was an uncoated calcium carbonate with a mean particle size of 1 ⁇ m and a typical particle aspect ratio of about 1.5.
  • CaC0 3 -3 was similar but had been pre-coated with stearic acid prior to the compounding step.
  • the stearic acid blend consisted of 50% C ls (stearic) acid, 42% C I ⁇ (palmitic) acid, 3% C 14 acid, 2% C 17 acid, 2% C IS (unsaturated) acid and 1% C i acid.

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Abstract

Un procédé pour fabriquer un film similaire à du papier comprend: a) l'extrusion sous forme de film ou de feuille d'épaisseur 100 à 2500 νm d'une composition de i) un composé polyéthylène d'un premier polyéthylène de densité élevée ayant un indice de fusion inférieur à 0,2 dg/min et d'un second polyéthylène à densité élevée ayant un indice de fusion d'au moins 20 dg/min, ii) un composé de charge de 5 à 25% en poids d'une charge lamellaire par exemple le talc, et de 15 à 50% en poids d'une charge ayant un faible coefficient d'exposition, par exemple du carbonate de calcium, et iii) jusqu'à environ 2% en poids d'au moins un acide organique C10-C24 basé sur la composition totale, par exemple l'acide stéarique; et b) l'orientation du film ou de la feuille au moins 4 fois dans au moins une direction, l'orientation étant effectuée à une température comprise entre la température d'étirage en ligne et la température de fusion de la composition, le film résultant ayant une épaisseur comprise entre 25 et 200 νm. Le composé de charge total représente une quantité de 30 à 60 % en poids, les pourcentages étant basés sur la quantité totale de la composition. Le rapport de poids entre le premier polyéthylène à densité élevée et le second polyéthylène à densité élevée est compris entre 20:80 et 80:20. Optionnellement, le mélange contient de 0 à 20 % en poids, basé sur le poids total du composé polyéthylène, d'un polyéthylène à faible densité ayant un indice de fusion compris entre 0,4 et 3,0 dg/min.
PCT/CA1993/000385 1992-09-17 1993-09-17 Film similaire a du papier et procede et compositions pour le fabriquer WO1994006849A1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AU48124/93A AU4812493A (en) 1992-09-17 1993-09-17 Paper-like film and method and compositions for making it

Applications Claiming Priority (2)

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GB9219656.7 1992-09-17
GB929219656A GB9219656D0 (en) 1992-09-17 1992-09-17 Paper-like film and method and compositions for making it

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WO1994006849A1 true WO1994006849A1 (fr) 1994-03-31

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PCT/CA1993/000385 WO1994006849A1 (fr) 1992-09-17 1993-09-17 Film similaire a du papier et procede et compositions pour le fabriquer

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AU (1) AU4812493A (fr)
GB (1) GB9219656D0 (fr)
MX (1) MX9305696A (fr)
WO (1) WO1994006849A1 (fr)

