EP0960156A1 - Procede de modification de produits ou de produits semi-finis en matieres de moulage comprenant des melanges de matieres thermoplastiques - Google Patents

Procede de modification de produits ou de produits semi-finis en matieres de moulage comprenant des melanges de matieres thermoplastiques

Info

Publication number
EP0960156A1
EP0960156A1 EP98908050A EP98908050A EP0960156A1 EP 0960156 A1 EP0960156 A1 EP 0960156A1 EP 98908050 A EP98908050 A EP 98908050A EP 98908050 A EP98908050 A EP 98908050A EP 0960156 A1 EP0960156 A1 EP 0960156A1
Authority
EP
European Patent Office
Prior art keywords
acid
ester
molding compositions
amide
mixtures
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Withdrawn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
EP98908050A
Other languages
German (de)
English (en)
Inventor
Ralf Schledjewski
Dirk Schultze
Gunter Weber
Rainhard Koch
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.)
Dow Produktions und Vertriebs GmbH and Co oHG
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 EP0960156A1 publication Critical patent/EP0960156A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L77/00—Compositions of polyamides obtained by reactions forming a carboxylic amide link in the main chain; Compositions of derivatives of such polymers
    • C08L77/12—Polyester-amides
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/06—Biodegradable

Definitions

  • This invention relates to a method for modifying products or semi-finished products made of multi-phase plastic molding compositions.
  • the latter are preferably made of
  • thermoplastics built up The processes according to the invention are characterized by modification of density and / or surface structure, which are achieved by selective biodegradation of one or more of the polymer resins used for their production.
  • the molding compositions are made using mixtures of thermoplastic materials with good biodegradability and those with poor or no biodegradability are obtained.
  • the methods of vlodification according to the invention are superior to the methods known from the prior art for removing certain components
  • Modified matrix properties are advantageous, for example, if porous membrane structures are to be achieved which optimally have a defined pore structure
  • the wrappings known according to the prior art are nowadays particularly welded obtained from possibly deep-drawn, anatomically formed preforms. For this purpose, thicker, thermoplastic formable films are required that do not have the unpleasant handle of a comparatively smooth, glossy film that is typical for plastics
  • the task was therefore to adjust the surface of the film to make it pleasant to touch.
  • the mattness of the plastic article had to be improved.
  • the mat properties should be specifically influenced.
  • Processes which are particularly suitable according to the invention for modifying objects and / or semi-finished products made from polymer-resin molding compositions are distinguished in that the partial biodegradation takes place under uniform and defined ambient conditions with regard to temperature, pH value and ambient medium
  • the methods according to the invention are based on the at least partial degradation of at least one phase of the plastic objects from multi-phase plastic Mixtures
  • biodegradable thermoplastic resins have been used as a recipe component
  • Polymer mixtures, blends or blends can be prepared by mechanically mixing melts, latices or solutions of two separately produced polymer resins or m-situ polymerisation of monomers in the presence of a pre-formed polymer resin
  • the polymer resins which are usually in the form of bales, granules or powders, are mixed in kneaders or with extruders.
  • the thermoplastic polymer resins suitable according to the invention are heated above the glass or melting temperature Good mixing is achieved at higher temperatures and / or under strong shear fields
  • the Polvmer resins used for the thermal shaping are subjected to a premixing in a softened state in a compounding step.
  • Suitable tools for such a mixing step are suitable the compounding tools known in their type. Tools with several screws, but especially the two-screw kneaders popular for compounding, have proven to be advantageous
  • Suitable methods for modifying plastic articles are particularly suitable according to the invention if they have a readily biodegradable thermoplastic resin content of at least 30% by weight and a less biodegradable thermoplastic resin content of at least 15% by weight
  • thermoplastic formulation components are particularly preferred as thermoplastic formulation components
  • Biodegradable resins or resin mixtures or foils are defined in accordance with DIN ⁇ 4 900 (draft 1996) with regard to their biodegradability
  • biodegradable resins which are particularly qualified for the composition of suitable molding compositions come from the group of the ester-amide copolymer resins
  • thermoplastic ester-amide copolymers for the inventive
  • Mixtures are preferably made of predominantly linear, thermoplastic ester
  • A) an ester fraction from linear and / or cycloahphatic bifunctional alcohols for example ethylene glycol, hexanediol or butanediol, preferably butanediol or cyclohexanedimethanol and, if appropriate, small amounts of high-functionality alcohols, for example 1,2,3-propanediol or neopentyl glycol, and also from linear and / or cycloahphatic bifunctional acids, for example succinic acid, adipic acid, cyclohexanedicar bonic acid, preferably adipic acid and additional, if appropriate, small amounts of highly functional acids, for example T ⁇ mellithsaure or
  • ester portion from acid- and alcohol-functionalized building blocks for example hydroxybutyric acid or hydroxypropane acid or their derivatives, for example ⁇ -caprolactone
  • ester fraction A) and / or B) is at least 30% by weight based on the sum of A), B), C) and D)
  • the biodegradable and compostable polyester amides preferably have a molecular weight of at least 10,000 g / mol and have a statistical distribution of the starting materials (monomers) in the polymer
  • the task was to provide molding materials that were as soft as possible with a pleasant feel and good buildability. This also included inexpensive manufacture and processing
  • the object is particularly preferably achieved in that soft-elastic molding compositions are obtained by mixing thermoplastic polyurethanes with polyester amide copolymer resins.
  • Thermoplastic polyurethanes are composed of soft and hard segregates, which means that the molding composition can be permanently softened. Molding compositions which have at least one per - Manent soft-modified thermoplastic component with poorer biodegradability
