EP3833709A1 - Procédé de production d'un film comprenant un polymère thermoplastique et une charge inorganique - Google Patents

Procédé de production d'un film comprenant un polymère thermoplastique et une charge inorganique

Info

Publication number
EP3833709A1
EP3833709A1 EP19749625.0A EP19749625A EP3833709A1 EP 3833709 A1 EP3833709 A1 EP 3833709A1 EP 19749625 A EP19749625 A EP 19749625A EP 3833709 A1 EP3833709 A1 EP 3833709A1
Authority
EP
European Patent Office
Prior art keywords
film
stretching
inorganic filler
transverse direction
longitudinal direction
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.)
Pending
Application number
EP19749625.0A
Other languages
German (de)
English (en)
Inventor
Jan Barth
Roland Lund
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.)
Brueckner Maschinenbau GmbH and Co KG
Original Assignee
Brueckner Maschinenbau GmbH and Co KG
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 Brueckner Maschinenbau GmbH and Co KG filed Critical Brueckner Maschinenbau GmbH and Co KG
Publication of EP3833709A1 publication Critical patent/EP3833709A1/fr
Pending legal-status Critical Current

Links

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
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C55/00—Shaping by stretching, e.g. drawing through a die; Apparatus therefor
    • B29C55/02—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets
    • B29C55/10—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial
    • B29C55/12—Shaping by stretching, e.g. drawing through a die; Apparatus therefor of plates or sheets multiaxial biaxial
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K3/00—Use of inorganic substances as compounding ingredients
    • C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
    • C08K3/013—Fillers, pigments or reinforcing additives
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/04—Homopolymers or copolymers of ethene
    • C08L23/06—Polyethene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/10—Homopolymers or copolymers of propene
    • C08L23/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/16—Elastomeric ethene-propene or ethene-propene-diene copolymers, e.g. EPR and EPDM rubbers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L23/00—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers
    • C08L23/02—Compositions of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Compositions of derivatives of such polymers not modified by chemical after-treatment
    • C08L23/18—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms
    • C08L23/20—Homopolymers or copolymers of hydrocarbons having four or more carbon atoms having four to nine carbon atoms
    • C08L23/22—Copolymers of isobutene; Butyl rubber ; Homo- or copolymers of other iso-olefins
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B38/00—Ancillary operations in connection with laminating processes
    • B32B38/0012—Mechanical treatment, e.g. roughening, deforming, stretching
    • B32B2038/0028—Stretching, elongating
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B2323/00—Polyalkenes
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B32—LAYERED PRODUCTS
    • B32B—LAYERED PRODUCTS, i.e. PRODUCTS BUILT-UP OF STRATA OF FLAT OR NON-FLAT, e.g. CELLULAR OR HONEYCOMB, FORM
    • B32B27/00—Layered products comprising a layer of synthetic resin
    • B32B27/32—Layered products comprising a layer of synthetic resin comprising polyolefins
    • B32B27/327—Layered products comprising a layer of synthetic resin comprising polyolefins comprising polyolefins obtained by a metallocene or single-site catalyst
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2323/00—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers
    • C08J2323/02—Characterised by the use of homopolymers or copolymers of unsaturated aliphatic hydrocarbons having only one carbon-to-carbon double bond; Derivatives of such polymers not modified by chemical after treatment
    • C08J2323/10—Homopolymers or copolymers of propene
    • C08J2323/12—Polypropene
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J2491/00—Characterised by the use of oils, fats or waxes; Derivatives thereof
    • C08J2491/06—Waxes
    • 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
    • C08K2003/262—Alkali metal carbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2203/00—Applications
    • C08L2203/16—Applications used for films

Definitions

  • thermoplastic polymer and inorganic filler
  • the present invention relates to a method for producing a film comprising at least 20% by weight of thermoplastic polymer and 50 to 75% by weight of inorganic filler, and comprises the steps: providing the mixture, melting the mixture, producing a film (cast film) from the mixture, cooling the film to produce a film, stretching the film in the longitudinal direction and in the transverse direction, the particle size of the inorganic filler being at most 5 ⁇ m and the stretching ratio in the longitudinal direction and in the transverse direction being at least 3.5. Films produced by this process and their use are also the subject of the present invention.