Cited By (22)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0623646A2 (fr) * 1993-05-05 1994-11-09 BP Chemicals PlasTec GmbH Matériau d'emballage pour la fabrication de boîtes pliantes
US5762840A (en) * 1996-04-18 1998-06-09 Kimberly-Clark Worldwide, Inc. Process for making microporous fibers with improved properties
US5853965A (en) * 1997-05-23 1998-12-29 Eastman Kodak Company Photographic element with bonding layer on oriented sheet
US5866282A (en) * 1997-05-23 1999-02-02 Eastman Kodak Company Composite photographic material with laminated biaxially oriented polyolefin sheets
US5874205A (en) * 1997-05-23 1999-02-23 Eastman Kodak Company Photographic element with indicia on oriented polymer back sheet
US5888683A (en) * 1997-05-23 1999-03-30 Eastman Kodak Company Roughness elimination by control of strength of polymer sheet in relation to base paper
US5888643A (en) * 1997-05-23 1999-03-30 Eastman Kodak Company Controlling bending stiffness in photographic paper
US5888681A (en) * 1997-05-23 1999-03-30 Eastman Kodak Company Photographic element with microvoided sheet of opalescent appearance
US5902720A (en) * 1997-05-23 1999-05-11 Eastman Kodak Company Photographic element that resists curl using oriented sheets
US5935690A (en) * 1997-05-23 1999-08-10 Eastman Kodak Company Sheets having a microvoided layer of strength sufficient to prevent bend cracking in an imaging member
WO2002102593A1 (fr) * 2001-06-20 2002-12-27 Byron Le Roux Materiau polymere de type papier
WO2003014200A1 (fr) * 2001-08-09 2003-02-20 Equistar Chemicals, Lp Film en polyethylene haute densite oriente, compositions, et procede d'elaboration correspondant
CN1105636C (zh) * 1998-03-25 2003-04-16 香港商龙盟环保纸(集团)有限公司 环保纸的制造方法
US6887923B2 (en) 2002-12-11 2005-05-03 Equistar Chemicals, L.P. Processing aids for enhanced machine direction orientation rates and property enhancement of polyolefin films using hydrocarbon waxes
KR100465176B1 (ko) * 1997-06-27 2005-05-18 삼성토탈 주식회사 통기성필름의제조방법
US6946203B1 (en) 2002-12-31 2005-09-20 Exxon Mobil Oil Corporation Multilayer polyolefin substrate with low density core and stiff outer layers
WO2007015120A1 (fr) 2005-08-04 2007-02-08 Alfonso Alejandro Pira Papier synthetique
US7211620B2 (en) * 2005-01-25 2007-05-01 Plasticos, Flexibles S.A. Foldable polyolefin films
WO2009124989A1 (fr) * 2008-04-09 2009-10-15 Toray Plastics Europe Film plastique extrude charge en particules metalliques, procede d'obtention et utilisations dudit film
WO2011088060A2 (fr) 2010-01-12 2011-07-21 Greenrock, Ltd. Film « paper-like » et son procédé de fabrication
WO2014159105A1 (fr) 2013-03-14 2014-10-02 Frito-Lay North America, Inc. Composition et procédé pour fabriquer un film d'emballage flexible
WO2019027336A1 (fr) * 2017-08-01 2019-02-07 "Ass-3" - Biuro Exportu, Importu I Marketingu Ewa Skoczeń Papier

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EP0454870A1 (fr) * 1989-11-16 1991-11-06 Mitsui Petrochemical Industries, Ltd. Resine pour films et procede de production de films utilisant cette resine
WO1992000188A1 (fr) * 1990-06-26 1992-01-09 Clopay Corporation Papiers synthetiques non etires et procedes de production desdits papiers

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JPS497055B1 (fr) * 1970-12-29 1974-02-18
US4082880A (en) * 1973-11-22 1978-04-04 Du Pont Of Canada Limited Paper-like thermoplastic film
US4341880A (en) * 1980-02-26 1982-07-27 Oji Yuka Goseishi Kabushiki Kaisha Resin compositions of improved hue
US4528235A (en) * 1982-08-05 1985-07-09 Allied Corporation Polymer films containing platelet particles
EP0454870A1 (fr) * 1989-11-16 1991-11-06 Mitsui Petrochemical Industries, Ltd. Resine pour films et procede de production de films utilisant cette resine
WO1992000188A1 (fr) * 1990-06-26 1992-01-09 Clopay Corporation Papiers synthetiques non etires et procedes de production desdits papiers

