EP1129130A1 - Materiau polymere semi-cristallin thermoplastique contenant des agents de nucleation nanoscopiques, et pieces moulees extremement transparentes produites a partir dudit materiau - Google Patents

Materiau polymere semi-cristallin thermoplastique contenant des agents de nucleation nanoscopiques, et pieces moulees extremement transparentes produites a partir dudit materiau

Info

Publication number
EP1129130A1
EP1129130A1 EP99947457A EP99947457A EP1129130A1 EP 1129130 A1 EP1129130 A1 EP 1129130A1 EP 99947457 A EP99947457 A EP 99947457A EP 99947457 A EP99947457 A EP 99947457A EP 1129130 A1 EP1129130 A1 EP 1129130A1
Authority
EP
European Patent Office
Prior art keywords
polyamide
material according
particles
polymer
molded parts
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Withdrawn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
EP99947457A
Other languages
German (de)
English (en)
Inventor
Holger Eggers
Gregor Kaschel
Rainer Brandt
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.)
Wipak Walsrode GmbH and Co KG
Original Assignee
Wolff Walsrode AG
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 Wolff Walsrode AG filed Critical Wolff Walsrode AG
Publication of EP1129130A1 publication Critical patent/EP1129130A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K7/00—Use of ingredients characterised by shape
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • 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
    • 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