  • Films comprising plastics and fillers have been known for a long time. Foils the thermoplastic polymer and Inorganic fillers have been proposed as a substitute for paper.
  • Polyolefin films with filler content that are intended as paper substitute are divided into different groups depending on the proportion of the filler. If the filler content is below 50% by weight, one speaks more of a synthetic paper (also “SynPa”) or an FPO film (“Filled Polyolefin Films”). Stone papers (also called “stone paper” or “stone paper”) are highly filled polyolefin films that contain calcium carbonate particles and a polyolefin, such as polypropylene or polyethylene. In certain circumstances, a mixture of both plastics can be used. One speaks of stone paper when the filler content is greater than or equal to 50%.
  • Synthetic paper is usually a bi-axially stretched product, but the calcium carbonate filling levels are significantly lower than with stone paper.
  • the fill levels of such synthetic papers are well below 50% by weight calcium carbonate.
  • an elasticity module of at least about 500 MPa and a tensile strength of at least about 15 MPa in the longitudinal and transverse directions are required.
  • the calcium carbonate content should be at least 50% by weight in order to reduce costs and keep the carbon dioxide balance as low as possible.
  • the density should not be significantly above 1 g / cm 3 .
  • a low density with the same mechanical properties leads to resource conservation and cost reduction
  • Today's recycling processes sort products according to their density. If the density is significantly more than 1 g / cm 3 , the film is not added to the polyolefin recycling stream and is removed from the material cycle. However, a high calcium carbonate content increases the density, so that a high calcium carbonate content and a low density are contradictory requirements.
  • a reduction in density can be achieved by stretching the film in the longitudinal direction, which in turn affects the elasticity module and the tensile strength of the film.
  • the film should have both a high proportion of filler, low density and good mechanical properties. Among the mechanical properties, good tensile strength and a good elastic modulus are particularly desirable.
  • the film should also have good printability. Good foldability is also desirable. Description of the invention
  • the present invention relates to a method for producing a film comprising at least one thermoplastic polymer and at least one inorganic filler, comprising the steps:
  • thermoplastic polymer Providing a mixture comprising at least one thermoplastic polymer and at least one inorganic filler
  • the proportion of the thermoplastic polymer in the film being at least 20% by weight
  • the proportion of the inorganic filler in the film being in the range from 50 to 75% by weight and the particle size of the inorganic filler is at most 5 ⁇ m, characterized in that the stretch ratio in the longitudinal direction is at least 3.5 and the stretch ratio in the transverse direction is also at least 3.5.
  • the stretch ratio of the film in the longitudinal direction is equal to the length of the film after the stretching divided by the length of the film before stretching.
  • the stretch ratio of the film in the transverse direction is equal to the width of the film after stretching divided by the width of the film before stretching.
  • the production process leads to a film with good mechanical properties and good printability.
  • the proportion of filler is less than 50% by weight, the carbon dioxide balance is less favorable and the costs of production are higher. If the proportion of filler is above 75% by weight, stretching is not possible. If less than 20% by weight of thermoplastic polymer is used, stretching is likewise not possible and / or the mechanical properties and the printability suffer. If the film contains no further components apart from the thermoplastic polymer and the inorganic filler, the proportion of the thermoplastic polymer is at least 25% by weight. All data in percent by weight (% by weight) relate to the total mass of the film.
  • the stretching ratios are less than 3.5, the printability suffers too, in particular the standard deviation of the film thickness becomes too great.
  • the density of the film drops when stretched.
  • the film therefore has too high a density.
  • the mechanical properties suffer and the surface of the film becomes uneven, which affects printability.
  • the manufacturing method according to the invention leads to the fact that the stretching in the longitudinal and transverse directions can take place in a controlled manner.
  • This is preferred
  • the mixture melted in a mixing and processing unit.
  • the unit is particularly preferably selected from the group consisting of single-screw extruder, twin-screw extruder (co-rotating), bus kneader or planetary roller extruder. Extruders are very particularly preferred, and extruders are most preferably selected from the group consisting of single-screw extruder and twin-screw extruder (co-rotating).
