EP1261661A1 - Filled epsilon-caprolactone based polymer compositions, method for preparing same and articles based on said compositions - Google Patents

Filled epsilon-caprolactone based polymer compositions, method for preparing same and articles based on said compositions

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Publication number
EP1261661A1
EP1261661A1 EP01901174A EP01901174A EP1261661A1 EP 1261661 A1 EP1261661 A1 EP 1261661A1 EP 01901174 A EP01901174 A EP 01901174A EP 01901174 A EP01901174 A EP 01901174A EP 1261661 A1 EP1261661 A1 EP 1261661A1
Authority
EP
European Patent Office
Prior art keywords
calcium carbonate
compositions according
compositions
particles
articles
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.)
Withdrawn
Application number
EP01901174A
Other languages
German (de)
French (fr)
Inventor
Dino Manfredi
Ivan Claeys
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Solvay SA
Original Assignee
Solvay SA
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 Solvay SA filed Critical Solvay SA
Priority to EP01901174A priority Critical patent/EP1261661A1/en
Publication of EP1261661A1 publication Critical patent/EP1261661A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/24—Acids; Salts thereof
    • C08K3/26—Carbonates; Bicarbonates
    • C08K2003/265—Calcium, strontium or barium carbonate
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/13—Hollow or container type article [e.g., tube, vase, etc.]
    • Y10T428/1352—Polymer or resin containing [i.e., natural or synthetic]
    • Y10T428/1397—Single layer [continuous layer]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/249921—Web or sheet containing structurally defined element or component
    • Y10T428/249953—Composite having voids in a component [e.g., porous, cellular, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/29—Coated or structually defined flake, particle, cell, strand, strand portion, rod, filament, macroscopic fiber or mass thereof
    • Y10T428/2982—Particulate matter [e.g., sphere, flake, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

  • compositions based on charged ⁇ -caprolactone polymer process for their preparation and articles based on these compositions
  • the invention relates to compositions based on ⁇ -caprolactone polymer containing calcium carbonate, a process for their preparation and articles (films, foams, bottles, plates and sheets) based on these compositions.
  • the polymers of ⁇ -caprolactone have good biodegradability, which makes them attractive for various applications where this property is required.
  • films used for making trash bags films for agriculture, films for packaging, shrouds or diapers; mosses, vials and thermoformed products including for example pots for young plants.
  • These polymers can also be used in the form of plates.
  • mineral fillers are commonly used.
  • mineral fillers Another disadvantage of mineral fillers is that they cannot generally be used at high concentration in compositions based on polymer of ⁇ -caprolactone, under penalty of deterioration in the appearance of the films produced (due in particular to the presence of hard spots and a rough feel, due to poor dispersion and the presence of agglomerates).
  • compositions based on ⁇ -caprolactone polymer containing as filler calcium carbonate which, not only do not have these drawbacks, but in addition may lead to an improvement in the mechanical properties of the articles manufactured at basis of these compositions.
  • the invention firstly relates to compositions based on a polymer of ⁇ -caprolactone comprising at least one polymer of -caprolactone and calcium carbonate.
  • compositions according to the invention contain more than 25% by weight of calcium carbonate.
  • compositions according to the invention comprise at least 30% by weight of calcium carbonate.
  • compositions according to the invention comprise up to 80% by weight of calcium carbonate, preferably up to 50% by weight of calcium carbonate.
  • F ⁇ -caprolactone polymers is intended to denote both homopolymers of ⁇ -caprolactone and copolymers with a preponderant content of ⁇ -caprolactone, for example at least 50% by weight, with other monomers, preferably with d other cyclic lactones.
  • cyclic lactones there may be mentioned for example ⁇ -propiolactone, ⁇ -butyrolactone, ⁇ -valerolactone, l, 4-dioxane-2-one, l, 4-dioxepane-2-one, 1, 5-dioxepane-2-one, glycolide (1,4-dioxane-2,5-dione) and their substituted derivatives as well as L-lactide, D-lactide, DL-lactide.
  • the polymers of ⁇ -caprolactone are preferably homopolymers of ⁇ -caprolactone.
  • the polymers of ⁇ -caprolactone involved in the compositions according to the invention may be polymers of unbranched ⁇ -caprolactone or polymers of branched ⁇ -caprolactone, that is to say having a level of non-zero connections.
  • the branched ⁇ -caprolactone polymers preferably have a gel content (rate of polymers insoluble in chloroform extracted using a soxhlet after 8 hours) less than or equal to 0.5%, in a particularly preferred manner equal to zero. They may have been obtained by a melt reaction in an extruder in the presence of a radical generator.
  • the radical generator is usually used in an amount sufficient to allow a non-zero connection rate of the polymers of ⁇ -caprolactone to be obtained while avoiding the gel formation.
  • radical generator it is possible, for example, to use 2,5-dimethyl-2,5-di-t-butylperoxy-hexane (DHBP).
  • the calcium carbonate has very good dispersibility in the polymers of ⁇ -caprolactone, and does not tend to form agglomerates in these polymers.
  • the calcium carbonate of the compositions according to the invention is usually in the form of particles, which preferably have one or more of the particle size characteristics mentioned below. Particle size curves were obtained for calcium carbonate of compositions according to the invention, showing the existence of particles of relatively small size and a narrow distribution of particle sizes.
  • the average diameter of the calcium carbonate particles is less than 5 ⁇ m. Preferably, it is less than 3 ⁇ m. In a particularly preferred manner, it is less than or equal to 1.5 ⁇ m. Very particularly preferably, it is less than 1 ⁇ m. In the case of narrow particle size distributions, the median particle diameter has a value very close to that of the mean diameter.
  • mean diameter is meant for the purposes of the present invention, the mean diameter measured by light diffraction with a Coulter LS 230 laser granulometer using the PIDS (Polarization Intensity Differential Scattering) measurement system.
  • the fraction of sodium carbonate particles having a diameter greater than 25 ⁇ m is usually less than 0.04% by volume, and preferably zero.
  • the fraction of calcium carbonate particles having a diameter greater than 10 ⁇ m is less than 3% by volume, preferably less than 1% by volume and particularly preferably less than or equal to 0.5% by volume.
  • the fraction of calcium carbonate particles having a diameter of less than 0.1 ⁇ m is generally greater than 2% by volume.
  • the high cutoff i.e. the particle diameter value which is such that at least 99% by weight of the particles has a diameter less than this value
  • the calcium carbonate of the compositions according to the invention may be of synthetic origin or of natural origin.
  • calcium carbonate is usually obtained by the carbonation of a lime milk or by the reaction between sodium carbonate and calcium hydroxide.
  • the calcium carbonate of the compositions according to the invention is of natural origin and comes from ground marble.
  • Examples of such calcium carbonates Figure calcium carbonate F ⁇ LMLE K ® 400 marketed by ECC International.
  • the calcium carbonate advantageously contains less than 0.5% of moisture, and preferably it contains less than 0.3% of moisture.
  • the calcium carbonate of the compositions according to the invention is usually in the form of coated particles.
  • the coating of the calcium carbonate particles represents less than 3% by weight, preferably less than 2% by weight, particularly preferably less than 1.5% by weight of the calcium carbonate particles.
  • the coating comprises one or more fatty acids chosen from saturated and unsaturated fatty acids having a chain of 8 to 26 carbon atoms. Good results have been obtained with saturated fatty acids.
  • caprylic acid C
  • capric acid Ceo
  • lauric acid C 1
  • myristic acid C H
  • palmitic acid C 16
  • stearic acid C ⁇ 8
  • arachidic acid C 0
  • behenic acid C 22
  • lignoceric acid C 24
  • unsaturated fatty acids there may be mentioned for example lauroleic acid (C 12 ), myristoleic acid (C ⁇ 4 ), palmitoleic acid (Ci ⁇ ), oleic acid (C ⁇ 8 ), ricinoleic acid (C ⁇ 8 ), linoleic acid (C ⁇ ) and linolenic acid (C 18 ).
  • the calcium carbonate in the compositions according to the invention comprises fatty acids linked to the particles of calcium carbonate and fatty acids not linked to the particles of calcium carbonate.
  • the proportion of fatty acids not linked to the particles of calcium carbonate is less than 0.5% by weight relative to the weight of calcium carbonate. It is preferably less than 0.1%, and particularly preferably, it is less than 0.05% by weight relative to the weight of calcium carbonate. More particularly preferably, the proportion of fatty acids not linked to calcium carbonate is less than 0.02% by weight relative to the weight of calcium carbonate. This concentration is measured by extraction with diethyl ether, as described in Examples of the present application (chemical analysis of the calcium carbonate Filmlink ® 400).
  • the calcium carbonate of the compositions according to the invention contains less than 2.5% by weight of impurities.
  • impurities can include carbonates, metal oxides and / or silicas.
  • the impurities in the coating can include, for example, fatty acids other than those mentioned above, fatty alcohols and aliphatic esters.
  • the calcium carbonate used is sold by ECC International under the brand Filmlink ®, in particular under the name Filmlink ® 400 Powder.
  • ECC International the technical sheet issued by the firm ECC International, dated June
  • compositions of the invention can be prepared by any suitable method. Good results are obtained if they are prepared by means of the process according to the invention.
  • the invention therefore also relates to a process for the preparation of compositions according to the invention, as defined above, according to which at least one polymer of ⁇ -caprolactone and of carbonate is melt-mixed in an extruder. calcium.
  • melt reaction is meant for the purposes of the present invention, any reaction in the substantial absence of solvent and at a temperature at least equal to the melting temperature of the polymers of ⁇ -caprolactone.
  • extruder is intended to denote any continuous device comprising at least one feed zone and, at its outlet, a discharge zone preceded by a compression zone, the latter forcing the molten mass to pass through the zone d 'evacuation.
  • the evacuation zone can also be followed by a granulation device or a device giving the extruded material a profiled shape, such as a film or a bottle parison.
  • a granulation device or a device giving the extruded material a profiled shape, such as a film or a bottle parison.
  • use will be made of known extruders based on the work of two screws, whether they are co-or counter-rotating or of BUSS type extruders.
  • the polymers of ⁇ -caprolactone may have been branched before the preparation of the compositions according to the invention as explained above or they can be branched during the preparation of the compositions according to the invention by performing the melt mixing in the presence of a radical generator.
  • the radical generator is usually used in an amount sufficient to allow a non-zero connection rate of the polymers of ⁇ -caprolactone to be obtained while avoiding the formation of a gel.
  • radical generator it is possible to use, for example, 2,5-dimethyl-2,5-di-t-butylperoxyhexane (DHBP).
  • Another subject of the invention is articles obtained from the compositions according to the invention as defined above.
  • compositions according to the invention can be obtained by using the compositions according to the invention by extrusion, by thermoforming or by injection.
  • the articles are obtained by using the compositions according to the invention by extrusion.
  • the articles according to the invention advantageously have an impact resistance, determined according to standard ISO 7765-1 A (1988), improved compared to that of similar articles obtained by the same implementation technique from reference compositions. identical, but devoid of calcium carbonate.
  • compositions according to the invention can be obtained from the composition according to the invention under consideration, by dissolving the latter, for example in chloroform, by completely eliminating, by any suitable method which does not affect the polymer, for example by filtering, the mineral fillers present and by evaporating the solvent so as to recover the solid polymer to then use it.
