CA2347086A1 - Polymeric, semicrystalline thermoplastic material with nanoscale nucleating agent and high transparent molded parts produced therefrom - Google Patents
Polymeric, semicrystalline thermoplastic material with nanoscale nucleating agent and high transparent molded parts produced therefrom Download PDFInfo
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- CA2347086A1 CA2347086A1 CA002347086A CA2347086A CA2347086A1 CA 2347086 A1 CA2347086 A1 CA 2347086A1 CA 002347086 A CA002347086 A CA 002347086A CA 2347086 A CA2347086 A CA 2347086A CA 2347086 A1 CA2347086 A1 CA 2347086A1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
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- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
-
- 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
- B32B27/18—Layered products comprising a layer of synthetic resin characterised by the use of special additives
- B32B27/20—Layered products comprising a layer of synthetic resin characterised by the use of special additives using fillers, pigments, thixotroping agents
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- 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
- C08K3/34—Silicon-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
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- 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
- C08K9/00—Use of pretreated ingredients
- C08K9/10—Encapsulated ingredients
-
- 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
- C08J2377/00—Characterised by the use of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Derivatives of such polymers
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- 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
- C08K2201/011—Nanostructured additives
Abstract
The invention relates to a polymeric, semicrystalline thermoplastic material containing nucleating particles with a size smaller than 100 nm in dispersed form and to the molded parts produced using said material.
Description
Polymeric, partially crystalline thermoplastic material with a nanoscale nucleating went and highly transparent mouldings produced therefrom The present invention relates to a polymeric, partially crystalline thermoplastic material which contains particles having a nucleating action of a size of less than 100 nm nanoscale nucleating agents in dispersed form. Mouldings produced therefrom are distinguished by excellent transparency combined with elevated gloss together with elevated dimensional stability and hardness. The present invention accordingly also provides mouldings, in particular films, which are produced in zones or in their entirety using the material according to the invention as the sole constituent or as a blend component. Advantages in comparison with polymeric materials containing conventional nucleating agents reside in the extremely fine-grained and highly crystalline crystal structure which may be established and, in particular, the accompanying transparency. The nucleating agent itself has no influence upon transparency.
Nucleating agents for polymeric, partially crystalline thermoplastic materials are of considerable significance. They bring about an elevated nucleation rate and thus a speed of crystallisation which, over a wide temperature, i.e. supercooling, range, is distinctly raised in comparison with non-nucleated systems. As a consequence, in conventional industrial cooling processes from the melt, they give rise to a high degree of crystallinity. This is explained, using polyamide 6 and the nucleating agents talcum and kaolin by way of example, in Kohan (ed.), Nylon Plastics Handbook, Hanser Publishers, Munich, 1995.
Applicational advantages of nucleated polymeric materials reside in increased rigidity and hardness due to the crystalline fractions combined with greater toughness, abrasion resistance and surface hardness and, due to the fine crystalline structure obtained even with conventional nucleating agents, in appreciably improved transparency and increased gloss of the mouldings produced therefrom, in ~r~,~ ss ;~3 comparison with non-nucleated polymeric materials. Due to the rapid and extensive crystallisation which occurs during cooling from the melt, crystallisation in the moulding is very largely complete after the shaping process. In contrast, in non-nucleated systems, cooling which is excessively rapid relative to the speed of crystallisation may give rise to a metastable state, which results in post-crystallisation of the moulding over a relatively long period after the shaping process. As a result of the reduction in specific volume of the polymer which accompanies crystallisation, this gives rise to post-shrinkage of the corresponding moulding. This is in principle undesirable. Moreover, faster production rates may be achieved in many shaping processes, such as for example injection moulding, with more rapidly crystallising moulding compositions.
It is prior art to used nucleating systems, in particular in the form of dispersed, finely divided inorganic solid particles. WO 8802763 in particular mentions in this connection talcum, mica, kaolin and, secondarily, substances such as asbestos, aluminium, silicates, silver bromide, graphite, molybdenum disulfide, lithium fluoride, sodium phenylphosphinate, magnesium oxide, mercury bromide, mercury chloride, cadmium acetate, lead acetate, silver chloride, diatomaceous earth and the like. The stated systems are added in concentrations between one thousandth of a percent and one percent, relative to the total weight of the nucleated polymer.