  • the melt is preferably extruded to produce the film.
  • the melt is preferably discharged via a Breitschiitz nozzle.
  • a cooling roller is preferably used for cooling.
  • an air knife is preferably used, which applies the melt to the cooling roll. This makes it possible to produce a smooth, flat film that has cooled as evenly as possible.
  • a process according to the invention is therefore particularly preferred for producing a film comprising at least one thermoplastic polymer and at least one inorganic filler, comprising the steps:
  • the proportion of the thermoplastic polymer in the film is at least 20% by weight
  • the proportion of the inorganic filler in the film is in the range from 50 to 75% by weight and the particle size of the inorganic filler is at most 5 ⁇ m, characterized in that net that the stretch ratio in the longitudinal direction is at least 3.5 and the stretch ratio in the transverse direction if at least 3.5.
  • the cooling roll temperature is preferably between 30 and 100 ° C. Lower temperatures are preferred in order to achieve rapid cooling. If the inorganic filler in the film is more than 60% by weight, however, the temperature is preferably 80 to 100 ° C. and particularly preferably 95 to 100 ° C. At lower temperatures, the melt or the melt film cannot be applied evenly to the chill roll, which leads to uneven cooling. A film with homogeneous properties over the entire surface of the film cannot be obtained or can only be obtained with difficulty. The resulting film is then preferably cooled to room temperature (usually 23 ° C).
  • the cooled, non-stretched film is stretched lengthways and crossways. This is preferably done by sequential stretching.
  • the film is stretched first in the longitudinal and then in the transverse direction.
  • simultaneous stretching is also possible, with the film which has not yet been stretched being stretched simultaneously in the longitudinal and transverse directions.
  • the film is preferably fed to a longitudinal stretching unit (MDO) during the sequential stretching and stretched in the longitudinal direction (machine direction (MD)) at temperatures of 130 to 165 ° C.
  • MD machine direction
  • TDO transverse furnace stretched in the transverse direction (cross-machine direction (TD)).
  • the transverse stretching is preferably carried out at temperatures in the range from 145 to 175 ° C., particularly preferably in the range from 150 to 170 ° C., very particularly preferably in the range from 155 to 165 ° C. and most preferably in the range from 158 to 162 ° C. In particular 160 ° C are suitable. These are the temperatures of the film.
  • a method according to the invention is preferred, which is characterized in that the stretching ratios in the longitudinal direction and in the transverse direction are in the range from 3.5 to 7.5, particularly preferably in the range from 4 to 7.
  • a method according to the invention is very particularly preferred, which is characterized in that the stretching ratio in the longitudinal direction is in a range from 4 to
  • the properties of the film in particular the density and the mechanical properties, are in a balanced relationship within the specified ranges. This applies in particular to the narrower areas.
  • the stretching ratios in the longitudinal direction and in the transverse direction can differ. This can serve to adjust the mechanical properties in the longitudinal and transverse directions so that they are as similar as possible.
  • Another important property of paper is its rigidity. Both in processing and in use, the film according to the invention should therefore have a stiffness similar to that of classic paper, if possible.
  • the rigidity of the The film obtained according to the method is also influenced by the stretching ratio.
  • the films according to the invention preferably also have the same mechanical properties in the longitudinal and transverse directions.
  • the stretch ratio in the transverse direction is preferably 0.4 to 0.6 above the stretch ratio in the longitudinal direction. This applies in particular to sequential drawing.
  • the film is stretched, it is preferably subjected to a heat treatment (also “curing” or “annealing”).
  • a heat treatment also “curing” or “annealing”.
  • the stretching of the last stretching process is maintained.
  • the tensile forces that act on the film are not reduced and the dimensions of the film are retained.
  • the temperature of the film during the heat treatment is preferably approximately at the level of the temperature used during the stretching or slightly above it.
  • the temperature of the film during the heat treatment is particularly preferably 5 to 20 ° C. and very particularly preferably 5 to 15 ° C. above the last temperature used during the stretching.
  • Relaxation is also preferably carried out.
  • the transverse stretching of the last stretching process at the beginning of the relaxation is slightly reduced. For this, the tensile forces acting on the film are reduced and the film contracts slightly.