  • the implementation can be done for example by pressing or extrusion.
  • the articles according to the invention can be chosen from the following categories of articles: films, foams, bottles, plates and sheets.
  • the articles according to the invention are films, which can advantageously be obtained by blow molding or by extrusion in a flat die.
  • the examples which follow serve to illustrate the invention without however limiting its scope.
  • Calcium carbonate used in the inventive examples 2, 3, 4, 6, 8, 9 and 10 is calcium carbonate Filmlink ® 400 marketed by ECC International.
  • Carboxylic acids present in calcium carbonate FILMLINK 400 were dosed according to the method described below.
  • FILMLINK ® 400 calcium carbonate was subjected to hydrolysis with 12 N HCl for 1 hour at reflux. The aqueous phase, cooled, was extracted with diethyl ether. The extract was washed with distilled water until acidity was reached and then filtered over anhydrous sodium sulfate. It was then dried in a vacuum oven to constant weight.
  • the different components were identified by thin layer chromatography and quantified by gas chromatography.
  • the fraction of organic matter coating the calcium carbonate particles had a composition as given in Table 1.
  • the impurities in the coating were fatty alcohols and aliphatic fatty esters.
  • thermogravimetric analysis was performed on samples of 4 grams of calcium carbonate Filmlink ® 400, deposited without compaction on platinum tulips.
  • the analyzer used was a TA1 thermobalance from Mettler No. 32760, operating under Anatech software. The tests were carried out under dry air sweep.
  • the particle size distribution of FILMLINK ® 400 calcium carbonate particles was measured by light diffraction with a Coulter LS 230 laser particle sizer using the Polarization Intensity Differential Scattering (PIDS) measurement system.
  • PIDS Polarization Intensity Differential Scattering
  • This device measures the size distribution of particles in suspension in a carrier liquid.
  • the particles were used as marketed, that is to say in the coated state. They were presuspended in isopropanol, then injected into the granulometer. The measurement was carried out for 90 seconds.
  • the values of the various parameters were directly provided by the software adapted to the granulometer used. The measurements were made without the application of ultrasound. An average particle diameter of 1.5 ⁇ m was observed.
  • the fraction of particles with a diameter less than 0.1 ⁇ m was 2.4
  • the extruder used was the WERNER & PFLEIDERER ZSK ® 40 co-rotating twin screw extruder.
  • the diameter of the screws is 40 mm and their length is 1360 mm.
  • the screw rotation speed is 200 rpm (rotations per minute).
  • the extruder has been arranged so that it successively comprises a feed zone, a material melting zone, a homogenization zone, optionally a reaction zone, optionally a zone for introducing carbonate of calcium and any additives and an evacuation zone preceded by a compression zone. Each of these areas was at a very specific temperature.
  • the supply zone for polymers of ⁇ -caprolactone was at a temperature less than or equal to 20 ° C.
  • the melting zone of the material was at a temperature of 130 ° C.
  • the homogenization zone was at a temperature of 130 ° C.
  • the reaction zone was at a temperature of 180 ° C.
  • the area where calcium carbonate and optional additives, such as stabilizers, were introduced, was at a temperature of 180 ° C.
  • the compression zone was at a temperature of 180 ° C.
  • the evacuation area was at a temperature of 180 ° C.
  • the extruder was equipped with a gorse die.
  • the product was cooled in a water tank, then granulated and dried.
  • Films were produced by blow-molding from the compositions obtained according to Examples 1 to 6 on the WERNER & PFLEIDERER ZSK ® 40 extruder, using a second extruder.
  • a DOLCI 20 type extruder was used. This single screw extruder was used to bring the material to the molten state (75-150 ° C) before forcing it through an annular die 30 mm in diameter and 0, 75 mm air gap (28.5 mm core), oriented perpendicular to the axis of the extruder, so that the product leaves vertically upwards.
  • a BATTENFELD 45 extruder was also used, having an annular die of 80 mm in diameter and 0.9 mm of air gap.
  • the material flow was adjusted by changing the speed of rotation of the screw.
  • the tubular parison was then inflated by an internal air pressure and cooled externally by an air flow at distributed room temperature uniformly around the bubble thus formed a few centimeters above the die.
  • the swelling rate (defined as equal to the ratio of the diameter of the bubble to the diameter of the die) was adjusted by adjusting the internal air pressure.
  • the bubble was then gradually flattened by 2 guides, then pinched between 2 rollers, at least one of which is rubberized and at least one of which is driven.
  • the tubular parison was therefore also stretched in the axial direction by the two pinch rollers.
  • the stretching rate (defined as equal to the ratio of the speed of the film at the winding to the speed of the film at the die) was adjusted by varying the speed of the pinch rollers.
  • the final film thickness is a function of the die air gap, the swelling rate and the stretch rate.
  • Films were produced by extrusion in a flat die from the compositions obtained according to Examples 7 to 10 on the WERNER & PFLEIDERER ZSK ® 40 extruder, using a second extruder.
  • a Troester UP 30 type extruder was used. This single screw extruder was used to bring the material to the molten state (70-140 ° C) before forcing it through a 300 mm flat die of the Johnson 300 type / 2.
  • the molten polymer film was then collected on a Reifenhauser type chill-roll at 15 ° C.
  • the film thickness is a function of the material flow and the line speed. Characterization of the films obtained
  • DHBP 2,5-dimethyl-2,5-di-t-butylperoxyhexane LUPERSOL ® sold under the trademark 101 by Peroxid-Chemie, mixed with carbon dioxide, was sprayed onto poly- ⁇ -caprolactone using an appropriate introduction device.
  • the DHBP was introduced at a rate of 1 g per kg of poly- ⁇ -caprolactone mixture.
  • a film (No. 1) containing no filler material was produced by extrusion blow molding on a DOLCI 20 extruder from the composition according to Example 1 in the manner described above and under the conditions given below.
  • Film No. 1 has a smooth appearance and is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 63 g for a thickness of 58 ⁇ m.
  • Example 2 (according to the invention)
  • the example 1 was repeated, but added 30 weight%, based on the final composition, of a powder coated marketed under the designation Filmlink ® calcium carbonate 400 by ECC International in the introduction of the area calcium carbonate from the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
  • a film (No. 2) was produced from the composition according to Example 2 in the same way as in Example 1 and with the conditions listed below.
  • Film No. 2 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 74 g for a film with a thickness of 56 ⁇ m. or, surprisingly, an improved impact resistance compared to Example 1, which showed a lower resistance value for a greater thickness.
  • the film has an appearance as smooth as the film obtained according to Example 1.
  • Example 3 (according to the invention)
  • Example 1 was repeated by adding 40% by weight, relative to the final composition, of coated calcium carbonate marketed under the name Filmlink ® 400 by ECC International in the insertion area of the calcium carbonate of the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
  • a film (No. 3) was produced from the composition according to Example 3 in the same way as in Example 1 and with the conditions given below.
  • Film No. 3 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 278 g for a film only 28 ⁇ m thick.
  • ISO standard 7765-1 method A
  • an impact resistance was obtained which is far superior to that of Example 1, for a film which is, however, twice as thin.
  • the film always retains a smooth appearance.
  • Example 4 (according to the invention)
  • Example 1 was repeated by adding 50% by weight, relative to the final composition, of coated calcium carbonate marketed under the name Filmlink ® 400 by ECC International in the insertion area of the calcium carbonate of the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
  • a film (No. 4) was produced starting from the composition according to Example 4 in the same manner as in Example 1 and with the conditions listed below.
  • Film No. 4 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 110 g.
  • a composition according to Example 1 was used for the manufacture of a film (No. 5) by blow molding on a Battenfeld 45 extruder as described above with the conditions given below.
  • Film No. 5 is characterized by an impact resistance of less than 40 g. Indeed, it breaks at each impact of the lightest projectile available with a mass equal to 40 g.
  • Example 6 (according to the invention)
  • Example 2 A composition according to Example 2 containing 30% by weight, relative to the final composition, of a calcium carbonate powder coated marketed under the designation Filmlink ® 400 by ECC International, was used for the manufacture of a film by extrusion blow molding on a Battenfeld 45 extruder as described above.
  • a film (N ° 6) was produced from this composition with the conditions listed below.
  • the film No. 6 is characterized by an impact resistance measured according to ISO standard 7765.1 of 167 g, ie a value much higher than that obtained with the film produced in Example 5, which has a similar thickness. It has a smooth appearance.
  • a mixture of 50% by weight of the poly- ⁇ -caprolactone CAP A ® 650 sold by SOLVAY and 50% by weight of the poly- ⁇ -caprolactone CAP A ® 680 sold by SOLVAY was introduced into the feeding zone d '' a WERNER & PFLEIDERER ZSK ® 40 extruder with a throughput of 30 kg / h and has moved through the different areas of the extruder.
  • a film (No. 7) containing no filler material was produced by extrusion in a flat die on a Troester UP 30 extruder from the composition according to Example 7 in the manner described above and under the conditions given above. -Dessous.
  • Film No. 7 has a smooth appearance and is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 125 g for a thickness of 77 ⁇ m.
  • Example 7 was repeated, but added 30 weight%, based on the final composition, of a powder coated marketed under the designation Filmlink ® calcium carbonate 400 by ECC International in the introduction of the area calcium carbonate from the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
  • a film (No. 8) was produced starting from the composition according to Example 8 in the same manner as in Example 7 and with the conditions listed below.
  • Film No. 8 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 717 g for a film with a thickness of 97 ⁇ m. or a significantly improved impact resistance compared to Example 7.
  • the film has an appearance as smooth as the film obtained according to Example 7.
  • Example 9 (according to the invention)
  • Example 7 was repeated by adding 40% by weight, relative to the final composition, of coated calcium carbonate marketed under the name Filmlink ® 400 by ECC International in the insertion area of the calcium carbonate of the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
  • a film (No. 9) was produced starting from the composition according to Example 9 in the same manner as in Example 7 and with the conditions listed below.
  • Film No. 9 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of more than 1140 g for a film of 84 ⁇ m thickness.
  • ISO standard 7765-1 method A
  • an impact resistance was obtained which is far superior to that of Example 7.
  • the film always retains a smooth appearance.
  • Example 10 (according to the invention)
  • Example 7 was reproduced by adding 50% by weight, relative to the final composition, of coated calcium carbonate sold under / 53401
  • a film (No. 10) was produced starting from the composition according to Example 10 in the same manner as in Example 7 and with the conditions listed below.
  • Film No. 10 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 591 g.
  • the film retains a smooth appearance, without hard spots, which is an exceptional result.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Extrusion Moulding Of Plastics Or The Like (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Biological Depolymerization Polymers (AREA)

Abstract

The invention concerns epsilon -caprolactone based polymer compositions comprising at least an epsilon -caprolactone polymer and calcium carbonate. The invention also concerns the method for making said compositions which are used for making articles, in particular films obtained preferably by extrusion blow moulding or by slot die extrusion.