In addition to the solid particles which act as crystallisation nuclei, plasticising substances are frequently added to the polymer. In this manner, the glass transition temperature of the polymer may be reduced and the temperature range over which crystal growth may still occur around the nuclei is extended downwards to lower temperatures. While this indeed does not give rise to a more fine-grained structure than without the addition of such substances, it does result in an overall higher degree of crystallinity at an identical spherulite count. Suitable substances are, for example, polymers with a molecular weight which imparts a waxy consistency to the polymer. Polyolefins, polyoxides, polysulfides and/or fatty acid derivatives, in particular fatty acid amides, may be used.
Nucleating agents for polymeric, partially crystalline thermoplastic materials are of considerable significance. They bring about an elevated nucleation rate and thus a speed of crystallisation which, over a wide temperature, i.e. supercooling, range, is distinctly raised in comparison with non-nucleated systems. As a consequence, in conventional industrial cooling processes from the melt, they give rise to a high degree of crystallinity. This is explained, using polyamide 6 and the nucleating agents talcum and kaolin by way of example, in Kohan (ed.), Nylon Plastics Handbook, Hanser Publishers, Munich, 1995.
Applicational advantages of nucleated polymeric materials reside in increased rigidity and hardness due to the crystalline fractions combined with greater toughness, abrasion resistance and surface hardness and, due to the fine crystalline structure obtained even with conventional nucleating agents, in appreciably improved transparency and increased gloss of the mouldings produced therefrom, in ~r~,~ ss ;~3 comparison with non-nucleated polymeric materials. Due to the rapid and extensive crystallisation which occurs during cooling from the melt, crystallisation in the moulding is very largely complete after the shaping process. In contrast, in non-nucleated systems, cooling which is excessively rapid relative to the speed of crystallisation may give rise to a metastable state, which results in post-crystallisation of the moulding over a relatively long period after the shaping process. As a result of the reduction in specific volume of the polymer which accompanies crystallisation, this gives rise to post-shrinkage of the corresponding moulding. This is in principle undesirable. Moreover, faster production rates may be achieved in many shaping processes, such as for example injection moulding, with more rapidly crystallising moulding compositions.
It is prior art to used nucleating systems, in particular in the form of dispersed, finely divided inorganic solid particles. WO 8802763 in particular mentions in this connection talcum, mica, kaolin and, secondarily, substances such as asbestos, aluminium, silicates, silver bromide, graphite, molybdenum disulfide, lithium fluoride, sodium phenylphosphinate, magnesium oxide, mercury bromide, mercury chloride, cadmium acetate, lead acetate, silver chloride, diatomaceous earth and the like. The stated systems are added in concentrations between one thousandth of a percent and one percent, relative to the total weight of the nucleated polymer.
In addition to the solid particles which act as crystallisation nuclei, plasticising substances are frequently added to the polymer. In this manner, the glass transition temperature of the polymer may be reduced and the temperature range over which crystal growth may still occur around the nuclei is extended downwards to lower temperatures. While this indeed does not give rise to a more fine-grained structure than without the addition of such substances, it does result in an overall higher degree of crystallinity at an identical spherulite count. Suitable substances are, for example, polymers with a molecular weight which imparts a waxy consistency to the polymer. Polyolefins, polyoxides, polysulfides and/or fatty acid derivatives, in particular fatty acid amides, may be used.
In the case of polyamide, for example, talcum is predominantly used as a nucleating agent. The size of the particles used is here in the range from approx. 1 to S
pm with typical polyamide loading rates ranging from one thousandth to approx. one tenth of S one weight percent. Higher filling rates than this prove inadvisable for various reasons. Accordingly, above a content of approx. 1000 ppm, it is not possible to bring about any further acceleration of crystallisation, but instead the particles themselves greatly increase haze due to their size and refractive index, which differs from that of the polymeric matrix. A fatty acid amide, in particular ethylenebisstearamide, is frequently added as a plasticising component for the purpose described above. Nucleation may be improved by surface modification of the particles, for example with citric acid.
It has also been known for a relatively long period to add very fine solid particles of a size of below one micrometre to polymeric matrices and, in particular, polyamides.
Such systems are primarily used to increase mechanical rigidity, gas barrier properties and heat resistance and to reduce the cycle time in, for example, injection moulding, flammability or moisture absorption in hydrophilic systems. Systems which, unlike the above-stated nucleated polyamides, retain their transparency despite a higher rate of addition of the nanoscale particles, have also been described.
Nanoscale fillers having a nucleating action or the benefits thereof have, however, not been described in the literature.