  • This relaxation can be carried out in the longitudinal direction, in the transverse direction or in the directions.
  • the stretching is preferably reduced by up to 20%, particularly preferably by 2 to 15% and very particularly preferably by 5 to 10%.
  • the temperature of the film during relaxation is preferably at the same level as in the previous process step or slightly below. Preferably lies the temperature of the film by 5 to 20 ° C below the temperature of the previous process step.
  • the matrix of the thermoplastic polymer partially detaches from the inorganic filler and cavities arise in the film, which can negatively influence the mechanical properties and other properties of the film.
  • these cavities can at least partially be closed again and the shrinkage behavior, the mechanical properties, such as tensile strength and elasticity module and the final density of the film can be improved and / or adjusted.
  • the edge of the film is then preferably cut off.
  • a surface treatment is preferably carried out. This can be, for example, a corona, plasma or flame treatment. Such a surface treatment results in a significantly improved surface tension. This is useful, for example, if subsequent printing or coating is to be carried out. Corona treatment is preferably carried out.
  • the film can be rolled up by a winder.
  • a typical method according to the invention is therefore a method for producing a film comprising at least one thermoplastic polymer and at least one inorganic filler, comprising the steps:
  • thermoplastic polymer in the film being at least 20% by weight, the proportion of the inorganic filler in the film in the range from 50 to 75% by weight. -% and the particle size of the inorganic filler is at most 5 ym, characterized in that the stretch ratio in the longitudinal direction is at least 3.5 and the stretch ratio in the transverse direction is also at least 3.5.
  • the thermoplastic polymer preferably comprises at least one polymer which is selected from the group consisting of polyethylene, polypropylene, polystyrene, polyethylene terephthalate, recycled polymers thereof or mixtures thereof. The use of these polymers leads to particularly advantageous properties of the film.
  • the thermoplastic polymer particularly preferably comprises a polymer which is selected from the group consisting of polyethylene, polypropylene or mixtures thereof. Polyethylene and polypropylene are particularly inexpensive and result in particularly stable films.
  • the thermoplastic polymer particularly preferably comprises polypropylene. It most preferably consists of it. Preferably, however, the thermoplastic polymer does not include poly lactic acid.
  • the polypropylene used preferably has a melt mass flow rate (MFR, also melt mass flow rate) according to ISO 1133 in the range from 0.1 to 25 g / 10 min, particularly preferably in the range from 0.5 to 20 g / 10 min and most preferably from 0.5 to 5 g / 10 min.
  • the polyethylene used preferably has a melt mass flow rate (MFR, also melt mass flow rate) according to ISO 1133 in the range from 0.02 to 15 g / 10 min, particularly preferably in the range from 0.02 to 1.2 g / 10 min.
  • the inorganic filler is preferably selected from the group consisting of calcium carbonate, coal dust, calcium sulfate, barium sulfate, kaolin, mica, zinc oxide, Dolomite, calcium silicate, glass, silicates, chalk, talc, pigment, titanium dioxide, silicon dioxide, bentonite, clay, di atomite and mixtures thereof.
  • glass can be used in the form of glass fibers or hollow microparticles made of glass.
  • calcium carbonate is very particularly preferred.
  • the filler consists of calcium carbonate.
  • Calcium carbonate gives the film according to the invention a white color and good mechanical properties. Calcium carbonate is also an easily accessible natural resource.
  • the proportion of the inorganic filler in the film is preferably in the range from 50 to 70% by weight, particularly preferably in the range from 55 to 65% by weight. This applies in particular to calcium carbonate.
  • the inorganic filler is used in the form of a powder.
  • the particle size of the inorganic filler is preferably at most 5 ⁇ m, particularly preferably at most 3 ⁇ m and most preferably at most 2 ⁇ m. If the particles are too large, the mechanical properties and the printability of the film are insufficient. It is further preferred that the particle size of the inorganic filler is at least 0.1 ⁇ m, preferably at least 0.5 ⁇ m. If the particles are too small, the workability of the melt and the film are insufficient. In addition, such fine powders tend to develop dust, which causes problems during processing. This size information applies in particular to calcium carbonate. All particle sizes given here are average particle sizes that are measured by laser diffractometry.