Description

Compositions à base de polymère de l' ε-caprolactone chargées, procédé pour leur préparation et articles à base de ces compositions Compositions based on charged ε-caprolactone polymer, process for their preparation and articles based on these compositions
L'invention concerne des compositions à base de polymère de l'ε- caprolactone contenant du carbonate de calcium, un procédé pour leur préparation et des articles (films, mousses, flacons, plaques et feuilles) à base de ces compositions.The invention relates to compositions based on ε-caprolactone polymer containing calcium carbonate, a process for their preparation and articles (films, foams, bottles, plates and sheets) based on these compositions.
Les polymères de l'ε-caprolactone ont une bonne biodégradabilité, ce qui les rend attractifs pour diverses applications où cette propriété est requise.The polymers of ε-caprolactone have good biodegradability, which makes them attractive for various applications where this property is required.
On peut citer parmi celles-ci, les films utilisés pour la réalisation de sacs poubelles, de films pour l'agriculture, de films pour l'emballage, de linceuls ou de couches-culottes; les mousses, les flacons et les produits thermoformés dont par exemple les pots pour jeunes plantes. Ces polymères peuvent également être mis en œuvre sous forme de plaques.Among these, mention may be made of films used for making trash bags, films for agriculture, films for packaging, shrouds or diapers; mosses, vials and thermoformed products including for example pots for young plants. These polymers can also be used in the form of plates.
Pour diminuer le coût de revient des articles produits à partir de ces polymères, on utilise couramment des matières de charge minérales.To reduce the cost price of articles produced from these polymers, mineral fillers are commonly used.
L'utilisation de telles matières de charge dans les compositions de polymères de l'ε-caprolactone pose divers problèmes, en particulier pour leurs applications sous forme de films. Ainsi, il est connu que la présence de telles matières de charge dans des compositions à base de ces polymères provoque habituellement, après la mise en œuvre de celles-ci, notamment sous forme de films, une détérioration des propriétés mécaniques, notamment de leur résistance au choc. Cet inconvénient est particulièrement gênant lorsqu'on met en œuvre les compositions sous forme de films, notamment à usage de sacs poubelles.The use of such fillers in the compositions of polymers of ε-caprolactone poses various problems, in particular for their applications in the form of films. Thus, it is known that the presence of such fillers in compositions based on these polymers usually causes, after the implementation of these, in particular in the form of films, a deterioration of the mechanical properties, in particular of their resistance. to shock. This drawback is particularly troublesome when the compositions are used in the form of films, in particular for the use of trash bags.
Un autre inconvénient des charges minérales est qu'elles ne peuvent généralement pas être utilisées à concentration élevée dans des compositions à base de polymère de l' ε-caprolactone, sous peine de détérioration de l'aspect des films produits (du fait notamment de la présence de points durs et d'un toucher rugueux, dus à une mauvaise dispersion et à la présence d'agglomérats).Another disadvantage of mineral fillers is that they cannot generally be used at high concentration in compositions based on polymer of ε-caprolactone, under penalty of deterioration in the appearance of the films produced (due in particular to the presence of hard spots and a rough feel, due to poor dispersion and the presence of agglomerates).
Le Demandeur a à présent découvert que, contrairement aux idées reçues, il était possible d'obtenir des compositions à base de polymère de l'ε- caprolactone contenant comme matière de charge du carbonate de calcium qui, non seulement ne présentent pas ces inconvénients, mais en outre peuvent conduire à une amélioration des propriétés mécaniques des articles fabriqués à base de ces compositions.The Applicant has now discovered that, contrary to popular belief, it was possible to obtain compositions based on ε-caprolactone polymer containing as filler calcium carbonate which, not only do not have these drawbacks, but in addition may lead to an improvement in the mechanical properties of the articles manufactured at basis of these compositions.
On a en effet observé que, de manière surprenante, on pouvait obtenir des articles présentant des propriétés mécaniques non détériorées, voire améliorées, en utilisant, dans les compositions de polymères de l' ε-caprolactone, des particules de carbonate de calcium, même à concentration élevée.It has in fact been observed that, surprisingly, it was possible to obtain articles having undamaged or even improved mechanical properties by using, in the compositions of polymers of ε-caprolactone, particles of calcium carbonate, even at high concentration.
L'invention a tout d'abord pour objet des compositions à base de polymère de l'ε-caprolactone comprenant au moins un polymère de l' -caprolactone et du carbonate de calcium.The invention firstly relates to compositions based on a polymer of ε-caprolactone comprising at least one polymer of -caprolactone and calcium carbonate.
Les compositions suivant l'invention comportent plus de 25 % en poids de carbonate de calcium. De manière préférée, les compositions suivant l'invention comportent au moins 30 % en poids de carbonate de calcium.The compositions according to the invention contain more than 25% by weight of calcium carbonate. Preferably, the compositions according to the invention comprise at least 30% by weight of calcium carbonate.
Habituellement, les compositions suivant l'invention comportent jusqu'à 80 % en poids de carbonate de calcium, de préférence jusqu'à 50 % en poids de carbonate de calcium. Par polymères de Fε-caprolactone, on entend désigner aussi bien les homopolymères de l'ε-caprolactone que les copolymères à teneur prépondérante en ε-caprolactone, par exemple au moins 50 % en poids, avec d'autres monomères, de préférence avec d'autres lactones cycliques. Parmi ces lactones cycliques, on peut citer par exemple la β-propiolactone, la γ-butyrolactone, la δ-valérolactone, la l,4-dioxane-2-one, la l,4-dioxépane-2-one, la 1,5-dioxépane- 2-one, le glycolide (l,4-dioxane-2,5-dione) et leurs dérivés substitués ainsi que le L-lactide, le D-lactide, le DL-lactide.Usually, the compositions according to the invention comprise up to 80% by weight of calcium carbonate, preferably up to 50% by weight of calcium carbonate. The term “Fε-caprolactone polymers” is intended to denote both homopolymers of ε-caprolactone and copolymers with a preponderant content of ε-caprolactone, for example at least 50% by weight, with other monomers, preferably with d other cyclic lactones. Among these cyclic lactones, there may be mentioned for example β-propiolactone, γ-butyrolactone, δ-valerolactone, l, 4-dioxane-2-one, l, 4-dioxepane-2-one, 1, 5-dioxepane-2-one, glycolide (1,4-dioxane-2,5-dione) and their substituted derivatives as well as L-lactide, D-lactide, DL-lactide.
Les polymères de l' ε-caprolactone sont de préférence des homopolymères de l' ε-caprolactone. Les polymères de l' ε-caprolactone intervenant dans les compositions selon l'invention peuvent être des polymères de l'ε-caprolactone non ramifiés ou des polymères de l'ε-caprolactone ramifiés, c'est-à-dire présentant un taux de branchements non nul.The polymers of ε-caprolactone are preferably homopolymers of ε-caprolactone. The polymers of ε-caprolactone involved in the compositions according to the invention may be polymers of unbranched ε-caprolactone or polymers of branched ε-caprolactone, that is to say having a level of non-zero connections.
Les polymères de l'ε-caprolactone ramifiés présentent de préférence un taux de gel (taux de polymères insolubles dans le chloroforme extraits au moyen d'un soxhlet après 8 heures) inférieur ou égal à 0,5 %, de manière particulièrement préférée égal à zéro. Ils peuvent avoir été obtenus par une réaction en masse fondue dans une extrudeuse en présence d'un générateur de radicaux. Dans ce cas, le générateur de radicaux est habituellement mis en oeuvre en une quantité suffisante pour permettre d'obtenir un taux de branchement non nul des polymères de l'ε-caprolactone tout en évitant la formation d'un gel. A titre de générateur de radicaux, on peut utiliser par exemple du 2,5-diméthyl-2,5-di-t-butylperoxy-hexane (DHBP).The branched ε-caprolactone polymers preferably have a gel content (rate of polymers insoluble in chloroform extracted using a soxhlet after 8 hours) less than or equal to 0.5%, in a particularly preferred manner equal to zero. They may have been obtained by a melt reaction in an extruder in the presence of a radical generator. In this case, the radical generator is usually used in an amount sufficient to allow a non-zero connection rate of the polymers of ε-caprolactone to be obtained while avoiding the gel formation. As radical generator, it is possible, for example, to use 2,5-dimethyl-2,5-di-t-butylperoxy-hexane (DHBP).
Avantageusement, le carbonate de calcium présente une très bonne aptitude à la dispersion dans les polymères de l'ε-caprolactone, et n'a pas tendance à former des agglomérats dans ces polymères.Advantageously, the calcium carbonate has very good dispersibility in the polymers of ε-caprolactone, and does not tend to form agglomerates in these polymers.
Il est important de préciser que les caractéristiques du carbonate de calcium utilisé dans les compositions suivant l'invention qui sont données ci-après sont des caractéristiques mesurées ou décrites pour le carbonate de calcium avant son incorporation dans les compositions suivant l'invention. Le carbonate de calcium des compositions suivant l'invention est habituellement sous forme de particules, qui présentent de préférence une ou plusieurs des caractéristiques granulométriques mentionnées ci-après. On a obtenu pour du carbonate de calcium de compositions suivant l'invention des courbes granulométriques montrant l'existence de particules de relativement petite taille et une distribution étroite de tailles de particules.It is important to specify that the characteristics of the calcium carbonate used in the compositions according to the invention which are given below are characteristics measured or described for the calcium carbonate before its incorporation in the compositions according to the invention. The calcium carbonate of the compositions according to the invention is usually in the form of particles, which preferably have one or more of the particle size characteristics mentioned below. Particle size curves were obtained for calcium carbonate of compositions according to the invention, showing the existence of particles of relatively small size and a narrow distribution of particle sizes.
Le diamètre moyen des particules de carbonate de calcium est inférieur à 5 μm. De manière préférée, il est inférieur à 3 μm. De manière particulièrement préférée, il est inférieur ou égal à 1,5 μm. De manière tout particulièrement préférée, il est inférieur à 1 μm. Dans le cas de distributions étroites de tailles de particules, le diamètre médian des particules a une valeur très proche de celle du diamètre moyen.The average diameter of the calcium carbonate particles is less than 5 μm. Preferably, it is less than 3 μm. In a particularly preferred manner, it is less than or equal to 1.5 μm. Very particularly preferably, it is less than 1 μm. In the case of narrow particle size distributions, the median particle diameter has a value very close to that of the mean diameter.
Par diamètre moyen, on entend désigner, aux fins de la présente invention, le diamètre moyen mesuré par diffraction de la lumière avec un granulomètre laser Coulter LS 230 en utilisant le système de mesure PIDS (Polarization Intensity Differential Scattering).By mean diameter is meant for the purposes of the present invention, the mean diameter measured by light diffraction with a Coulter LS 230 laser granulometer using the PIDS (Polarization Intensity Differential Scattering) measurement system.
La fraction des particules de carbonate de sodium ayant un diamètre supérieur à 25 μm est habituellement inférieure à 0,04 % en volume, et de préférence nulle.The fraction of sodium carbonate particles having a diameter greater than 25 μm is usually less than 0.04% by volume, and preferably zero.
La fraction des particules de carbonate de calcium ayant un diamètre supérieur à 10 μm est inférieure à 3 % en volume, de manière préférée inférieure à 1 % en volume et de manière particulièrement préférée inférieure ou égale à 0,5 % en volume.The fraction of calcium carbonate particles having a diameter greater than 10 μm is less than 3% by volume, preferably less than 1% by volume and particularly preferably less than or equal to 0.5% by volume.