EP 358 415 describes a moulding composition comprising a polyamide resin with a phyllosilicate uniformly dispersed therein, wherein the individual layers of the phyllosilicates may exhibit thicknesses of around 1 nm and side lengths of up to 1 pm. As a result of suitable maceration, the layers are separately present in the polyamide matrix and are spaced apart by approx. 10 nm. Mouldings, such as for example films, produced with this material made from polyamide 6 as the base polymer are characterised by significantly increased oxygen barrier properties and WO 00/2351'2 PCT/EP99/07348 rigidity in comparison with those made from pure polyamide 6. To the same extent, toughness falls appreciably. Surface slip properties are improved. The transparency of single layer amorphously quenched flat films and of water-cooled blown films with the structure polyamide mixture/coupling agent/PE-LD is unchanged relative to pure polyamide 6.
WO 9304118 and WO 9311190 and WO 9304117 disclose polymer nanocomposites which likewise comprise lamellar particles of a thickness of a few nanometres.
In particular, composites made from PA 6 and montmorillonite or from PA 6 and silicates are described. These materials may be converted into films. The advantages of such films in comparison with those without nanoscale particles are higher rigidity, greater wet strength, better dimensional stability, higher gas barrier properties and lower water absorption. The effect of the added particles upon transparency is not described.
EP 810 259 also describes a polyamide moulding composition comprising nanodisperse fillers. The burner action desired therein for the polyamide may be improved by the addition of sufficiently finely divided oxides, oxyhydrates or carbonates. The particles preferably have a diameter of less than 100 nm. The patent also describes multilayer films comprising at least one layer made from this moulding composition, wherein the stated intention for using said moulding compositions is always to improve oxygen barrier properties. However, the optical properties of the films made therefrom are impaired in comparison with the system without the additive.
WO 980346 also describes the use of nanodisperse fillers for improving the burner properties of polyesters. Such a polymer comprising a fraction of between 0.1 and 10% of lamellar mineral dispersed therein with a particle thickness of below 100 nm is distinguished by elevated oxygen barrier properties and strength while retaining transparency and is suitable, for example, for the production of packaging films.
pm with typical polyamide loading rates ranging from one thousandth to approx. one tenth of S one weight percent. Higher filling rates than this prove inadvisable for various reasons. Accordingly, above a content of approx. 1000 ppm, it is not possible to bring about any further acceleration of crystallisation, but instead the particles themselves greatly increase haze due to their size and refractive index, which differs from that of the polymeric matrix. A fatty acid amide, in particular ethylenebisstearamide, is frequently added as a plasticising component for the purpose described above. Nucleation may be improved by surface modification of the particles, for example with citric acid.
It has also been known for a relatively long period to add very fine solid particles of a size of below one micrometre to polymeric matrices and, in particular, polyamides.
Such systems are primarily used to increase mechanical rigidity, gas barrier properties and heat resistance and to reduce the cycle time in, for example, injection moulding, flammability or moisture absorption in hydrophilic systems. Systems which, unlike the above-stated nucleated polyamides, retain their transparency despite a higher rate of addition of the nanoscale particles, have also been described.
Nanoscale fillers having a nucleating action or the benefits thereof have, however, not been described in the literature.
EP 358 415 describes a moulding composition comprising a polyamide resin with a phyllosilicate uniformly dispersed therein, wherein the individual layers of the phyllosilicates may exhibit thicknesses of around 1 nm and side lengths of up to 1 pm. As a result of suitable maceration, the layers are separately present in the polyamide matrix and are spaced apart by approx. 10 nm. Mouldings, such as for example films, produced with this material made from polyamide 6 as the base polymer are characterised by significantly increased oxygen barrier properties and WO 00/2351'2 PCT/EP99/07348 rigidity in comparison with those made from pure polyamide 6. To the same extent, toughness falls appreciably. Surface slip properties are improved. The transparency of single layer amorphously quenched flat films and of water-cooled blown films with the structure polyamide mixture/coupling agent/PE-LD is unchanged relative to pure polyamide 6.
WO 9304118 and WO 9311190 and WO 9304117 disclose polymer nanocomposites which likewise comprise lamellar particles of a thickness of a few nanometres.
In particular, composites made from PA 6 and montmorillonite or from PA 6 and silicates are described. These materials may be converted into films. The advantages of such films in comparison with those without nanoscale particles are higher rigidity, greater wet strength, better dimensional stability, higher gas barrier properties and lower water absorption. The effect of the added particles upon transparency is not described.
EP 810 259 also describes a polyamide moulding composition comprising nanodisperse fillers. The burner action desired therein for the polyamide may be improved by the addition of sufficiently finely divided oxides, oxyhydrates or carbonates. The particles preferably have a diameter of less than 100 nm. The patent also describes multilayer films comprising at least one layer made from this moulding composition, wherein the stated intention for using said moulding compositions is always to improve oxygen barrier properties. However, the optical properties of the films made therefrom are impaired in comparison with the system without the additive.