  • the values given are dso values, i.e. they indicate the value at which 50% of the particles are smaller than the specified value.
  • a method according to the invention which is characterized in that the film additionally comprises up to 25% by weight of at least one polyolefin elastomer.
  • the at least one polyolefin elastomer is particularly preferably selected from the group consisting of polyisobutylene, ethylene-propylene rubber and ethylene-propylene-diene monomer rubber (EPDM rubber).
  • EPDM rubber ethylene-propylene-diene monomer rubber
  • a method according to the invention according to one of the preceding claims which is characterized in that the film comprises auxiliary substances (additives). Also preferred is a method according to the invention, which is characterized in that the film comprises at least one auxiliary which is selected from the group consisting of adhesion promoters, dispersants, stabilizers, lubricants, antistatic agents, solid plasticizers, activating agents, promoters, Anti-aging agents, agents for preventing burn marks, binders, heat-resistant agents, initiator agents, polymerization catalysts, emulsifiers, plasticizers, heat stabilizers, light stabilizers, flame retardants and mold release agents.
  • the film particularly preferably contains dispersants.
  • Dispersants allow the stretching of films with a high proportion of filler and lead to a smooth surface. Furthermore, foils which contain dispersants have particularly uniform thicknesses.
  • the film preferably comprises up to 5% of auxiliary substances.
  • the film particularly preferably contains auxiliaries in an amount in the range from 1 to 5% by weight.
  • the film particularly preferably contains stretching aids, which are preferably selected from the group consisting of po- polyethylene waxes and polypropylene waxes. The most preferred are polypropylene waxes. In game suitable for commercially available polyethylene waxes and butt lypropylenwachse type Licocenes ® from Clariant in Frankfurt / Main, Germany.
  • the film according to the invention can be a film with only a single layer or a multilayer film.
  • Multi-layer films are preferably produced by co-extrusion.
  • Co-extrusion offers the possibility of varying the filler content in the individual layers and, if necessary, adapting them to the requirements. In particular, the surface properties can be optimized.
  • Co-extrusion also offers the possibility of significantly reducing the cooling roller temperatures (to approx. 30 ° C) by significantly reducing the filler content in the outer layers.
  • a method according to the invention which is characterized in that the film has a tensile strength in the longitudinal direction and in the transverse direction of at least 15 MPa, preferably of at least 18 MPa and particularly preferably of at least 20 MPa.
  • tensile strength is necessary so that the films can be used similarly to paper and have sufficient strength for the further processing of the film.
  • an inventive method is preferred, which is characterized in that the tensile strength of the film in the transverse direction is not more than 50%, preferably not more than 40% and very particularly preferably not more than 30% of the tensile strength of the film in Longitudinal direction deviates. If the tensile strengths in the longitudinal and transverse directions too differ greatly from each other, the foils splice up too easily during processing and are therefore unusable.
  • the film has a modulus of elasticity in the longitudinal and transverse directions of at least 150 MPa, preferably of at least 300 MPa, very particularly preferably of at least 500 MPa, even more preferably of at least 800 MPa and most preferably be at least 1000 MPa. It is further preferred that the modulus of elasticity of the film in the transverse direction is not more than 50%, preferably not more than 30% and very particularly preferably not more than 20% and most preferably not more than 10% of the modulus of elasticity of the film in Longitudinal direction deviates.
  • these values for the elastic modulus of the film according to the invention confer paper-like properties.
  • the thickness of the film is preferably 5 ⁇ m to 1 mm, particularly preferably 10 ⁇ m to 300 ⁇ m and very particularly preferably 20 ⁇ m to 180 ⁇ m.
  • the particle size of the filler is preferably not greater than half the thickness of the film, particularly preferably not greater than one fifth of the thickness of the film.
  • a method according to the invention which is characterized in that the standard deviation of the thickness of the film is not more than 30%, preferably not more than 20%, particularly preferably not more than 10% and most preferably not more than 5% ,
  • the thickness is preferably determined using a conventional film thickness measuring device. To determine the standard deviation, 30 measurements are preferably used, which are carried out over the entire width of the film. A small standard deviation of the film thickness leads to good printability of the foils, since the color can be applied more evenly during printing.