La fraction des particules de carbonate de calcium ayant un diamètre inférieur à 0, 1 μm est en général supérieure à 2 % en volume. La coupure haute (c'est-à-dire la valeur de diamètre de particule qui est telle qu'au moins 99 % en poids des particules a un diamètre inférieur à cette valeur) est avantageusement inférieure à 12 μm, et de manière particulièrement préférée inférieure à 10 μm. De manière tout particulièrement préférée, elle est inférieure à 8 μm.The fraction of calcium carbonate particles having a diameter of less than 0.1 μm is generally greater than 2% by volume. The high cutoff (i.e. the particle diameter value which is such that at least 99% by weight of the particles has a diameter less than this value) is advantageously less than 12 μm, and in a particularly preferred manner less than 10 μm. Very particularly preferably, it is less than 8 μm.
Le carbonate de calcium des compositions suivant l'invention peut être d'origine synthétique ou d'origine naturelle.The calcium carbonate of the compositions according to the invention may be of synthetic origin or of natural origin.
Lorsqu'il est d'origine synthétique, le carbonate de calcium est habituellement obtenu par la carbonatation d'un lait de chaux ou par la réaction entre le carbonate de sodium et l'hydroxyde de calcium.When it is of synthetic origin, calcium carbonate is usually obtained by the carbonation of a lime milk or by the reaction between sodium carbonate and calcium hydroxide.
De préférence, le carbonate de calcium des compositions selon l'invention est d'origine naturelle et provient de marbre broyé. Parmi les exemples de tels carbonates de calcium figure le carbonate de calcium FΣLMLE K® 400 commercialisé par ECC International.Preferably, the calcium carbonate of the compositions according to the invention is of natural origin and comes from ground marble. Examples of such calcium carbonates Figure calcium carbonate FΣLMLE K ® 400 marketed by ECC International.
Le carbonate de calcium contient avantageusement moins de 0,5 % d'humidité, et de manière préférée, il contient moins de 0,3 % d'humidité. Le carbonate de calcium des compositions selon l'invention se présente habituellement sous forme de particules enrobées. L'enrobage des particules de carbonate de calcium représente moins de 3 % en poids, de préférence moins de 2 % en poids, de manière particulièrement préférée moins de 1,5 % en poids des particules de carbonate de calcium. L'enrobage comprend un ou plusieurs acides gras choisis parmi les acides gras saturés et insaturés ayant une chaîne de 8 à 26 atomes de carbone. De bons résultats ont été obtenus avec des acides gras saturés.The calcium carbonate advantageously contains less than 0.5% of moisture, and preferably it contains less than 0.3% of moisture. The calcium carbonate of the compositions according to the invention is usually in the form of coated particles. The coating of the calcium carbonate particles represents less than 3% by weight, preferably less than 2% by weight, particularly preferably less than 1.5% by weight of the calcium carbonate particles. The coating comprises one or more fatty acids chosen from saturated and unsaturated fatty acids having a chain of 8 to 26 carbon atoms. Good results have been obtained with saturated fatty acids.
Parmi les acides gras saturés, on peut citer par exemple l'acide caprylique (C ), l'acide caprique (Cio), l'acide laurique (C1 ), l'acide myristique (CH), l'acide palmitique (C16), l'acide stéarique (Cι8), l'acide arachidique (C 0), l'acide béhénique (C22), et l'acide lignocérique (C24).Among the saturated fatty acids, there may be mentioned for example caprylic acid (C), capric acid (Cio), lauric acid (C 1 ), myristic acid (C H ), palmitic acid ( C 16 ), stearic acid (Cι 8 ), arachidic acid (C 0 ), behenic acid (C 22 ), and lignoceric acid (C 24 ).
Parmi les acides gras insaturés, on peut citer par exemple l'acide lauroléique (C12), l'acide myristoléique (Cι4), l'acide palmitoléique (Ciό), l'acide oléique (Cι8), l'acide ricinoléique (Cι8), l'acide linoléique (Cι ) et l'acide linolénique (C18).Among the unsaturated fatty acids, there may be mentioned for example lauroleic acid (C 12 ), myristoleic acid (Cι 4 ), palmitoleic acid (Ciό), oleic acid (Cι 8 ), ricinoleic acid (Cι 8 ), linoleic acid (Cι) and linolenic acid (C 18 ).
Lorsque du carbonate de calcium est traité avec un agent comprenant un ou plusieurs acides gras pour obtenir un enrobage des particules, une partie de ces acides gras se lie chimiquement au carbonate de calcium. Dans le cadre de la présente invention, on parlera alors d'acides gras liés aux particules ou chemisorbés.When calcium carbonate is treated with an agent comprising one or more fatty acids to obtain a coating of the particles, part of these fatty acids binds chemically to calcium carbonate. In the context of the present invention, we will then speak of fatty acids linked to particles or chemisorbed.
Une autre partie de ces acides gras, soit n'ayant pas réagi, soit ayant, le cas échéant, réagi avec des ions Ca "1" présents dans le carbonate de calcium ne se lie pas chimiquement aux dites particules de carbonate de calcium. Dans le cadre de la présente invention, on parlera dans ce cas d'acides gras libres, non liés aux particules ou physisorbés. Le carbonate de calcium dans les compositions selon l'invention comporte des acides gras liés aux particules de carbonate de calcium et des acides gras non liés aux particules de carbonate de calcium.Another part of these fatty acids, either unreacted or having, if necessary if necessary, reacted with Ca "1" ions present in calcium carbonate does not chemically bond to said particles of calcium carbonate. In the context of the present invention, we will speak in this case of free fatty acids, not linked to particles or physisorbed. The calcium carbonate in the compositions according to the invention comprises fatty acids linked to the particles of calcium carbonate and fatty acids not linked to the particles of calcium carbonate.
Dans les compositions suivant l'invention, la proportion d'acides gras non liés aux particules de carbonate de calcium est de moins de 0,5 % en poids par rapport au poids du carbonate de calcium. Elle est de manière préférée de moins de 0,1 %, et de manière particulièrement préférée, elle est de moins de 0,05 % en poids par rapport au poids du carbonate de calcium. De manière plus particulièrement préférée, la proportion des acides gras non liés au carbonate de calcium est de moins de 0,02 % en poids par rapport au poids du carbonate de calcium. Cette concentration est mesurée par extraction au diéthyléther, selon la procédure décrite dans les exemples de la présente demande (Analyses chimiques du carbonate de calcium FILMLINK®400).In the compositions according to the invention, the proportion of fatty acids not linked to the particles of calcium carbonate is less than 0.5% by weight relative to the weight of calcium carbonate. It is preferably less than 0.1%, and particularly preferably, it is less than 0.05% by weight relative to the weight of calcium carbonate. More particularly preferably, the proportion of fatty acids not linked to calcium carbonate is less than 0.02% by weight relative to the weight of calcium carbonate. This concentration is measured by extraction with diethyl ether, as described in Examples of the present application (chemical analysis of the calcium carbonate Filmlink ® 400).
De préférence, le carbonate de calcium des compositions suivant l'invention contient moins de 2,5 % en poids d'impuretés. Ces impuretés peuvent comprendre des carbonates, des oxydes métalliques et/ou des silices. Lorsqu'il s'agit d'un carbonate de calcium enrobé, les impuretés de l'enrobage peuvent comprendre par exemple des acides gras autres que ceux mentionnés ci-dessus, des alcools gras et des esters aliphatiques.Preferably, the calcium carbonate of the compositions according to the invention contains less than 2.5% by weight of impurities. These impurities can include carbonates, metal oxides and / or silicas. In the case of a coated calcium carbonate, the impurities in the coating can include, for example, fatty acids other than those mentioned above, fatty alcohols and aliphatic esters.
Parmi les carbonates de calcium que l'on peut utiliser pour les compositions selon l'invention, on peut citer par exemple ceux décrits dans la demande internationale WO 99/28050.Among the calcium carbonates which can be used for the compositions according to the invention, mention may, for example, be made of those described in international application WO 99/28050.
De manière préférée, le carbonate de calcium utilisé est celui commercialisé par ECC International sous la marque FILMLINK®, en particulier sous l'appellation FILMLINK® 400 Powder. La fiche technique émise par la firme ECC International, datée de juinPreferably, the calcium carbonate used is sold by ECC International under the brand Filmlink ®, in particular under the name Filmlink ® 400 Powder. The technical sheet issued by the firm ECC International, dated June
1998 est incorporée par référence. Cette fiche comprend deux pages intitulées respectivement "FILMLINK 400 Additive Technology Product Description and Application Guideline" et "FILMLINK® 400 Powder". Un graphique donnant une distribution typique de la taille des particules de la poudre de carbonate de calcium FILMLINK® 400 figure sur cette seconde page. Pour compléter l'identification, on notera que cette fiche comporte les indications "T1351" et "AOT" dans son coin inférieur droit.1998 is incorporated by reference. This sheet includes two pages entitled "FILMLINK 400 Additive Technology Product Description and Application Guideline" and "FILMLINK ® 400 Powder" respectively. A graph of a typical size distribution of calcium carbonate powder particles Filmlink ® 400 is on the second page. To complete the identification, it will be noted that this sheet includes the indications "T1351" and "AOT" in its lower right corner.
A toutes fins utiles, la plupart des caractéristiques de la poudre de carbonate de calcium enrobé commercialisée par ECC International sous l'appellation FILMLINK® 400 telles qu'elles figurent sur la fiche technique de ce produit à la disposition du Demandeur sont reproduites ci-dessous, en traduction française. Description du produit Poudre FILMLINK®400For all practical purposes, most of the characteristics of the coated calcium carbonate powder sold by ECC International under the name FILMLINK ® 400 as they appear on the technical sheet of this product available to the Applicant are reproduced below , in French translation. Product description FILMLINK ® 400 powder
- Diamètre moyen 1,2 μm - Coupure haute 8 μm- Average diameter 1.2 μm - High cut 8 μm
- Blancheur contrôlée- Controlled whiteness
- Enrobage organophile- Organophilic coating
- Densité - 2,71 g/cm3 - Density - 2.71 g / cm 3
- Humidité maximale 0,2 % Caractéristiques mesurées à l'expédition- Maximum humidity 0.2% Characteristics measured upon shipment
- Brillance Hunter D-25 : 95 % minimum (avant traitement de surface)- Hunter D-25 shine: 95% minimum (before surface treatment)
- Teinte YI-1 : 0,3-1,1 maximum (avant traitement de surface)- YI-1 shade: 0.3-1.1 maximum (before surface treatment)
- Résidu au tamis de 325 mailles : 0,005 % maximum- Residue in a 325 mesh sieve: 0.005% maximum
- Résidu au tamis de 500 mailles : 0,010 % maximum - Humidité : 0,20 % maximum- Residue in a 500 mesh sieve: 0.010% maximum - Humidity: 0.20% maximum
- Taille moyenne des particules : 1-1,4 μm- Average particle size: 1-1.4 μm
- Enrobage, 0,8-1,2 % en poids(acide stéarique, grade haute pureté, approuvé comme additif alimentaire par la Fédéral Drug Administration)- Coating, 0.8-1.2% by weight (stearic acid, high purity grade, approved as a food additive by the Federal Drug Administration)
Analyse chimique typique (% en poids), avant traitement de surface - Humidité : maximum 0,2 %Typical chemical analysis (% by weight), before surface treatment - Humidity: maximum 0.2%
- Carbonate de calcium CaCO3 : 97,6 %- CaCO 3 calcium carbonate: 97.6%
- Carbonate de magnésium MgCO3 : 1,5 %- Magnesium carbonate MgCO 3 : 1.5%
- Oxyde d'aluminium : Al2O3 : 0,18 %- Aluminum oxide: Al 2 O 3 : 0.18%
- Oxyde de fer : Fe2O3 : 0,08 % - Silice : SiO2 : 0,2 %- Iron oxide: Fe 2 O 3 : 0.08% - Silica: SiO 2 : 0.2%
- Oxyde de manganèse : MnO : 0,004 %- Manganese oxide: MnO: 0.004%
- Métaux lourds : moins de 40 ppm Caractéristiques physiques typiques- Heavy metals: less than 40 ppm Typical physical characteristics
- Taille moyenne des particules (avant traitement de surface): 1,2 microns - Brillance à sec - Hunter D-25 (avant traitement de surface) : 95- Average particle size (before surface treatment): 1.2 microns - Dry gloss - Hunter D-25 (before surface treatment): 95
- Poids spécifique apparent En vrac 720 kg/m3 Compacté 100 kg/m3 - Absorption d'huile rub out 16- Apparent specific weight Bulk 720 kg / m 3 Compacted 100 kg / m 3 - Oil absorption rub out 16
Les compositions de l'invention peuvent être préparées par tout procédé approprié. De bons résultats sont obtenus si elles sont préparées au moyen du procédé selon l'invention.The compositions of the invention can be prepared by any suitable method. Good results are obtained if they are prepared by means of the process according to the invention.