WO 980346 also describes the use of nanodisperse fillers for improving the burner properties of polyesters. Such a polymer comprising a fraction of between 0.1 and 10% of lamellar mineral dispersed therein with a particle thickness of below 100 nm is distinguished by elevated oxygen barrier properties and strength while retaining transparency and is suitable, for example, for the production of packaging films.
In the light of the prior art, the object arises of providing a melt-processable, polymeric, partially crystalline material which may be processed using typical industrial shaping processes to yield a moulding, which exhibits very good transparency, elevated gloss, elevated rigidity and toughness, elevated hardness and abrasion resistance and, once shaped, exhibits only slight post-shrinkage.
This has been achieved according to the invention by the provision of a material made from a partially crystalline polymer comprising a phase of inorganic solid particles dispersed therein, which material is characterised in that the extent of the particles in at least one direction freely selectable for each particle is, on a number-weighted average of all particles, less than 100 nm.
According to the invention, the materials according to the invention may be produced from a partially crystalline polymer comprising a phase of inorganic solid particles 1 S dispersed therein in that the polymer containing inorganic solid particles and optionally further conventional additives is melted in an extruder and the completely molten polymer is then cooled at a cooling rate of between 30° and 40°C per minute, wherein crystalline structures are obtained.
The nanoscale particles may preferably be incorporated into the partially crystalline polymer using conventional processes used to disperse solids in polymers.
A material according to the invention is preferably obtainable by melting the polymer containing inorganic solid particles in an extruder and cooling the completely molten polymer at a cooling rate of between 30° and 40°C per minute.
The partially crystalline polymer may be any desired crystallisable polymer.
Ideally suitable polymers are those which are selected from the group of polymers comprising polyamide, polyethylene, ethylene-based copolymers, polypropylene, propylene-based copolymers, polyvinyl chloride, polyacetals, polyketones, polyesters and copolyesters and polyurethane. Partially crystalline polymers which may preferably be used comprise polyamide in the form of aliphatic or aromatic homo-and copolyamides and the mixtures thereof, in particular polyamide 6, polyamide 10, polyamide 12, polyamide 66, polyamide 610, polyamide 6I, polyamide 612, polyamide 6/66, polyamide 6I/6T, polyamide MXD6, polyamide 6/6I, polyamide 6/6T, polyamide 6/IPDI and copolyamides or mixtures thereof.
The advantages of the invention are particularly pronounced if very small nanoscale particles are selected.
The size of the particles is thus preferably less than SO nm, still more preferably less than 10 nm in at least one direction freely selectable for each particle on a number-weighted average of all particles.
The solid nanoscale particles preferably have an approximately spherical shape, but may also be lamellar or of a unidirectionally extensive form. Amorphous particles may also be used. Agglomerates of such particles may also be used.
The solid nanoscale particles may have a modified surface enabling increased affinity towards the surrounding polymer.
Suitable quantities of the solid nanoscale particles to be added are between 10 and 10000 ppm, preferably between 100 and 5000 ppm, relative to the total weight of the material. It was surprising in this connection that even at elevated contents of nanoscale particles in the material, the achievable transparency and achievable gloss of mouldings produced therefrom are not impaired.
Apart from the solid nanoscale particles, the material may also contain further conventionally used additives in conventional quantities. Examples are lubricants, stabilisers, processing auxiliaries, antiblocking agents, fillers, dyes and the like. It is particularly suitable to add macromolecular substances which, before addition, are in a waxy state at room temperature.
_7_ The material according to the invention may be melt processed to yield mouldings, in particular films. These mouldings may contain the material in zones or throughout; in the zones containing the material, they may consist of the material alone or as a S mixture of two or more different materials according to the invention with further polymers or other materials.
Using the material according to the invention, it is possible to provide a material which, in typical industrial shaping processes from the melt, gives rise to highly crystalline mouldings which exhibit not only elevated rigidity, hardness and abrasion resistance but also elevated toughness. While the cooling rate does indeed in principle here have an influence upon the action of the nanoscale particles, any action discernible in the moulding only occurs at cooling rates of greater than 200°C/s.
It was not to be expected that the mouldings should additionally exhibit outstanding transparency and gloss properties.
The mouldings which may be produced from this material are fiu~thermore also distinguished by surprisingly low shrinkage after the shaping process.