  • the density of the film is less than 1.1 g / cm 3 , preferably less than 1.0 g / cm 3 , very particularly preferably less than 0.9 g / cm 3 and most preferably less than 0.8 g / cm 3 .
  • the film is not assigned to the polyolefinic recycling stream in conventional recycling processes and is sorted out of the material cycle. The lower the density, the safer the film according to the invention is assigned to the polyolefinic recycling stream.
  • Another aspect of the present invention is a film produced by a method according to the invention.
  • one aspect of the present invention is a film which comprises at least one thermoplastic polymer in an amount of at least 20% by weight and an inorganic filler in an amount in the range from 50 to 75% by weight, wherein the thermoplastic polymer at least a polymer comprises selected from the group consisting of polyethylene, polypropylene and mixtures thereof, wherein the particle size of the inorganic filler is in a range from 0.1 ⁇ m to 5 ⁇ m and the thickness of the film is in a range from 20 ⁇ m to 180 ym and is characterized in that the standard deviation of the thickness of the film is not more than 20%.
  • the standard deviation of the thickness of the film is particularly preferably not more than 10% and most preferably not more than 5%.
  • Another aspect of the present invention is the use of the films produced by the process according to the invention or the films according to the invention in carrier bags, packaging, pouches for food, as paper substitution in aluminum & paper laminates, newspapers, notebooks, calendars, posters, labels, books , Menu cards, etc., the packaging for example tea bags or packaging for other foodstuffs such.
  • B. can include the butter wrap and it can be pouches for food, for example, poches for flour.
  • Illustration 1
  • Figure 1 shows a film after stretching at different stretching ratios.
  • Figure 2 shows a film after stretching at different stretching ratios.
  • Figure 2 shows a micrograph of a film according to the invention without a dispersant.
  • Figure 3 shows a microscopic picture of a film according to the invention with a dispersant.
  • Figure 4 shows the profile of the stretching in the transverse direction to Example 4, sample roll 1 and sample roll 3.
  • Figure 5 shows the profile of the stretching in the transverse direction to Example 4, sample roll 1 and sample roll 3.
  • Figure 5 shows the temperature profile when stretching in the transverse direction to example 4, sample roll 1.
  • Figure 6 shows the temperature profile when stretching in the transverse direction to example 4, sample roll 3.
  • Figure 7 shows the profile of the stretching in the transverse direction to Example 5.
  • Figure 8 shows the profile of the stretching in the transverse direction to Example 5.
  • Figure 8 shows the temperature profile when stretching in the transverse direction to Example 5.
  • this example shows that the lines in the middle of the foils run more parallel at higher stretching ratios than at lower stretching ratios.
  • the squares are approximately as large in area as the central square.
  • stretching ratios above 3 stretching are more uniform than stretching ratios up to 3. This results in a more uniform thickness of the film at stretching ratios above 3 and thus also a lower standard deviation of the film thickness. This leads to significantly better printability and better mechanical properties of the films.
  • MFR-PP melt mass flow rate according to ISO 1133
  • the polypropylene homopolymer “Moplen®.” was used as polypropylene with a melt mass flow rate of 2 g / 10 min HP2624 "from LyondellBasell, Rotterdam, The Netherlands.
  • the polypropylene homopolymer” Sabic® PP 576P from Sabic, Riyadh, Saudi Arabia was used as polypropylene with a melt mass flow rate of 19 g / 10 min.
  • dispersant 2% of the dispersant “Licowax® OP powder” from Clariant, Frankfurt / Main, Germany was added.
  • stabilizing agents 1000 ppm of the acid scavenger "DHT -4A "from Kisuma Chemicals, Vendam, the Netherlands and 500 ppm” Irganox B561 "from BASF SE, Ludwigshafen, Germany.
  • Table 2 shows some properties of the films obtained with a calcium carbonate content of 60 and 70 wt. -%:
  • the Castfilm 1 (CF1) shows a very good standard deviation of the thickness, good values for the tensile strength and still adequate values for the elasticity module. CF1 thus offers a balanced distribution of properties and can be used in many applications as a paper substitute.