L'invention concerne dès lors également un procédé pour la préparation de compositions suivant l'invention, telles que définies ci-dessus, selon lequel on mélange en masse fondue dans une extrudeuse au moins un polymère de l'ε- caprolactone et du carbonate de calcium.The invention therefore also relates to a process for the preparation of compositions according to the invention, as defined above, according to which at least one polymer of ε-caprolactone and of carbonate is melt-mixed in an extruder. calcium.
Par réaction en masse fondue, on entend désigner aux fins de la présente invention, toute réaction en l'absence substantielle de solvant et à une température au moins égale à la température de fusion des polymères de l'ε- caprolactone. Par extrudeuse, on entend désigner tout dispositif continu comprenant au moins une zone d'alimentation et, à sa sortie, une zone d'évacuation précédée d'une zone de compression, cette dernière forçant la masse fondue à passer au travers de la zone d'évacuation. La zone d'évacuation peut en outre être suivie d'un dispositif de granulation ou d'un dispositif donnant à la matière extrudée une forme profilée, telle qu'un film ou une paraison de flacon. Avantageusement, il sera fait appel à des extrudeuses connues basées sur le travail de deux vis, qu'elles soient co- ou contra-rotatives ou à des extrudeuses type BUSS.By melt reaction is meant for the purposes of the present invention, any reaction in the substantial absence of solvent and at a temperature at least equal to the melting temperature of the polymers of ε-caprolactone. The term “extruder” is intended to denote any continuous device comprising at least one feed zone and, at its outlet, a discharge zone preceded by a compression zone, the latter forcing the molten mass to pass through the zone d 'evacuation. The evacuation zone can also be followed by a granulation device or a device giving the extruded material a profiled shape, such as a film or a bottle parison. Advantageously, use will be made of known extruders based on the work of two screws, whether they are co-or counter-rotating or of BUSS type extruders.
Lorsque les compositions selon l'invention font intervenir des polymères de l' ε-caprolactone qui sont ramifiés, les polymères de l' ε-caprolactone peuvent avoir été ramifiés préalablement à la préparation des compositions selon l'invention comme explicité ci-dessus ou ils peuvent être ramifiés au moment de la préparation des compositions selon l'invention en effectuant le mélange en masse fondue en présence d'un générateur de radicaux. Dans ce cas, le générateur de radicaux est habituellement mis en œuvre en une quantité suffisante pour permettre d'obtenir un taux de branchement non nul des polymères de l' ε-caprolactone tout en évitant la formation d'un gel. A titre de générateur de radicaux, on peut utiliser par exemple du 2,5-diméthyl-2,5-di-t- butylperoxyhexane (DHBP).When the compositions according to the invention involve polymers of ε-caprolactone which are branched, the polymers of ε-caprolactone may have been branched before the preparation of the compositions according to the invention as explained above or they can be branched during the preparation of the compositions according to the invention by performing the melt mixing in the presence of a radical generator. In this case, the radical generator is usually used in an amount sufficient to allow a non-zero connection rate of the polymers of ε-caprolactone to be obtained while avoiding the formation of a gel. As radical generator, it is possible to use, for example, 2,5-dimethyl-2,5-di-t-butylperoxyhexane (DHBP).
L'invention a encore pour objet des articles obtenus à partir des compositions suivant l'invention telles que définies ci-dessus.Another subject of the invention is articles obtained from the compositions according to the invention as defined above.
Ces articles peuvent être obtenus par mise en œuvre des compositions selon l'invention par extrusion, par thermoformage ou par injection. De préférence, les articles sont obtenus par mise en oeuvre des compositions suivant l'invention par extrusion.These articles can be obtained by using the compositions according to the invention by extrusion, by thermoforming or by injection. Preferably, the articles are obtained by using the compositions according to the invention by extrusion.
Les articles selon l'invention ont avantageusement une résistance au choc, déterminée suivant la norme ISO 7765-1 A (1988), améliorée par rapport à celle d'articles similaires obtenus par la même technique de mise en oeuvre à partir de compositions de référence identiques, mais dépourvues de carbonate de calcium.The articles according to the invention advantageously have an impact resistance, determined according to standard ISO 7765-1 A (1988), improved compared to that of similar articles obtained by the same implementation technique from reference compositions. identical, but devoid of calcium carbonate.
Les conditions de la technique de mise en oeuvre pour les articles selon l'invention sont analogues et aussi proches que possible de celles utilisées pour les articles similaires et sont connues de l'homme du métier.The conditions of the processing technique for the articles according to the invention are analogous and as close as possible to those used for similar articles and are known to those skilled in the art.
Il est possible d'obtenir par fabrication directe une telle composition de référence, dépourvue de carbonate de calcium, correspondant à une composition déterminée suivant l'invention.It is possible to obtain, by direct manufacture, such a reference composition, devoid of calcium carbonate, corresponding to a composition determined according to the invention.
Il est également possible d'obtenir une telle composition à partir de la composition suivant l'invention considérée, en solubilisant celle-ci par exemple dans du chloroforme, en éliminant totalement, par toute méthode appropriée ne portant pas atteinte au polymère, par exemple par filtrage, les charges minérales présentes et en évaporant le solvant de façon à récupérer le polymère solide pour le mettre ensuite en œuvre. La mise en oeuvre peut se faire par exemple par pressage ou extrusion.It is also possible to obtain such a composition from the composition according to the invention under consideration, by dissolving the latter, for example in chloroform, by completely eliminating, by any suitable method which does not affect the polymer, for example by filtering, the mineral fillers present and by evaporating the solvent so as to recover the solid polymer to then use it. The implementation can be done for example by pressing or extrusion.
Les articles suivant l'invention peuvent être choisis parmi les catégories d'articles suivantes : films, mousses, flacons, plaques et feuilles. De préférence, les articles suivant l'invention sont des films, qui peuvent être avantageusement obtenus par extrusion soufflage ou par extrusion en filière plate. Les exemples qui suivent servent à illustrer l'invention sans pour autant en limiter la portée. Carbonate de calciumThe articles according to the invention can be chosen from the following categories of articles: films, foams, bottles, plates and sheets. Preferably, the articles according to the invention are films, which can advantageously be obtained by blow molding or by extrusion in a flat die. The examples which follow serve to illustrate the invention without however limiting its scope. Calcium carbonate
Le carbonate de calcium utilisé dans les exemples selon l'invention 2, 3, 4, 6, 8, 9 et 10 est le carbonate de calcium FILMLINK® 400 commercialisée par ECC International.Calcium carbonate used in the inventive examples 2, 3, 4, 6, 8, 9 and 10 is calcium carbonate Filmlink ® 400 marketed by ECC International.
Des analyses chimiques, des mesures thermogravimétriques, des mesures granulométriques et une mesure de la surface spécifique ont été effectuées sur le carbonate de calcium FILMLINK® 400 avant de procéder à la réalisation des compositions. Ces analyses et les résultats observés sont détaillés ci-après. Analyses chimiques du carbonate de calcium FILMLINK® 400Chemical analyzes, thermogravimetric measurements, particle size measurements and measurement of specific surface area were performed on calcium carbonate Filmlink ® 400 prior to the completion of the compositions. These analyzes and the results observed are detailed below. Chemical analyzes of FILMLINK ® 400 calcium carbonate
Les acides carboxyliques présents dans le carbonate de calcium FILMLINK 400 ont été dosés suivant la méthode décrite ci-après.Carboxylic acids present in calcium carbonate FILMLINK 400 were dosed according to the method described below.
Du carbonate de calcium FILMLINK® 400 a été soumis à une hydrolyse à l'HCl 12 N pendant 1 heure à reflux. La phase aqueuse, refroidie, a été extraite par du diéthyléther. L'extrait a été lavé par de l'eau distillée jusqu'à fin d'acidité et ensuite filtré sur du sulfate de sodium anhydre. Il a alors été séché en étuve sous vide jusqu'à poids constant.FILMLINK ® 400 calcium carbonate was subjected to hydrolysis with 12 N HCl for 1 hour at reflux. The aqueous phase, cooled, was extracted with diethyl ether. The extract was washed with distilled water until acidity was reached and then filtered over anhydrous sodium sulfate. It was then dried in a vacuum oven to constant weight.
Les différents composants ont été identifiés par chromatographie sur couche mince et quantifiés en chromatographie en phase gazeuse.The different components were identified by thin layer chromatography and quantified by gas chromatography.
Les mêmes techniques mises en œuvre sans effectuer d'hydrolyse avant l'étape d'extraction au diéthyléther ont permis de déterminer quelle est la proportion d'acides gras libres, qui ne sont pas liés chimiquement avec le carbonate de calcium.The same techniques used without carrying out hydrolysis before the diethyl ether extraction step made it possible to determine what is the proportion of free fatty acids, which are not chemically bound with calcium carbonate.
Il a résulté de ces analyses que la teneur totale en matière organique était de 1 % en poids, et que la composition de la fraction organique comportait majoritairement des acides gras.It resulted from these analyzes that the total organic matter content was 1% by weight, and that the composition of the organic fraction mainly comprised fatty acids.
La fraction des matières organiques enrobant les particules de carbonate de calcium présentait une composition telle que donnée au tableau 1.The fraction of organic matter coating the calcium carbonate particles had a composition as given in Table 1.
Tableau 1Table 1
Le solde représentait un peu plus de 6 % en poids. Aucune fraction non identifiée de l'extrait ne représentait plus de 0,2 % en poids de la matière organique. Parmi les impuretés de l'enrobage, on a trouvé des alcools gras et des esters gras aliphatiques.The balance was just over 6% by weight. No unidentified fraction of the extract represented more than 0.2% by weight of the organic matter. Among the impurities in the coating were fatty alcohols and aliphatic fatty esters.