The material according to the invention may in particular readily be processed to yield flexible films. The present invention accordingly also provides films comprising one or more layers containing at least one such material alone or in a mixture.
_g_ Examples Single layer flat films were made from polyamide using the process typical for this purpose. The moulding composition was melted in an extruder and cast through a S slot die onto a temperature-controlled, rotating casting roll. The casting roll had a diameter of 1100 mm, wherein the film contacted the casting roll over an angle of 190°. The tangential velocity of the surface of the casting roll was 30 m/min. The . resultant films have a thickness of 50 pm.
Comparative Example 1 A polyamide 6 film was produced at a casting roll temperature of 30°C. The polyamide 6 used has a crystallite melting point of 22U°C and a relative viscosity in 98% sulfuric acid of 3.6. It contains 600 ppm of ethylenebisstearamide and is I S nucleated with approx. 150 ppm of talcum.
Comparative Example 2 The film from Comparative Example 1 was produced at a casting roll temperature of 100°C. All other conditions are the same as in Comparative Example 1.
Example 3 Using the production conditions as in Comparative Example 2, a film was produced from polyamide 6 with 0.2 wt.% of montmorillonite. The montmorillonite is dispersed in the polyamide in macerated form, where it forms lamellar units of a thickness of approx. 1 nm with a characteristic diameter of approx. 100 to 1000 nm.
The polyamide contains no further nucleating agent.
Example 4 Finn from Example 3 produced with a casting roll temperature of 30°C as in Comparative Example 1.
Example 5 Film from Example 3 with a montmorillonite content of 0.4%.
Comparative Example 6 Film from Comparative Example 2 with a polyamide 6 as in Comparative Example 2, but containing no talcum.
I S The following measurements were made on the Examples according to the invention and Comparative Examples which were produced.
- Tensile modulus to DIN EN ISO 527 in the longitudinal direction of the film as a measure of rigidity in a test atmosphere of 23°C and 0% relative humidity in a period of between 24 and 36 hours after production of the film.
- Flex crack resistance as a measure of film toughness. Flex crack resistance is measured at a temperature of 23°C and relative humidity of 0% by rolling up a specimen in a single layer to form a cylinder of length 198 mm and circumference 280 mm and fastening it at both ends in suitably shaped clamps. The free length of the cylinder formed by the film between the clamps is 192 mm. While being simultaneously rotated by 440° around the axis of symmetry which describes the cylinder, the clamps are brought to a distance of 40 mm apart for a predetermined number of cycles and at a frequency of 35 cycles per minute. The films to be tested are previously kept for 3 days in an atmosphere of 23°C and 0% relative atmospheric humidity.
The number of cracks which occur in the film after the predetermined number of strokes may be determined by wetting the film on one side with ammonia solution while the other side of the film is simultaneously in contact with a sheet of blueprint paper. The number of blue/black spots on the blueprint paper caused by ammonia which are discernible after 15 minutes is deemed to be the number of flex cracks in the tested portion of film. The value is here obtained as an average of the individual values from two test specimens.
Film shrinkage after heat treatment in water at 121 °C for 30 minutes. The change in length in both longitudinal and transverse direction of a square piece of film of an edge length of 100 mm was determined at 23°C and 0%
relative humidity by measurement before and after heat treatment and a shrinkage value per unit area was calculated from these measurements.
- Haze to ASTM D 1003.
- Gloss on the casting roll side of the film at an angle of 20° to DIN
67 530.
The results are shown in Table 6 below:
Feature (unit) Example (Ex.) or Comparative Example (CEx.) CEx. CEx. Ex. Ex. Ex. CEx.
Gloss 155 121 163 166 164 105 (gloss units) Haze (%) 0.4 7.5 0.7 0.5 0.5 12.3 Number of holes 1 8.5 2 1.5 3 11.5 after 250 strokes Modulus of elasticity630 1490 1610 1530 1720 1450 (MPa) Shrinkage (%) 9.3 3.4 2.3 2.7 2.0 4.6 Properties of the Examples according to the invention and Comparative Examples
This has been achieved according to the invention by the provision of a material made from a partially crystalline polymer comprising a phase of inorganic solid particles dispersed therein, which material is characterised in that the extent of the particles in at least one direction freely selectable for each particle is, on a number-weighted average of all particles, less than 100 nm.
According to the invention, the materials according to the invention may be produced from a partially crystalline polymer comprising a phase of inorganic solid particles 1 S dispersed therein in that the polymer containing inorganic solid particles and optionally further conventional additives is melted in an extruder and the completely molten polymer is then cooled at a cooling rate of between 30° and 40°C per minute, wherein crystalline structures are obtained.