  • Castfilm 3 (CF3) performs best in every respect. It has the best standard deviation of film thickness, the lowest density reduction and the best mechanical properties. CF1 and CF3 differ only in the use of a dispersant ("lubricant").
  • Figure 2 shows SEM images of sample cross sections of CF1 after stretching at 500x and 1000x magnification and Figure 3 shows corresponding microscopic images of the surface of CF3.
  • CF1 has a high porosity. They are large oval openings that form around the calcium carbonate crystals. Here the tension between the calcium carbonate particles and the polymer is apparently partially broken by the tensile stress and relatively large openings and thus bumps are formed.
  • the dispersant the so-called cavitation, i.e.
  • the dispersant thus prevents the formation of larger openings around the calcium carbonate particles and leads to a more uniform surface of the film and thus to lower standard deviations in the film thickness. Surprisingly this leads to an excellent standard deviation of the film thickness of only 2.64%.
  • the density of CF3 is only slightly higher than that of CF1, but is still significantly below 1 g / cm 3 .
  • the tensile strength in the longitudinal and transverse directions is well above 20 MPa and the tensile strength in the transverse direction only deviates by approximately 28% from the tensile strength in the longitudinal direction. This should prevent splicing of the film to a sufficient extent during further processing. With almost 1000 MPa, the elasticity modules are sufficiently high in both directions and hardly differ from each other (about 14%).
  • stone paper In order to be able to replace classic paper as fully as possible, stone paper should have a tensile strength of at least about 20 MPa and an elastic modulus of around 1000 MPa. An elastic modulus in the range of 800 to 1200 MPa is acceptable in this context. Foldability and splicing should also resemble the behavior of classic paper. CF3 ideally fulfills all of these conditions.
  • CF6 and CF7 show the effect of calcium carbonate particles with a larger particle size of more than 5 ym. The mechanical properties have deteriorated significantly. These foils are no longer suitable for all applications in which paper is usually used. However, they are still useful for many applications. However, for these examples too, the standard deviation of the film thickness is still in an acceptable range. A comparison of CF6 and CF7 also shows the positive effect of the dispersant on the standard deviation of the film thickness.
  • Table 3 shows two of the optical properties of the films, the opacity and the whiteness: Table 3:
  • the standard deviation of the film thickness in the CF3 is further improved by the larger stretching ratios, which leads to an extremely low value of only 1.90%.
  • the effect of the larger stretching ratios is very low.
  • the use of a dispersant increases the positive effect of a large stretch ratio.
  • the film was stretched sequentially. First with a stretch ratio of 5 stretched in the longitudinal direction and then with a stretching ratio in the transverse direction. Thereafter, after the stretching in the transverse direction, a heat treatment was carried out with a relaxation of 10% in the transverse direction, that is to say a reduction in the stretching ratio from 5 to 4.5 in the transverse direction.
  • the temperatures during stretching and during heat treatment are listed in Table 5.
  • Figure 4 shows the stretching profile in the stretching furnace when stretching in the transverse direction to the two tests, sample roll 1 and sample roll 2, both of which were carried out with the film obtained as described above.
  • the stretching furnace is divided into zones ZI to Z9, with ZI to Z3 being preheating zones, Z4 and Z5 zones in which stretching is carried out (“stretching"), Z6 and Z7 zones in which heat treatment (" Annealing ") is carried out without stretching, Z8 is a zone in which the film is relaxed (“ relaxation ”) and Zone 9 is a zone in which both relaxation and cooling are carried out (“Relaxation &Cooling").
  • Figure 4 shows in which zone by how much stretching.
  • Figure 5 shows the temperature profile of the furnace temperature for sample roll 1
  • Figure 6 shows the temperature profile of the furnace temperature for sample roll 2.
  • the furnace temperatures for the individual zones ZI to Z9 are given separately, so when looking at Figures 4 to 6, the correlation between the zone of the stretching furnace, the furnace temperature and the stretching ratio is given for both experiments.
  • the temperature in sample roll 1 is before, at the beginning and during the R Elaxation increased (compare zones Z7 and Z8).