Par ailleurs, une analyse des acides gras libres a révélé la présence de 0,09 g d'acide palmitique et de 0,05 g d'acide stéarique par kg de produit FILMLINK® 400. Le total des acides gras non liés aux particules de carbonate de calcium était donc de 0,14 g/kg , soit 0,014 % en poids de produit FILMLINK® 400. Mesures thermogravimétriques du carbonate de calcium FILMLINK® 400Furthermore, an analysis of free fatty acids revealed the presence of 0.09 g of palmitic acid and 0.05 g of stearic acid per kg of FILMLINK ® 400 product. The total fatty acids not linked to the calcium carbonate particles was therefore 0.14 g / kg, ie 0.014% by weight of product FILMLINK ® 400. Thermogravimetric measurements of calcium carbonate FILMLINK ® 400
Une analyse thermogravimétrique a été effectuée sur des échantillons de 4 grammes de carbonate de calcium FILMLINK® 400, déposés sans tassement sur des tulipes de platine. L'analyseur utilisé était une thermobalance TA1 de Mettler N° 32760, fonctionnant sous un logiciel Anatech. Les tests ont été effectués sous balayage d'air sec.A thermogravimetric analysis was performed on samples of 4 grams of calcium carbonate Filmlink ® 400, deposited without compaction on platinum tulips. The analyzer used was a TA1 thermobalance from Mettler No. 32760, operating under Anatech software. The tests were carried out under dry air sweep.
Lors d'un premier essai, on a effectué un chauffage à 0,5 K/minute de 20 à 200 °C, et lors d'un second essai, on a effectué le chauffage à 1 K/minute de 20 à 400 °C. Les résultats exprimés en perte de poids sont reproduits ci-dessous.During a first test, heating was carried out at 0.5 K / minute from 20 to 200 ° C, and during a second test, heating was carried out at 1 K / minute from 20 to 400 ° C . The results expressed in weight loss are reproduced below.
Mesures granulométriques du carbonate de calcium FILMLINK® 400Particle size measurements of FILMLINK ® 400 calcium carbonate
On a effectué des mesures de la distribution de la taille des particules de carbonate de calcium FILMLINK® 400 par diffraction de la lumière avec un granulomètre laser Coulter LS 230 en utilisant le système de mesure PIDS (Polarization Intensity Differential Scattering). Cet appareil mesure la distribution de taille de particules en suspension dans un liquide porteur. Les particules ont été utilisées telles que commercialisées, c'est-à-dire à l'état enrobé. Elles ont été mises en présuspension dans de l'isopropanol, puis injectées dans le granulomètre. La mesure a été effectuée pendant 90 secondes. Les valeurs des différents paramètres ont été directement fournies par le logiciel adapté au granulomètre utilisé. Le mesures ont été faites sans application d'ultrasons. On a observé un diamètre moyen des particules de 1,5 μm. La fraction des particules ayant un diamètre inférieur à 0, 1 μm était de 2,4The particle size distribution of FILMLINK ® 400 calcium carbonate particles was measured by light diffraction with a Coulter LS 230 laser particle sizer using the Polarization Intensity Differential Scattering (PIDS) measurement system. This device measures the size distribution of particles in suspension in a carrier liquid. The particles were used as marketed, that is to say in the coated state. They were presuspended in isopropanol, then injected into the granulometer. The measurement was carried out for 90 seconds. The values of the various parameters were directly provided by the software adapted to the granulometer used. The measurements were made without the application of ultrasound. An average particle diameter of 1.5 μm was observed. The fraction of particles with a diameter less than 0.1 μm was 2.4
% en volume ; la fraction des particules ayant un diamètre supérieur à 10 μm était de 0,5 % en volume, et la fraction de particules ayant un diamètre de plus de 25 μm était de 0,003 % en volume, c'est-à-dire tout à fait négligeable. On a également observé une coupure haute de 7,4 μm. Mesure de la surface spécifique du carbonate de calcium FILMLINK® 400 La surface spécifique a été mesurée suivant la méthode BET. La valeur trouvée était de 1,4 m2/g. Fabrication des compositions% in volume ; the fraction of particles having a diameter greater than 10 μm was 0.5% by volume, and the fraction of particles having a diameter of more than 25 μm was 0.003% by volume, that is to say quite negligible. A 7.4 μm high cutoff was also observed. Measurement of the specific surface area of FILMLINK ® 400 calcium carbonate The specific surface area was measured according to the BET method. The value found was 1.4 m 2 / g. Manufacturing of the compositions
L'extrudeuse utilisée a été l'extrudeuse double vis co-rotative WERNER & PFLEIDERER ZSK® 40. Le diamètre des vis est de 40 mm et leur longueur est de 1360 mm. La vitesse de rotation des vis est de 200 rpm (rotations par minute). L'extrudeuse a été aménagée de manière à ce qu'elle comprenne successivement une zone d'alimentation, une zone de fusion de la matière, une zone d'homogénéisation, facultativement une zone de réaction, facultativement une zone d'introduction du carbonate de calcium et d'additifs éventuels et une zone d'évacuation précédée d'une zone de compression. Chacune de ces zones se trouvait à une température bien spécifique.The extruder used was the WERNER & PFLEIDERER ZSK ® 40 co-rotating twin screw extruder. The diameter of the screws is 40 mm and their length is 1360 mm. The screw rotation speed is 200 rpm (rotations per minute). The extruder has been arranged so that it successively comprises a feed zone, a material melting zone, a homogenization zone, optionally a reaction zone, optionally a zone for introducing carbonate of calcium and any additives and an evacuation zone preceded by a compression zone. Each of these areas was at a very specific temperature.
La zone d'alimentation en polymères de l' ε-caprolactone se trouvait à une température inférieure ou égale à 20 °C.The supply zone for polymers of ε-caprolactone was at a temperature less than or equal to 20 ° C.
La zone de fusion de la matière se trouvait à une température de 130 °C.The melting zone of the material was at a temperature of 130 ° C.
La zone d'homogénéisation se trouvait à une température de 130 °C. La zone de réaction se trouvait à une température de 180 °C.The homogenization zone was at a temperature of 130 ° C. The reaction zone was at a temperature of 180 ° C.
La zone d'introduction du carbonate de calcium et d'additifs éventuels comme par exemple des agents stabilisants, se trouvait à une température de 180°C.The area where calcium carbonate and optional additives, such as stabilizers, were introduced, was at a temperature of 180 ° C.
La zone de compression était à une température de 180 °C. La zone d'évacuation était à une température de 180 °C.The compression zone was at a temperature of 180 ° C. The evacuation area was at a temperature of 180 ° C.
L'extrudeuse était munie d'une filière ajonc. Le produit a été refroidi dans un bac à eau puis granulé et séché. Fabrication de films par extrusion soufflageThe extruder was equipped with a gorse die. The product was cooled in a water tank, then granulated and dried. Film making by blow molding
Des films ont été réalisés par extrusion soufflage au départ des compositions obtenues selon les exemples 1 à 6 sur l'extrudeuse WERNER & PFLEIDERER ZSK® 40, au moyen d'une seconde extrudeuse.Films were produced by blow-molding from the compositions obtained according to Examples 1 to 6 on the WERNER & PFLEIDERER ZSK ® 40 extruder, using a second extruder.
On a utilisé une extrudeuse du type DOLCI 20. Cette extrudeuse monovis a été utilisée pour porter la matière à l'état fondu (75 - 150 °C) avant de la forcer à travers une filière annulaire de 30 mm de diamètre et de 0,75 mm d'entrefer (noyau de 28,5 mm), orientée perpendiculairement à l'axe de l'extrudeuse, de manière à ce que le produit sorte verticalement vers le haut.A DOLCI 20 type extruder was used. This single screw extruder was used to bring the material to the molten state (75-150 ° C) before forcing it through an annular die 30 mm in diameter and 0, 75 mm air gap (28.5 mm core), oriented perpendicular to the axis of the extruder, so that the product leaves vertically upwards.
On a également utilisé une extrudeuse BATTENFELD 45, ayant une filière annulaire de 80 mm de diamètre et de 0,9 mm d'entrefer.A BATTENFELD 45 extruder was also used, having an annular die of 80 mm in diameter and 0.9 mm of air gap.
Le débit de matière a été réglé en changeant la vitesse de rotation de la vis. La paraison tubulaire a alors été gonflée par une pression d'air intérieur et refroidie extérieurement par un flux d'air à température ambiante réparti uniformément autour de la bulle ainsi formée à quelques centimètres au dessus de la filière. Le taux de gonflement (défini comme égal au rapport du diamètre de la bulle sur le diamètre de la filière) a été réglé en ajustant la pression d'air intérieur. La bulle a ensuite été aplatie progressivement par 2 guides, puis pincée entre 2 rouleaux, dont au moins un est caoutchouté et au moins un est entraîné. La paraison tubulaire a donc également été étirée dans le sens axial par les deux rouleaux pinceurs. Le taux d'étirage (défini comme égal au rapport de la vitesse du film à l'enroulement sur la vitesse du film à la filière) a été ajusté en faisant varier la vitesse des rouleaux pinceurs. L'épaisseur finale du film est fonction de l'entrefer de la filière, du taux de gonflement et du taux d'étirage. Fabrication de films par extrusion en filière plateThe material flow was adjusted by changing the speed of rotation of the screw. The tubular parison was then inflated by an internal air pressure and cooled externally by an air flow at distributed room temperature uniformly around the bubble thus formed a few centimeters above the die. The swelling rate (defined as equal to the ratio of the diameter of the bubble to the diameter of the die) was adjusted by adjusting the internal air pressure. The bubble was then gradually flattened by 2 guides, then pinched between 2 rollers, at least one of which is rubberized and at least one of which is driven. The tubular parison was therefore also stretched in the axial direction by the two pinch rollers. The stretching rate (defined as equal to the ratio of the speed of the film at the winding to the speed of the film at the die) was adjusted by varying the speed of the pinch rollers. The final film thickness is a function of the die air gap, the swelling rate and the stretch rate. Film production by extrusion in a flat die
Des films ont été réalisés par extrusion en filière plate au départ des compositions obtenues selon les exemples 7 à 10 sur l'extrudeuse WERNER & PFLEIDERER ZSK® 40, au moyen d'une seconde extrudeuse. On a utilisé une extrudeuse du type Troester UP 30. Cette extrudeuse monovis a été utilisée pour porter la matière à l'état fondu (70 - 140 °C) avant de la forcer à travers une filière plate de 300 mm de type Johnson 300/2. Le film de polymère fondu a ensuite été collecté sur un tambour (chill-roll) de type Reifenhauser se trouvant à 15 °C. L'épaisseur du film est fonction du débit de matière et de la vitesse de la ligne. Caractérisation des films obtenusFilms were produced by extrusion in a flat die from the compositions obtained according to Examples 7 to 10 on the WERNER & PFLEIDERER ZSK ® 40 extruder, using a second extruder. A Troester UP 30 type extruder was used. This single screw extruder was used to bring the material to the molten state (70-140 ° C) before forcing it through a 300 mm flat die of the Johnson 300 type / 2. The molten polymer film was then collected on a Reifenhauser type chill-roll at 15 ° C. The film thickness is a function of the material flow and the line speed. Characterization of the films obtained
Des mesures de résistance au choc ont été réalisées sur les films obtenus. La résistance au choc a été mesurée selon la norme ISO 7765-1 (1988) (méthode A). Exemple 1 (comparatif)Impact resistance measurements were carried out on the films obtained. The impact resistance was measured according to ISO standard 7765-1 (1988) (method A). Example 1 (comparative)
Un mélange de 60 % en poids de la poly-ε-caprolactone CAP A® 650 vendue par SOLVAY et 40 % en poids de la poly-ε-caprolactone CAP A® 680 vendue par SOLVAY (dont la masse moléculaire moyenne en nombre, mesurée par chromatographie par perméation de gel est de 55 000 g/mole) a été introduit dans la zone d'alimentation d'une extrudeuse WERNER & PFLEIDERER ZSK® 40 avec un débit de 30 kg/h et s'est déplacé au travers des différentes zones de l'extrudeuse.A mixture of 60% by weight of the poly-ε-caprolactone CAP A ® 650 sold by SOLVAY and 40% by weight of the poly-ε-caprolactone CAP A ® 680 sold by SOLVAY (including the number average molecular weight, measured by gel permeation chromatography is 55,000 g / mole) was introduced into the feed zone of a WERNER & PFLEIDERER ZSK ® 40 extruder with a throughput of 30 kg / h and moved through the different extruder areas.