Definitions

  • the present invention relates to a polymeric, partially crystalline thermoplastic material which contains nucleating particles in the size range of less than 100 nm of nanoscale nucleating agents in dispersed form. Molded parts made from this are characterized by excellent transparency with high gloss as well as high dimensional stability and hardness.
  • the invention therefore also relates to molded parts, in particular foils, which are produced partially or entirely using the material according to the invention, as an exclusive component or as a mixed component.
  • Advantages over conventional polymeric materials containing nucleating agents are the extremely fine-grained and highly crystalline crystal structure, and in particular the associated transparency.
  • the nucleating agent itself influences the
  • Nucleating agents for polymeric, partially crystalline thermoplastic materials are of considerable importance. They cause a high nucleation rate and thus a crystallization rate that is suitable for a wide temperature, i.e.
  • hypothermia area is significantly increased compared to non-nucleated systems. As a result, they lead to a high degree of crystallization in conventional industrial cooling processes from the melt. This is illustrated using the example of polyamide 6 and the nucleating agents talc and kaolin in Kohan (ed.), Nylon Plastics Handbook, Hanser Publishers, Kunststoff 1995.
  • nucleated polymeric materials lie in the increased rigidity and hardness combined with higher toughness, abrasion resistance and surface hardness due to the crystalline components, as well as in the transparency and the noticeably improved properties of conventional nucleating agents compared to non-nucleated polymeric materials due to the fine crystalline structure an increased gloss of the molded parts made from it. Due to the rapid and extensive crystallization during cooling from the melt, most of the crystallization process in the molded part is already completed with the shaping process. In non-nucleated systems, on the other hand, metastable cooling can occur due to the rapid cooling in relation to the rate of crystallization
  • nucleating systems in particular in the form of dispersed, finely divided inorganic solid particles, is state of the art.
  • WO 8802763 mentions here in particular talc, mica, kaolin and, secondly, such substances as asbestos, aluminum, 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 .
  • Said systems are added in concentrations between one thousandth of a percent and one percent, based on the total weight of the nucleated polymer.
  • plasticizing substances are often added to the polymer.
  • the glass transition temperature of the polymer can be lowered and the temperature range in which crystal growth can still take place around the seeds can be expanded to lower temperatures.
  • Suitable substances are, for example, polymers with a molecular weight which gives the polymer a waxy consistency. It can Polyolefins, polyoxides, polysulfides and / or fatty acid derivatives, in particular fatty acid amides, can be used.
  • talc is mainly used as the nucleating agent for polyamide.
  • the size of the particles used is in the range from about 1 to
  • Matrix different refractive index itself very cloudy.
  • a fatty acid amide in particular ethylene bisstearylamide, is often added as the plasticizing component in the sense described above.
  • surface modification of the particles e.g. with citric acid the nucleation can be improved.
  • EP 358 415 describes a molding compound made of a polyamide resin with a layered silicate uniformly dispersed therein, the individual layers of the layered silicate having thicknesses of around 1 nm and side lengths up to 1 ⁇ m.
  • Layers are separated in the polyamide matrix by suitable digestion and are spaced apart by 10 nm.
  • Shaped parts, such as foils, made with this material from polyamide 6 as the base polymer are distinguished from those made from pure polyamide 6 by a significantly increased oxygen barrier and rigidity. Toughness decreases noticeably. The sliding properties are improved.
  • the transparency of single-layer amorphously quenched flat films and blown films with water cooling with the structure of polyamide mixture / bonding agent / PE-LD remains unchanged compared to pure polyamide 6.
  • WO 9304118 as well as WO 931 1190 and WO 9304117 disclose polymer nano
  • Composites with platelet-shaped particles in the thickness range of a few nanometers Composites of PA 6 and montmorillonite or PA 6 and silicates are described in particular. These materials can be processed into foils. The advantages of such films are higher stiffness, higher strength when wet, better dimensional stability, a higher gas barrier and lower water absorption compared to films without nanoscale particles. An effect of the added particles on the transparency is not described.
  • EP 810 259 also describes a polyamide molding material with nanodisperse fillers.
  • the barrier effect of the polyamide desired there can be improved by adding enough finely divided oxides, oxyhydrates or carbonates.
  • the particles preferably have a diameter of less than 100 nm.
  • the patent also describes multilayer films with at least one layer of this molding composition, the intention being to use the molding compositions mentioned, which is always an improvement in the oxygen barrier.
  • the optical properties of the films formed therefrom deteriorate compared to the non-additive system.
  • WO 980346 also describes the use of nanodisperse fillers to improve the barrier properties of polyesters.
  • a polymer with a platelet-shaped mineral dispersed in it between 0.1 and 10% and a particle thickness of less than 100 nm is characterized by a high oxygen barrier and strength while maintaining transparency and is suitable, for example, for the production of packaging films.
  • the task is to provide a polymeric, semi-crystalline material which can be processed as a melt and which can be processed into a molded part in typical industrial shaping processes and which has very good transparency, high gloss, high rigidity and toughness, high Has hardness and abrasion resistance and shrinks only slightly after shaping.