The nanoscale particles may preferably be incorporated into the partially crystalline polymer using conventional processes used to disperse solids in polymers.
A material according to the invention is preferably obtainable by melting the polymer containing inorganic solid particles in an extruder and cooling the completely molten polymer at a cooling rate of between 30° and 40°C per minute.
The partially crystalline polymer may be any desired crystallisable polymer.
Ideally suitable polymers are those which are selected from the group of polymers comprising polyamide, polyethylene, ethylene-based copolymers, polypropylene, propylene-based copolymers, polyvinyl chloride, polyacetals, polyketones, polyesters and copolyesters and polyurethane. Partially crystalline polymers which may preferably be used comprise polyamide in the form of aliphatic or aromatic homo-and copolyamides and the mixtures thereof, in particular polyamide 6, polyamide 10, polyamide 12, polyamide 66, polyamide 610, polyamide 6I, polyamide 612, polyamide 6/66, polyamide 6I/6T, polyamide MXD6, polyamide 6/6I, polyamide 6/6T, polyamide 6/IPDI and copolyamides or mixtures thereof.
The advantages of the invention are particularly pronounced if very small nanoscale particles are selected.
The size of the particles is thus preferably less than SO nm, still more preferably less than 10 nm in at least one direction freely selectable for each particle on a number-weighted average of all particles.
The solid nanoscale particles preferably have an approximately spherical shape, but may also be lamellar or of a unidirectionally extensive form. Amorphous particles may also be used. Agglomerates of such particles may also be used.
The solid nanoscale particles may have a modified surface enabling increased affinity towards the surrounding polymer.
Suitable quantities of the solid nanoscale particles to be added are between 10 and 10000 ppm, preferably between 100 and 5000 ppm, relative to the total weight of the material. It was surprising in this connection that even at elevated contents of nanoscale particles in the material, the achievable transparency and achievable gloss of mouldings produced therefrom are not impaired.
Apart from the solid nanoscale particles, the material may also contain further conventionally used additives in conventional quantities. Examples are lubricants, stabilisers, processing auxiliaries, antiblocking agents, fillers, dyes and the like. It is particularly suitable to add macromolecular substances which, before addition, are in a waxy state at room temperature.
_7_ The material according to the invention may be melt processed to yield mouldings, in particular films. These mouldings may contain the material in zones or throughout; in the zones containing the material, they may consist of the material alone or as a S mixture of two or more different materials according to the invention with further polymers or other materials.
Using the material according to the invention, it is possible to provide a material which, in typical industrial shaping processes from the melt, gives rise to highly crystalline mouldings which exhibit not only elevated rigidity, hardness and abrasion resistance but also elevated toughness. While the cooling rate does indeed in principle here have an influence upon the action of the nanoscale particles, any action discernible in the moulding only occurs at cooling rates of greater than 200°C/s.
It was not to be expected that the mouldings should additionally exhibit outstanding transparency and gloss properties.
The mouldings which may be produced from this material are fiu~thermore also distinguished by surprisingly low shrinkage after the shaping process.
The material according to the invention may in particular readily be processed to yield flexible films. The present invention accordingly also provides films comprising one or more layers containing at least one such material alone or in a mixture.
_g_ Examples Single layer flat films were made from polyamide using the process typical for this purpose. The moulding composition was melted in an extruder and cast through a S slot die onto a temperature-controlled, rotating casting roll. The casting roll had a diameter of 1100 mm, wherein the film contacted the casting roll over an angle of 190°. The tangential velocity of the surface of the casting roll was 30 m/min. The . resultant films have a thickness of 50 pm.
Comparative Example 1 A polyamide 6 film was produced at a casting roll temperature of 30°C. The polyamide 6 used has a crystallite melting point of 22U°C and a relative viscosity in 98% sulfuric acid of 3.6. It contains 600 ppm of ethylenebisstearamide and is I S nucleated with approx. 150 ppm of talcum.
Comparative Example 2 The film from Comparative Example 1 was produced at a casting roll temperature of 100°C. All other conditions are the same as in Comparative Example 1.
Example 3 Using the production conditions as in Comparative Example 2, a film was produced from polyamide 6 with 0.2 wt.% of montmorillonite. The montmorillonite is dispersed in the polyamide in macerated form, where it forms lamellar units of a thickness of approx. 1 nm with a characteristic diameter of approx. 100 to 1000 nm.
The polyamide contains no further nucleating agent.
Example 4 Finn from Example 3 produced with a casting roll temperature of 30°C as in Comparative Example 1.