Dans la zone de fusion de l'extrudeuse, le 2,5-diméthyl-2,5-di-t- butylperoxyhexane (DHBP) vendu sous la marque LUPERSOL® 101 par PEROXID CHEMIE, en mélange avec le dioxyde de carbone, a été pulvérisé sur la poly-ε-caprolactone au moyen d'un dispositif d'introduction approprié. Le DHBP a été introduit à raison de 1 g par kg de mélange de poly-ε-caprolactone.In the melting zone of the extruder, 2,5-dimethyl-2,5-di-t-butylperoxyhexane (DHBP) LUPERSOL ® sold under the trademark 101 by Peroxid-Chemie, mixed with carbon dioxide, was sprayed onto poly-ε-caprolactone using an appropriate introduction device. The DHBP was introduced at a rate of 1 g per kg of poly-ε-caprolactone mixture.
Un film (N° 1) ne contenant aucune matière de charge a été réalisé par extrusion soufflage sur une extrudeuse DOLCI 20 au départ de la composition selon l'exemple 1 de la manière décrite ci-dessus et avec les conditions reprises ci-dessous.A film (No. 1) containing no filler material was produced by extrusion blow molding on a DOLCI 20 extruder from the composition according to Example 1 in the manner described above and under the conditions given below.
Le film N° 1 a un aspect lisse et se caractérise par une résistance au choc mesurée suivant la norme ISO 7765-1 (méthode A) de 63 g pour une épaisseur de 58 μm. Exemple 2 (suivant l'invention)Film No. 1 has a smooth appearance and is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 63 g for a thickness of 58 μm. Example 2 (according to the invention)
L 'exemple 1 a été reproduit, en ajoutant toutefois 30 % en poids, par rapport à la composition finale, d'une poudre de carbonate de calcium enrobé commercialisé sous l'appellation FILMLINK® 400 par ECC International dans la zone d'introduction du carbonate de calcium de l'extrudeuse WERNER & PFLEIDERER ZSK® 40 décrite ci-dessus.The example 1 was repeated, but added 30 weight%, based on the final composition, of a powder coated marketed under the designation Filmlink ® calcium carbonate 400 by ECC International in the introduction of the area calcium carbonate from the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
Un film (N° 2) a été réalisé au départ de la composition selon l'exemple 2 de la même manière qu'à l'exemple 1 et avec les conditions reprises ci-dessous.A film (No. 2) was produced from the composition according to Example 2 in the same way as in Example 1 and with the conditions listed below.
Le film N° 2 se caractérise par une résistance au choc mesurée suivant la norme ISO 7765-1 (méthode A) de 74 g pour un film d'un épaisseur de 56 μm. soit, de manière surprenante, une résistance au choc améliorée par rapport à l'exemple 1, qui montrait une valeur de résistance moindre pour une épaisseur supérieure.Film No. 2 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 74 g for a film with a thickness of 56 μm. or, surprisingly, an improved impact resistance compared to Example 1, which showed a lower resistance value for a greater thickness.
Le film a une apparence aussi lisse que le film obtenu suivant l'exemple 1. Exemple 3 (suivant l'invention)The film has an appearance as smooth as the film obtained according to Example 1. Example 3 (according to the invention)
L'exemple 1 a été reproduit en ajoutant 40 % en poids, par rapport à la composition finale, de carbonate de calcium enrobé commercialisé sous l'appellation FILMLINK® 400 par ECC International dans la zone d'introduction du carbonate de calcium de l'extrudeuse WERNER & PFLEIDERER ZSK® 40 décrite ci-dessus.Example 1 was repeated by adding 40% by weight, relative to the final composition, of coated calcium carbonate marketed under the name Filmlink ® 400 by ECC International in the insertion area of the calcium carbonate of the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
Un film (N° 3) a été réalisé au départ de la composition selon l'exemple 3 de la même manière qu'à l'exemple 1 et avec les conditions reprises ci-dessous.A film (No. 3) was produced from the composition according to Example 3 in the same way as in Example 1 and with the conditions given below.
Le film N° 3 se caractérise par une résistance au choc mesurée suivant la norme ISO 7765-1 (méthode A) de 278 g pour un film de seulement 28 μm d'épaisseur. Ainsi, de manière extrêmement surprenante, on a obtenu une résistance au choc de très loin supérieure à celle de l'exemple 1, pour un film pourtant deux fois plus mince. Le film conserve toujours une apparence lisse. Exemple 4 (suivant l'invention)Film No. 3 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 278 g for a film only 28 μm thick. Thus, extremely surprisingly, an impact resistance was obtained which is far superior to that of Example 1, for a film which is, however, twice as thin. The film always retains a smooth appearance. Example 4 (according to the invention)
L'exemple 1 a été reproduit en ajoutant 50 % en poids, par rapport à la composition finale, de carbonate de calcium enrobé commercialisé sous l'appellation FILMLINK® 400 par ECC International dans la zone d'introduction du carbonate de calcium de l'extrudeuse WERNER & PFLEIDERER ZSK® 40 décrite ci-dessus.Example 1 was repeated by adding 50% by weight, relative to the final composition, of coated calcium carbonate marketed under the name Filmlink ® 400 by ECC International in the insertion area of the calcium carbonate of the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
Un film (N° 4) a été réalisé au départ de la composition selon l'exemple 4 de la même manière qu'à l'exemple 1 et avec les conditions reprises ci-dessous.A film (No. 4) was produced starting from the composition according to Example 4 in the same manner as in Example 1 and with the conditions listed below.
Le film N° 4 se caractérise par une résistance au choc mesurée suivant la norme ISO 7765-1 (méthode A) de 110 g.Film No. 4 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 110 g.
Même à cette très forte concentration en matière de charge, le film conserve une apparence lisse, sans points durs, ce qui constitue un résultat exceptionnel. Exemple 5 (comparatif)Even at this very high concentration of filler, the film retains a smooth appearance, without hard spots, which is an exceptional result. Example 5 (comparative)
Une composition suivant l'exemple 1 a été utilisée pour la fabrication d'un film (N° 5) par extrusion soufflage sur une extrudeuse Battenfeld 45 tel que décrite ci-dessus avec les conditions reprises ci-dessous.A composition according to Example 1 was used for the manufacture of a film (No. 5) by blow molding on a Battenfeld 45 extruder as described above with the conditions given below.
Le film N° 5 se caractérise par une résistance au choc inférieure à 40 g. En effet, il casse à chaque impact du projectile le plus léger disponible de masse égale à 40 g. Exemple 6 (suivant l'invention)Film No. 5 is characterized by an impact resistance of less than 40 g. Indeed, it breaks at each impact of the lightest projectile available with a mass equal to 40 g. Example 6 (according to the invention)
Une composition suivant l'exemple 2, contenant 30 % en poids, par rapport à la composition finale, d'une poudre de carbonate de calcium enrobé commercialisé sous l'appellation FILMLINK® 400 par ECC International, a été utilisée pour la fabrication d'un film par extrusion soufflage sur une extrudeuse Battenfeld 45 tel que décrite ci-dessus.A composition according to Example 2 containing 30% by weight, relative to the final composition, of a calcium carbonate powder coated marketed under the designation Filmlink ® 400 by ECC International, was used for the manufacture of a film by extrusion blow molding on a Battenfeld 45 extruder as described above.
Un film (N° 6) a été réalisé au départ de cette composition avec les conditions reprises ci-dessous.A film (N ° 6) was produced from this composition with the conditions listed below.
Le film N° 6 se caractérise par une résistance au choc mesurée suivant la norme ISO 7765.1 de 167 g soit une valeur très supérieure à celle obtenue avec le film produit à l'exemple 5, qui a une épaisseur similaire. Il présente un aspect lisse.The film No. 6 is characterized by an impact resistance measured according to ISO standard 7765.1 of 167 g, ie a value much higher than that obtained with the film produced in Example 5, which has a similar thickness. It has a smooth appearance.
Lors des tests de résistance au choc effectués sur les films obtenus selon l'invention, on constate que ceux-ci ne cassent pas de façon fragile avant la rupture. Le choc du projectile est amorti et fait peu de bruit. De plus, les films selon l'invention blanchissent aux alentours de la zone d'impact, ce qui est une indication d'un allongement non négligeable avant la rupture éventuelle. Exemple 7 (comparatif)During impact resistance tests carried out on the films obtained according to the invention, it is found that they do not break brittle before breaking. The impact of the projectile is absorbed and makes little noise. In addition, the films according to the invention whiten around the impact zone, which is an indication of a non-negligible elongation before possible rupture. Example 7 (comparative)
Un mélange de 50 % en poids de la poly-ε-caprolactone CAP A® 650 vendue par SOLVAY et 50 % en poids de la poly-ε-caprolactone CAP A® 680 vendue par SOLVAY a été introduit dans la zone d'alimentation d'une extrudeuse WERNER & PFLEIDERER ZSK® 40 avec un débit de 30 kg/h et s'est déplacé au travers des différentes zones de l'extrudeuse.A mixture of 50% by weight of the poly-ε-caprolactone CAP A ® 650 sold by SOLVAY and 50% by weight of the poly-ε-caprolactone CAP A ® 680 sold by SOLVAY was introduced into the feeding zone d '' a WERNER & PFLEIDERER ZSK ® 40 extruder with a throughput of 30 kg / h and has moved through the different areas of the extruder.
Un film (N° 7) ne contenant aucune matière de charge a été réalisé par extrusion en filière plate sur une extrudeuse Troester UP 30 au départ de la composition selon l'exemple 7 de la manière décrite ci-dessus et avec les conditions reprises ci-dessous.A film (No. 7) containing no filler material was produced by extrusion in a flat die on a Troester UP 30 extruder from the composition according to Example 7 in the manner described above and under the conditions given above. -Dessous.