  • the materials according to the invention can be produced from a partially crystalline polymer with a phase of inorganic solid particles dispersed therein by melting the polymer containing inorganic solid particles and, if appropriate, other customary additives in an extruder and then the completely melted polymer at a cooling rate between 30 ° and 40 ° C per minute cools, whereby crystalline structures arise.
  • the na ⁇ oscale particles can preferably be incorporated in the semi-crystalline polymer using conventional methods used for the dispersion of 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 melted polymer at a cooling rate between 30 ° and
  • the partially crystalline polymer can be any crystallizable polymer.
  • Polymers selected from the group of polymers comprising polyamide, polyethylene, copolymers based on ethylene, polypropylene, copolymers based on propylene, polyvinyl chloride, polyacetals, polyketones, polyesters and copolyesters and polyurethane are particularly suitable.
  • Polyamide in the form of aliphatic or aromatic homo- and copolyamides and their mixtures in particular polyamide 6, polyamide 10, polyamide 12, polyamide 66, polyamide 610, polyamide 61, polyamide 612, polyamide 6/66, polyamide 6I / 6T, can preferably be used as the partially crystalline polymer , Polyamide MXD 6, polyamide 6/61, polyamide 6 / 6T, polyamide 6 / IPDI and copolyamides or mixtures thereof are used.
  • the size of the particles is therefore preferably less than 50 nm, in a still more preferred form less than 10 nm in at least one direction, which can be chosen arbitrarily for each particle, in the number-weighted average of all particles.
  • the solid nanoscale particles preferably have an approximately spherical shape, but they can also have a platelet-shaped or unidirectionally expanded shape.
  • Amorphous particles can also be used. Agglomerates of such particles can also be used.
  • the solid nanoscale particles can have a modified surface which enables increased affinity for the surrounding polymer.
  • Suitable addition amounts of the solid nanoscale particles are between 10 and
  • the material can also contain other commonly used additives in conventional amounts.
  • examples are lubricants,
  • Stabilizers for processing aids, antiblocking agents, fillers, dyes and the like.
  • the addition of macromolecular substances which are present in a wax-like state at room temperature before the addition is particularly suitable.
  • the material according to the invention can be processed from the melt into molded parts, in particular foils. These molded parts can contain the material in regions or continuously, they can consist in the material-containing regions of the material alone or as a mixture of several different materials according to the invention, with other polymers or other materials.
  • the material according to the invention it is possible to provide a material which, in typical industrial shaping processes, leads from the melt to highly crystalline molded parts which have both high rigidity, hardness and abrasion resistance and also have high toughness.
  • the cooling rate has an influence on the effect of the nanoscale particles.
  • an effect on the properties that can be recognized in the molded part only occurs at cooling rates of more than 200 ° C./s.
  • the molded parts that can be produced from this material are also distinguished by a surprisingly low shrinkage following the molding process.
  • the material according to the invention can be processed particularly well into flexible films. Films with one or more layers containing at least one such material, alone or in a mixture, are therefore also the subject of the invention.
  • Single-layer flat films made of polyamide were produced using the typical process for this.
  • the mold was melted in an extruder and poured through a slot die onto a tempered, rotating casting roll.
  • the casting roll had a diameter of 1 100 mm, the film wrapped around the casting roll at an angle of 190 °.
  • the tangential speed of the surface of the casting roll was 30 m / min.
  • the films produced in this way have a thickness of 50 ⁇ m.
  • a film made of polyamide 6 was produced with a casting roll temperature of 30 ° C.
  • the polyamide 6 used has a crystallite melting point of 220 ° C and a relative viscosity in 98% sulfuric acid of 3.6. It contains 600 ppm
  • Ethylene bis stearyl amide and is nucleated with approx. 150 ppm talc.
  • the film from comparative example 1 was produced with a casting roll temperature of 100 ° C. All other conditions correspond to Comparative Example 1.
  • the polyamide contains no other nucleating agent.
  • Break resistance as a measure of the toughness of the film.
  • the kink resistance is measured at a temperature of 23 ° C and a relative humidity of 0% by rolling up a sample blank in a single layer to a cylinder with a length of 198 mm and a circumference of 280 mm and clamping it on both sides in appropriately shaped holders.
  • the free length of the cylinder formed by the film between the brackets is 192 mm.
  • the foils to be checked are previously kept in a climate of 23 ° C and 0% relative humidity for 3 days.
  • the number of breaks in the film in this way after the predetermined number of strokes can be determined by wetting the film with ammonia solution on one side while simultaneously contacting the other side of the film with a sheet of blueprint paper.
  • the number of blue-black spots on the blueprint paper caused by ammonia that can be recognized after 15 minutes is assigned to the number of fold breaks in the examined film section. The value is obtained as the average of the individual values from two test samples.
  • Shrink film after heat treatment in water at 121 ° C for 30 minutes The change in the length of a square film section with the edge lengths 100 mm at 23 ° C. and 0% relative humidity was determined by measurement before and after the heat treatment in both the longitudinal and transverse directions, and a shrinkage value based on the area was calculated therefrom.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Materials Engineering (AREA)
  • Manufacturing & Machinery (AREA)
  • Nanotechnology (AREA)
  • Physics & Mathematics (AREA)
  • Composite Materials (AREA)
  • Condensed Matter Physics & Semiconductors (AREA)
  • General Physics & Mathematics (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Processes Of Treating Macromolecular Substances (AREA)
  • Manufacture Of Macromolecular Shaped Articles (AREA)