Example 5 Film from Example 3 with a montmorillonite content of 0.4%.
Comparative Example 6 Film from Comparative Example 2 with a polyamide 6 as in Comparative Example 2, but containing no talcum.
I S The following measurements were made on the Examples according to the invention and Comparative Examples which were produced.
- Tensile modulus to DIN EN ISO 527 in the longitudinal direction of the film as a measure of rigidity in a test atmosphere of 23°C and 0% relative humidity in a period of between 24 and 36 hours after production of the film.
- Flex crack resistance as a measure of film toughness. Flex crack resistance is measured at a temperature of 23°C and relative humidity of 0% by rolling up a specimen in a single layer to form a cylinder of length 198 mm and circumference 280 mm and fastening it at both ends in suitably shaped clamps. The free length of the cylinder formed by the film between the clamps is 192 mm. While being simultaneously rotated by 440° around the axis of symmetry which describes the cylinder, the clamps are brought to a distance of 40 mm apart for a predetermined number of cycles and at a frequency of 35 cycles per minute. The films to be tested are previously kept for 3 days in an atmosphere of 23°C and 0% relative atmospheric humidity.
The number of cracks which occur in the film after the predetermined number of strokes may be determined by wetting the film on one side with ammonia solution while the other side of the film is simultaneously in contact with a sheet of blueprint paper. The number of blue/black spots on the blueprint paper caused by ammonia which are discernible after 15 minutes is deemed to be the number of flex cracks in the tested portion of film. The value is here obtained as an average of the individual values from two test specimens.
Film shrinkage after heat treatment in water at 121 °C for 30 minutes. The change in length in both longitudinal and transverse direction of a square piece of film of an edge length of 100 mm was determined at 23°C and 0%
relative humidity by measurement before and after heat treatment and a shrinkage value per unit area was calculated from these measurements.
- Haze to ASTM D 1003.
- Gloss on the casting roll side of the film at an angle of 20° to DIN
67 530.
The results are shown in Table 6 below:
Feature (unit) Example (Ex.) or Comparative Example (CEx.) CEx. CEx. Ex. Ex. Ex. CEx.
Gloss 155 121 163 166 164 105 (gloss units) Haze (%) 0.4 7.5 0.7 0.5 0.5 12.3 Number of holes 1 8.5 2 1.5 3 11.5 after 250 strokes Modulus of elasticity630 1490 1610 1530 1720 1450 (MPa) Shrinkage (%) 9.3 3.4 2.3 2.7 2.0 4.6 Properties of the Examples according to the invention and Comparative Examples
Claims (11)
1. Material made from a partially crystalline polymer comprising a phase of inorganic solid particles dispersed therein, characterised in that the extent of the particles in at least one direction freely selectable for each particle is, on a number-weighted average of all particles, less than 100 nm.
2. Material according to claim 1, characterised in that the partially crystalline polymer is selected from the group comprising polyamide, polyethylene, ethylene-based copolymers, polypropylene, propylene-based copolymers, polyvinyl chloride, polyacetates, polyketones, polyesters and copolyesters and polyurethane.
3. Material according to claim 1, characterised in that the partially crystalline polymer is selected from the group comprising polyamide 6, polyamide 10, polyamide 12, polyamide 66, polyamide 610, polyamide 6I, polyamide 612, polyamide 6/66, polyamide 6I/6T, polyamide MXD6, polyamide 6/6I, polyamide 6/6T, polyamide 6/IPDI and copolyamides or mixtures thereof.
4. Material according to one of claims 1 to 3, characterised in that the extent of the particles in at least one direction freely selectable for each particle is, on a number-weighted average of all particles, less than 100 nm.
5. Material according to one of claims 1 to 4, characterised in that the particles have approximately identical extents in all three spatial directions.
6. Material according to one of claims 1 to 5, characterised in that the proportion of the particles, relative to total weight of the material, is between 10 and 10000 ppm.
7. Material according to one of claims 1 to 6, characterised in that, apart from the polymer and the particles, it contains further conventional additives in conventional quantities.
8. Moulding which at least in zones contains at least one material according to one of claims 1 to 7 or contains a material mixture containing at least one material according to one of claims 1 to 7.
9. Film which contains in at least one layer at least one material according to one of claims 1 to 7 or a material mixture containing at least one material according to one of claims 1 to 7.
10. Process for the production of a material according to one of claims 1 to 7 and 11, characterised in that a) the polymer containing the inorganic solid particles is melted in an extruder and b) said polymer is then crystallised from the completely molten state at a cooling rate of between 30° and 40°C per minute.