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Cited By (40)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0623646A2 (fr) * 1993-05-05 1994-11-09 BP Chemicals PlasTec GmbH Matériau d'emballage pour la fabrication de boîtes pliantes
EP0623646A3 (fr) * 1993-05-05 1996-11-27 Bp Chemicals Plastec Gmbh Matériau d'emballage pour la fabrication de boîtes pliantes.
US5762840A (en) * 1996-04-18 1998-06-09 Kimberly-Clark Worldwide, Inc. Process for making microporous fibers with improved properties
US5888681A (en) * 1997-05-23 1999-03-30 Eastman Kodak Company Photographic element with microvoided sheet of opalescent appearance
US5935690A (en) * 1997-05-23 1999-08-10 Eastman Kodak Company Sheets having a microvoided layer of strength sufficient to prevent bend cracking in an imaging member
US5874205A (en) * 1997-05-23 1999-02-23 Eastman Kodak Company Photographic element with indicia on oriented polymer back sheet
US5888683A (en) * 1997-05-23 1999-03-30 Eastman Kodak Company Roughness elimination by control of strength of polymer sheet in relation to base paper
US5888643A (en) * 1997-05-23 1999-03-30 Eastman Kodak Company Controlling bending stiffness in photographic paper
US5853965A (en) * 1997-05-23 1998-12-29 Eastman Kodak Company Photographic element with bonding layer on oriented sheet
US5902720A (en) * 1997-05-23 1999-05-11 Eastman Kodak Company Photographic element that resists curl using oriented sheets
US5866282A (en) * 1997-05-23 1999-02-02 Eastman Kodak Company Composite photographic material with laminated biaxially oriented polyolefin sheets
US5968695A (en) * 1997-05-23 1999-10-19 Eastman Kodak Company Roughness elimination by control of strength of polymer sheet in relation to base paper
US6004732A (en) * 1997-05-23 1999-12-21 Eastman Kodak Company Controlling bending stiffness in photographic paper
US6007665A (en) * 1997-05-23 1999-12-28 Eastman Kodak Company Photographic element with indicia on oriented polymer back sheet
US6040036A (en) * 1997-05-23 2000-03-21 Eastman Kodak Company Sheets having a microvoided layer of strength sufficient to prevent bend cracking in an imaging member
US6043009A (en) * 1997-05-23 2000-03-28 Eastman Kodak Company Composite photographic material with laminated biaxially oriented polyolefin sheets
KR100465176B1 (ko) * 1997-06-27 2005-05-18 삼성토탈 주식회사 통기성필름의제조방법
CN1105636C (zh) * 1998-03-25 2003-04-16 香港商龙盟环保纸(集团)有限公司 环保纸的制造方法
WO2002102593A1 (fr) * 2001-06-20 2002-12-27 Byron Le Roux Materiau polymere de type papier
US6743845B2 (en) 2001-08-09 2004-06-01 Equistar Chemicals, L.P. Oriented high density polyethylene film, compositions and process suitable for preparation thereof
WO2003014200A1 (fr) * 2001-08-09 2003-02-20 Equistar Chemicals, Lp Film en polyethylene haute densite oriente, compositions, et procede d'elaboration correspondant
US6635701B2 (en) 2001-08-09 2003-10-21 Equistar Chemicals L.P. Oriented high density polyethylene film, compositions and process suitable for preparation thereof
US6887923B2 (en) 2002-12-11 2005-05-03 Equistar Chemicals, L.P. Processing aids for enhanced machine direction orientation rates and property enhancement of polyolefin films using hydrocarbon waxes
US6946203B1 (en) 2002-12-31 2005-09-20 Exxon Mobil Oil Corporation Multilayer polyolefin substrate with low density core and stiff outer layers
US7211620B2 (en) * 2005-01-25 2007-05-01 Plasticos, Flexibles S.A. Foldable polyolefin films
WO2007015120A1 (fr) 2005-08-04 2007-02-08 Alfonso Alejandro Pira Papier synthetique
JP2009503221A (ja) * 2005-08-04 2009-01-29 アレハンドロ ピラ，アルフォンソ 合成紙
US20110244206A1 (en) * 2008-04-09 2011-10-06 Maria Cristina Penache Extruded plastic film filled with metal particles, method of production and uses thereof
WO2009124989A1 (fr) * 2008-04-09 2009-10-15 Toray Plastics Europe Film plastique extrude charge en particules metalliques, procede d'obtention et utilisations dudit film
WO2011088060A3 (fr) * 2010-01-12 2011-11-24 Greenrock, Ltd. Film « paper-like » et son procédé de fabrication
WO2011088060A2 (fr) 2010-01-12 2011-07-21 Greenrock, Ltd. Film « paper-like » et son procédé de fabrication
US8889047B2 (en) 2010-01-12 2014-11-18 Greenrock, Ltd. Paper-like film and process for making it
US9676131B2 (en) 2010-01-12 2017-06-13 Greenrock, Ltd. Paper-like film and process for making it
US10011063B2 (en) 2010-01-12 2018-07-03 Greenrock, Ltd. Paper-like film and method for making it
US10766180B2 (en) 2010-01-12 2020-09-08 Greenrock, Ltd. Paper-like film and process for making it
WO2014159105A1 (fr) 2013-03-14 2014-10-02 Frito-Lay North America, Inc. Composition et procédé pour fabriquer un film d'emballage flexible
EP2969565A4 (fr) * 2013-03-14 2016-11-02 Frito Lay North America Inc Composition et procédé pour fabriquer un film d'emballage flexible
AU2014241349B2 (en) * 2013-03-14 2018-01-04 Frito-Lay North America, Inc. Composition and method for making a flexible packaging film
WO2019027336A1 (fr) * 2017-08-01 2019-02-07 "Ass-3" - Biuro Exportu, Importu I Marketingu Ewa Skoczeń Papier
PL422429A1 (pl) * 2017-08-01 2019-02-11 Skoczeń Ewa Ass-3 Biuro Exportu, Importu I Marketingu Papier

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MX9305696A (es) 1994-06-30
AU4812493A (en) 1994-04-12
GB9219656D0 (en) 1992-10-28

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