Abstract

L'invention concerne un matériau polymère semi-cristallin, thermoplastique qui contient sous forme dispersée des particules possédant une activité de nucléation, de taille inférieure à 100 nm. L'invention concerne également des pièces moulées produite à partir de ce matériau.
EP99947457A 1998-10-16 1999-10-04 Materiau polymere semi-cristallin thermoplastique contenant des agents de nucleation nanoscopiques, et pieces moulees extremement transparentes produites a partir dudit materiau Withdrawn EP1129130A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19847844 1998-10-16
DE19847844A DE19847844A1 (de) 1998-10-16 1998-10-16 Polymerer, teilkristalliner thermoplastischer Werkstoff mit nanoskaligem Nukleierungsmittel und daraus hergestellte hochtransparente Formteile
PCT/EP1999/007348 WO2000023512A1 (fr) 1998-10-16 1999-10-04 Materiau polymere semi-cristallin thermoplastique contenant des agents de nucleation nanoscopiques, et pieces moulees extremement transparentes produites a partir dudit materiau

Publications (1)

Publication Number Publication Date
EP1129130A1 true EP1129130A1 (fr) 2001-09-05

Family

ID=7884752

Family Applications (1)

Application Number Title Priority Date Filing Date
EP99947457A Withdrawn EP1129130A1 (fr) 1998-10-16 1999-10-04 Materiau polymere semi-cristallin thermoplastique contenant des agents de nucleation nanoscopiques, et pieces moulees extremement transparentes produites a partir dudit materiau

Country Status (6)

Country Link
EP (1) EP1129130A1 (fr)
JP (1) JP2002527594A (fr)
AU (1) AU6089299A (fr)
CA (1) CA2347086A1 (fr)
DE (1) DE19847844A1 (fr)
WO (1) WO2000023512A1 (fr)

Families Citing this family (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE10137460A1 (de) * 2001-08-02 2003-02-13 Woehr Richard Gmbh Eingabe- und/oder Anzeigevorrichtung
ATE343215T1 (de) * 2001-08-02 2006-11-15 Woehr Richard Gmbh Eingabe- und/oder anzeigevorrichtung
CH695687A5 (de) * 2002-09-06 2006-07-31 Ems Chemie Ag Polyamid-Formmassen mit ultrafeinen Füllstoffen und daraus herstellbare Lichtreflektier-Bauteile.
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 (de) * 2003-03-17 2004-12-16 Saehan Industries Inc. Gesättigter Polyester zur Formgebung mit hervorragender Kristallinität
DE102005007664A1 (de) * 2005-02-19 2006-08-31 Degussa Ag Transparente Formmasse
JP6124523B2 (ja) * 2012-07-12 2017-05-10 旭化成株式会社 高密度ポリエチレン樹脂組成物、及びその製造方法
WO2016199567A1 (fr) * 2015-06-11 2016-12-15 株式会社オートネットワーク技術研究所 Composition de revêtement de surface métallique et fil électrique recouvert pourvu d'une borne

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4749736A (en) * 1986-10-20 1988-06-07 Allied Corporation Nucleating system for polyamides
EP0358415A1 (fr) * 1988-09-06 1990-03-14 Ube Industries, Ltd. Matériau pour article moulé et film ayant des propriétés de barrière liquide ou gazeuse, méthode pour produire et utiliser ce matériau
DE19621308A1 (de) * 1996-05-28 1997-12-04 Bayer Ag Polyamidformmassen enthaltend nanodisperse Füllstoffe, sowie Folien oder Hohlkörper enthaltend eine entsprechende Polyamidschicht

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO0023512A1 *

Also Published As

Publication number Publication date
CA2347086A1 (fr) 2000-04-27
JP2002527594A (ja) 2002-08-27
AU6089299A (en) 2000-05-08
DE19847844A1 (de) 2000-04-20
WO2000023512A1 (fr) 2000-04-27

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