11. Material according to one of claims 1 to 7 obtainable by a) melting the polymer containing the inorganic solid particles in an extruder and b) cooling the completely molten polymer at a cooling rate of between 30° and 40°C per minute.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DE19847844A DE19847844A1 (en) | 1998-10-16 | 1998-10-16 | Polymer material for production of highly transparent, high-gloss film and moldings comprises partly crystalline polymer containing dispersed nano-scale inorganic particles as nucleating agent |
| DE19847844.5 | 1998-10-16 | ||
| PCT/EP1999/007348 WO2000023512A1 (en) | 1998-10-16 | 1999-10-04 | Polymeric, semicrystalline thermoplastic material with nanoscale nucleating agent and high transparent molded parts produced therefrom |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2347086A1 true CA2347086A1 (en) | 2000-04-27 |
Family
ID=7884752
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002347086A Abandoned CA2347086A1 (en) | 1998-10-16 | 1999-10-04 | Polymeric, semicrystalline thermoplastic material with nanoscale nucleating agent and high transparent molded parts produced therefrom |
Country Status (6)
| Country | Link |
|---|---|
| EP (1) | EP1129130A1 (en) |
| JP (1) | JP2002527594A (en) |
| AU (1) | AU6089299A (en) |
| CA (1) | CA2347086A1 (en) |
| DE (1) | DE19847844A1 (en) |
| WO (1) | WO2000023512A1 (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| ATE343215T1 (en) * | 2001-08-02 | 2006-11-15 | Woehr Richard Gmbh | INPUT AND/OR DISPLAY DEVICE |
| DE10137460A1 (en) * | 2001-08-02 | 2003-02-13 | Woehr Richard Gmbh | Input and/or display device, e.g. for electrical and electronic equipment, mobile telephones, has nano-coating with nano-scale particles or nano-structuring on exposed surface part(s) |
| CH695687A5 (en) * | 2002-09-06 | 2006-07-31 | Ems Chemie Ag | Polyamide molding materials with ultrafine fillers and produced therefrom Lichtreflektier components. |
| US7442333B2 (en) | 2003-01-30 | 2008-10-28 | Ems-Chemie Ag | Method for the production of polyamide nanocomposites, corresponding packaging materials and moulded bodies |
| DE10311709A1 (en) * | 2003-03-17 | 2004-12-16 | Saehan Industries Inc. | Saturated polyester for production of shaped components for a wide variety of purposes contains specified amounts of dispersed inorganic nanoparticles with a specified mean diameter range |
| DE102005007664A1 (en) * | 2005-02-19 | 2006-08-31 | Degussa Ag | Transparent molding compound |
| JP6124523B2 (en) * | 2012-07-12 | 2017-05-10 | 旭化成株式会社 | High density polyethylene resin composition and method for producing the same |
| CN111087927B (en) * | 2015-06-11 | 2021-09-28 | 株式会社自动网络技术研究所 | Composition for coating metal surface and covered electric wire with terminal |
Family Cites Families (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4749736A (en) * | 1986-10-20 | 1988-06-07 | Allied Corporation | Nucleating system for polyamides |
| EP0358415A1 (en) * | 1988-09-06 | 1990-03-14 | Ube Industries, Ltd. | Material for molded article and film having liquid or gas barrier property, method for producing the same and use of the same |
| DE19621308A1 (en) * | 1996-05-28 | 1997-12-04 | Bayer Ag | Polyamide molding compositions containing nanodisperse fillers, and films or hollow bodies containing a corresponding polyamide layer |
-
1998
- 1998-10-16 DE DE19847844A patent/DE19847844A1/en not_active Withdrawn
-
1999
- 1999-10-04 CA CA002347086A patent/CA2347086A1/en not_active Abandoned
- 1999-10-04 WO PCT/EP1999/007348 patent/WO2000023512A1/en not_active Application Discontinuation
- 1999-10-04 JP JP2000577232A patent/JP2002527594A/en active Pending
- 1999-10-04 EP EP99947457A patent/EP1129130A1/en not_active Withdrawn
- 1999-10-04 AU AU60892/99A patent/AU6089299A/en not_active Abandoned
Also Published As
| Publication number | Publication date |
|---|---|
| DE19847844A1 (en) | 2000-04-20 |
| JP2002527594A (en) | 2002-08-27 |
| WO2000023512A1 (en) | 2000-04-27 |
| AU6089299A (en) | 2000-05-08 |
| EP1129130A1 (en) | 2001-09-05 |
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