  • Table 6 shows the properties of the films obtained in this way:
  • a multilayer film with an ABA structure was produced from it by co-extrusion, B being the core and A the coatings.
  • the calcium carbonate The core content was 58% by weight and the calcium carbonate content in the coatings was 25% by weight.
  • the film was otherwise shown according to Example 1.
  • the film was first co-extruded and then cooled.
  • the film was then stretched sequentially, first with a stretch ratio of 5 in the longitudinal direction and then with a stretch ratio of 4.7 in the transverse direction. Thereby, a heat treatment was carried out after the transverse stretching. While the heat treatment was 6% relaxation
  • Transverse direction carried out that is to a final stretch ratio of 4.4 in the transverse direction.
  • the temperatures during stretching and during heat treatment are listed in Table 7.
  • Figure 7 shows the stretching profile in the stretching furnace when stretching in the transverse direction to sample roll 3.
  • the stretching furnace is divided into zones ZI to Z9, ZI to Z3 representing preheating zones, Z4 and Z5 zones in which stretching is carried out, Z6 and Z7 zones in which heat treatment (annealing ") is carried out without stretching, Z8 is a zone in which the film is relaxed (“ Relaxation ”) and Zone 9 is a zone in which it is both relaxed and cooled (“ Relaxation & Cooling ").
  • the film was first stretched to a longitudinal stretching ratio of 4.7, then held at this stretch ratio for a while and then relaxed to a final stretch ratio of 4.4.
  • Figure 7 shows in which zone by how much stretching.
  • Figure 8 shows the temperature profile of the furnace temperature for sample roll 3.
  • the furnace temperatures for the individual zones ZI to Z9 are shown separately.
  • the correlation between zone of the stretching furnace, furnace temperature and stretching ratio is therefore given in the overview of Figures 7 and 8.
  • Table 8 shows the properties of the film thus obtained:

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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)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Mechanical Engineering (AREA)
  • Shaping By String And By Release Of Stress In Plastics And The Like (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

La présente invention concerne un procédé de production d'un film comprenant au moins 20 % de polymère thermoplastique et 50 à 75 % de charge inorganique et comprend les étapes suivantes : fournir le mélange, faire fondre le mélange, produire un film à partir du mélange, refroidir le film pour produire un film, étirer le film dans la direction longitudinale et dans la direction transversale, la taille des particules de la charge inorganique étant au maximum de 5 µm et le rapport d'étirage dans la direction longitudinale et dans la direction transversale étant d'au moins 3,5. L'invention concerne également des films produits par ce procédé et leur utilisation.
EP19749625.0A 2018-08-10 2019-07-25 Procédé de production d'un film comprenant un polymère thermoplastique et une charge inorganique Pending EP3833709A1 (fr)

Applications Claiming Priority (2)

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DE102018119541.9A DE102018119541A1 (de) 2018-08-10 2018-08-10 Verfahren zur Herstellung einer Folie umfassend thermoplastisches Polymer und anorganischen Füllstoff
PCT/EP2019/070021 WO2020030433A1 (fr) 2018-08-10 2019-07-25 Procédé de production d'un film comprenant un polymère thermoplastique et une charge inorganique

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CN113480796B (zh) * 2021-06-16 2022-11-15 广州爱科琪盛塑料有限公司 一种透气膜及其制备方法
KR102532715B1 (ko) * 2021-12-20 2023-05-15 주식회사 애니켐 탄소중립 친환경 무기물 충진 폴리올레핀 수지조성물 및 이로부터 얻어지는 물품

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JP3021654U (ja) 1995-08-14 1996-02-27 南亜塑膠工業股▲ひん▼有限公司 多機能カレンダ
DE19622082C1 (de) 1996-05-31 1997-11-20 Brueckner Maschbau Verfahren zur Herstellung einer füllstoffhaltigen bedruckbaren Polymerfolie
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KR20210042113A (ko) 2021-04-16
WO2020030433A1 (fr) 2020-02-13
US11976176B2 (en) 2024-05-07
CN112566965A (zh) 2021-03-26
JP2021534016A (ja) 2021-12-09
US20210301101A1 (en) 2021-09-30

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