Le film N° 7 a un aspect lisse et se caractérise par une résistance au choc mesurée suivant la norme ISO 7765-1 (méthode A) de 125 g pour une épaisseur de 77 μm.Film No. 7 has a smooth appearance and is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 125 g for a thickness of 77 μm.
Exemple 8 (suivant l'invention)Example 8 (according to the invention)
L 'exemple 7 a été reproduit, en ajoutant toutefois 30 % en poids, par rapport à la composition finale, d'une poudre de carbonate de calcium enrobé commercialisé sous l'appellation FILMLINK® 400 par ECC International dans la zone d'introduction du carbonate de calcium de l'extrudeuse WERNER & PFLEIDERER ZSK® 40 décrite ci-dessus.The Example 7 was repeated, but added 30 weight%, based on the final composition, of a powder coated marketed under the designation Filmlink ® calcium carbonate 400 by ECC International in the introduction of the area calcium carbonate from the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
Un film (N° 8) a été réalisé au départ de la composition selon l'exemple 8 de la même manière qu'à l'exemple 7 et avec les conditions reprises ci-dessous.A film (No. 8) was produced starting from the composition according to Example 8 in the same manner as in Example 7 and with the conditions listed below.
Le film N° 8 se caractérise par une résistance au choc mesurée suivant la norme ISO 7765-1 (méthode A) de 717 g pour un film d'un épaisseur de 97 μm. soit une résistance au choc nettement améliorée par rapport à l'exemple 7.Film No. 8 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 717 g for a film with a thickness of 97 μm. or a significantly improved impact resistance compared to Example 7.
Le film a une apparence aussi lisse que le film obtenu suivant l'exemple 7. Exemple 9 (suivant l'invention)The film has an appearance as smooth as the film obtained according to Example 7. Example 9 (according to the invention)
L'exemple 7 a été reproduit en ajoutant 40 % en poids, par rapport à la composition finale, de carbonate de calcium enrobé commercialisé sous l'appellation FILMLINK® 400 par ECC International dans la zone d'introduction du carbonate de calcium de l'extrudeuse WERNER & PFLEIDERER ZSK® 40 décrite ci-dessus.Example 7 was repeated by adding 40% by weight, relative to the final composition, of coated calcium carbonate marketed under the name Filmlink ® 400 by ECC International in the insertion area of the calcium carbonate of the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
Un film (N° 9) a été réalisé au départ de la composition selon l'exemple 9 de la même manière qu'à l'exemple 7 et avec les conditions reprises ci-dessous.A film (No. 9) was produced starting from the composition according to Example 9 in the same manner as in Example 7 and with the conditions listed below.
Le film N° 9 se caractérise par une résistance au choc mesurée suivant la norme ISO 7765-1 (méthode A) de plus de 1140 g pour un film de 84 μm d'épaisseur. Ainsi, de manière extrêmement surprenante, on a obtenu une résistance au choc de très loin supérieure à celle de l'exemple 7. Le film conserve toujours une apparence lisse. Exemple 10 (suivant l'invention)Film No. 9 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of more than 1140 g for a film of 84 μm thickness. Thus, extremely surprisingly, an impact resistance was obtained which is far superior to that of Example 7. The film always retains a smooth appearance. Example 10 (according to the invention)
L'exemple 7 a été reproduit en ajoutant 50 % en poids, par rapport à la composition finale, de carbonate de calcium enrobé commercialisé sous /53401Example 7 was reproduced by adding 50% by weight, relative to the final composition, of coated calcium carbonate sold under / 53401
1717
l'appellation FILMLINK 400 par ECC International dans la zone d'introduction du carbonate de calcium de l'extrudeuse WERNER & PFLEIDERER ZSK® 40 décrite ci-dessus.the name FILMLINK 400 by ECC International in the zone for the introduction of calcium carbonate from the WERNER & PFLEIDERER ZSK ® 40 extruder described above.
Un film (N° 10) a été réalisé au départ de la composition selon l'exemple 10 de la même manière qu'à l'exemple 7 et avec les conditions reprises ci-dessous.A film (No. 10) was produced starting from the composition according to Example 10 in the same manner as in Example 7 and with the conditions listed below.
Le film N° 10 se caractérise par une résistance au choc mesurée suivant la norme ISO 7765-1 (méthode A) de 591 g.Film No. 10 is characterized by an impact resistance measured according to ISO standard 7765-1 (method A) of 591 g.
Même à cette très forte concentration en matière de charge, le film conserve une apparence lisse, sans points durs, ce qui constitue un résultat exceptionnel. Even at this very high concentration of filler, the film retains a smooth appearance, without hard spots, which is an exceptional result.

Claims

R E V E N D I C A T I O N SR E V E N D I C A T I O N S
1 - Compositions à base de polymère de l' ε-caprolactone comprenant au moins un polymère de l'ε- caprolactone et du carbonate de calcium.1 - Compositions based on ε-caprolactone polymer comprising at least one polymer of ε-caprolactone and calcium carbonate.
2 - Compositions suivant la revendication 1, caractérisées en ce qu'elles comportent plus de 25 % en poids de carbonate de calcium.2 - Compositions according to claim 1, characterized in that they comprise more than 25% by weight of calcium carbonate.
3 - Compositions suivant l'une quelconque des revendications précédentes, caractérisées en ce que le diamètre moyen des particules de carbonate de calcium est inférieur à 5 μm.3 - Compositions according to any one of the preceding claims, characterized in that the average diameter of the calcium carbonate particles is less than 5 μm.
4 - Compositions suivant l'une quelconque des revendications précédentes, caractérisées en ce que la fraction des particules de carbonate de calcium ayant un diamètre supérieur à 10 μm est inférieure à 3 % en volume.4 - Compositions according to any one of the preceding claims, characterized in that the fraction of the calcium carbonate particles having a diameter greater than 10 μm is less than 3% by volume.
5 - Compositions suivant l'une quelconque des revendications précédentes, caractérisées en ce que les particules de carbonate de calcium présentent une coupure haute inférieure à 12 μm.5 - Compositions according to any one of the preceding claims, characterized in that the calcium carbonate particles have a high cut-off of less than 12 μm.
6 - Compositions suivant la revendication 5, caractérisées en ce que le carbonate de calcium est d'origine naturelle et provient de marbre broyé.6 - Compositions according to claim 5, characterized in that the calcium carbonate is of natural origin and comes from ground marble.
7 - Compositions suivant l'une quelconque des revendications précédentes, caractérisées en ce que le carbonate de calcium contient moins de 0,5 % d'humidité.7 - Compositions according to any one of the preceding claims, characterized in that the calcium carbonate contains less than 0.5% moisture.
8 - Compositions suivant l'une quelconque des revendications précédentes, caractérisées en ce que le carbonate de calcium se présente sous forme de particules enrobées.8 - Compositions according to any one of the preceding claims, characterized in that the calcium carbonate is in the form of coated particles.
9 - Compositions suivant la revendication 8, caractérisées en ce que l'enrobage représente moins de 3 % en poids des particules de carbonate de calcium.9 - Compositions according to claim 8, characterized in that the coating represents less than 3% by weight of the calcium carbonate particles.
10 - Compositions suivant l'une quelconque des revendications 8 et 9, caractérisées en ce que l'enrobage comprend un ou plusieurs acides gras choisis parmi les acides gras saturés et insaturés ayant une chaîne de 8 à 26 atomes de carbone. 1 1 - Compositions suivant la revendication 10, caractérisées en ce que le carbonate de calcium comporte des acides gras liés aux particules de carbonate de calcium et des acides gras non liés aux particules de carbonate de calcium.10 - Compositions according to any one of claims 8 and 9, characterized in that the coating comprises one or more fatty acids chosen from saturated and unsaturated fatty acids having a chain of 8 to 26 carbon atoms. 1 1 - Compositions according to claim 10, characterized in that the calcium carbonate comprises fatty acids linked to the particles of calcium carbonate and fatty acids not linked to the particles of calcium carbonate.
12 - Compositions suivant la revendication 11, caractérisées en ce que la proportion d'acides gras non liés aux particules de carbonate de calcium est de moins de 0,5 % en poids par rapport au poids de carbonate de calcium.12 - Compositions according to claim 11, characterized in that the proportion of fatty acids not linked to the calcium carbonate particles is less than 0.5% by weight relative to the weight of calcium carbonate.
13 - Procédé pour la préparation de compositions suivant l'une quelconque des revendications précédentes, caractérisé en ce qu'on mélange en masse fondue dans une extrudeuse au moins un polymère de l' ε-caprolactone et du carbonate de calcium.13 - Process for the preparation of compositions according to any one of the preceding claims, characterized in that at least one polymer of ε-caprolactone and calcium carbonate is melt-mixed in an extruder.
14 - Articles obtenus à partir des compositions suivant l'une quelconque des revendications 1 à 12.14 - Articles obtained from the compositions according to any one of claims 1 to 12.
15 - Articles suivant la revendication 14, obtenus par mise en œuvre par extrusion des compositions suivant l'une quelconque des revendications 1 à 12.15 - Articles according to claim 14, obtained by implementation by extrusion of the compositions according to any one of claims 1 to 12.
16 - Articles suivant la revendication 15, caractérisés en ce qu'ils ont une résistance au choc, déterminée suivant la norme ISO 7765-1 A (1988), améliorée par rapport à celle d'articles similaires obtenus par la même technique de mise en oeuvre à partir de compositions de référence identiques, mais dépourvues de carbonate de calcium.16 - Articles according to claim 15, characterized in that they have an impact resistance, determined according to ISO standard 7765-1 A (1988), improved compared to that of similar articles obtained by the same setting technique works from identical reference compositions, but devoid of calcium carbonate.
17 - Articles suivant l'une quelconque des revendications 14 à 16, caractérisés en ce qu'ils sont choisis parmi les catégories d'articles suivantes : films, mousses, flacons, plaques et feuilles.17 - Articles according to any one of claims 14 to 16, characterized in that they are chosen from the following categories of articles: films, foams, bottles, plates and sheets.
18 - Articles suivant la revendication 17, caractérisés en ce qu'ils sont des films.18 - Articles according to claim 17, characterized in that they are films.
19 - Films suivant la revendication 18, caractérisé en ce qu'ils sont obtenus par extrusion soufflage ou par extrusion en filière plate. 19 - Films according to claim 18, characterized in that they are obtained by blow molding or by extrusion in a flat die.
EP01901174A 2000-01-20 2001-01-19 Filled epsilon-caprolactone based polymer compositions, method for preparing same and articles based on said compositions Withdrawn EP1261661A1 (en)

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EP00200231A EP1118636A1 (en) 2000-01-20 2000-01-20 Filled caprolactone based polymer compositions, process for their preparation and articles made thereform
EP00200231 2000-01-20
EP01901174A EP1261661A1 (en) 2000-01-20 2001-01-19 Filled epsilon-caprolactone based polymer compositions, method for preparing same and articles based on said compositions
PCT/EP2001/000578 WO2001053401A1 (en) 2000-01-20 2001-01-19 Filled epsilon-caprolactone based polymer compositions, method for preparing same and articles based on said compositions

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US20030129401A1 (en) 2003-07-10
JP2003535154A (en) 2003-11-25

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