  • the thermoplastic polyurethanes have been known for a long time and have a high chemical resistance. Their three basic components are Dnsocvanate short-chain diols - also known as chain extenders - and long-chain diols, the latter contributing to the elastic-soft properties.
  • thermoplastic polyurethanes In the case of commercially available thermoplastic polyurethanes, the aim is generally to combine good strength values, ie tensile and tear propagation resistance and great elasticity, ie high elongation and cold flexibility, an overview of the chemical structure, the production and properties and the resulting possible applications of thermoplastic polyurethanes e.g. Goyert and Hespe in Kunststoffe 68 (1978) 819-825 or Hepburn (ed.) in Polyurethane Elastomers, Applied Science Pubhshers, Barking 1982
  • thermoplastic polyurethane elastomers for the mixtures according to the invention are preferably composed of predominantly linear thermoplastic polyurethane elastomers, the long-chain diol components of which are made of Polvester or polyether, and which have a Shore hardness of preferably 75-95 A, particularly preferably 85-92 A, determined according to DEN 53 505
  • thermoplastic polyurethanes are, for example, under the trade names
  • thermoplastic polyurethanes have a molecular weight of at least 10,000 g / mol and have a block-like sequence of hard and soft segment starting materials (monomers) in the polymer resin
  • the objects or semifinished products to be modified according to the invention have elastic in the molding compositions which form them Urethane elastomer formulation components on whose soft segment phase are predominantly formed from ester soft segment building blocks
  • a particularly preferred object of the present invention is thus the modification of products and / or semi-finished products from molding compositions with soft-elastic behavior, which at least consist of thermoplastically processable polyurethane resins and Polvesteramide resins. Furthermore, the subject matter of this invention can then be seen that the films according to the invention made of resin mixtures have improved biological films made of thermoplastic polyurethanes in comparison with the prior art have
  • the polymer resins mixed for this invention already have multiphase structures in themselves, so that in the present invention there is mutual expansion of the network-like structures of the mixing partners must be assumed.
  • the mixtures according to the invention can be processed or shaped into molding materials or objects which do not have properties almost represent the corresponding proportional properties of the mixed polymer resins used
  • thermoplastic polyurethanes and polyester amide copolymers mix contractually in formulations, ie the properties of the blend components correspond proportionately to those of the pure raw material components used.
  • the mechanical strength properties of the resin mixtures according to the invention were not as customary as with incompatible plastics
  • Such demixing patterns are observed, for example, for mixtures of thermoplastic polyurethanes with low-density polyurethane resins, for which it is known to the skilled artisan that strengths are observed with these blends, which are below the level at values around 10 N / mm of pure polypropylene, there is also the fact that blends of this type have strongly anisotropic segregation structures in which the different phases are oriented towards processing Form domains
  • Objects or semifinished products, in particular foils, which are particularly suitable for the modification according to the invention are distinguished by the fact that they have a readily biodegradable thermoplastic resin fraction, preferably a co-polyester ester amide fraction of at least 30% by weight, and a less biodegradable thermoplastic resin fraction, in particular have polyurethane resin content of at least 15% by weight
  • the molding compound contains blends of thermoplastic
  • Resins for the production of suitable products and / or semi-finished products which can be modified according to the invention additionally comprise additives customary from the group
  • Particularly suitable inorganic additives come from the group comprehensively
  • V natural and synthetic silica or silicates also layered silicates
  • Preferred semi-finished products according to the invention for the modification process are films made from blends of at least two thermoplastic resins. Before modification, these preferably have a Shore D hardness of less than 55, measured in accordance with DIN 53505
  • a method for modifying plastic articles is suitable, wherein at least two of the Polvmer resins used as raw materials for the molding composition were previously subjected to a premixing in a softened state in a compounding step
  • a film was produced for which a prefabricated compound was used as the raw material.
  • the compound consisted of 82.5% by weight ester-amide copolymer resin with a Shore ⁇ hardness of large ⁇ 15% by weight of a TPU from the Shore -A-Harte 92 with polvbutylene adipate soft segments 1% by weight of silicates and 1% by weight of low molecular weight amide waxes
  • the Extrusionsein ⁇ chtung was operated at temperatures between 130 C C and 170 ° C
  • the compound melt stream was discharged into a blown film with a processing temperature of 190 ° C by a Ringspaltduse having a diameter of 1 10 mm, the annular melt web was cooled by blowing with air, then laid flat, trimmed in the edge area and wound in the form of 50 around thick single sheets.
  • the finishing according to the invention was carried out in a water buffer solution over a period of 60 min. This was heated to 37 ° C.
  • the pH was 6 5
  • a film was produced analogously to Example A with a thickness of 50 .mu.m.
  • the raw materials were brought together shortly before the extruder was drawn in, the composition of the blend being 29% by weight TPU 68 5% by weight ester-amide copolymer resin, 1.5% by weight -% silicate and 1% by weight - waxes is represented.
  • the processing parameters corresponded to example A, however the extrusion tool was only operated at temperatures of 130-180 ° C. the melt temperature was 200 ° C.
  • the finishing modification according to the invention was carried out analogously to example A.
  • a film was produced analogously to Example B in a thickness of 50 ⁇ m.
  • the composition of the blend was 58 5% by weight ester-amide copolymer 39 5 % By weight of TPU, 1% by weight of waxes and 1% by weight of silicate lay.
  • the finishing modification according to the invention was carried out analogously to Example A.
  • a TPU film was produced under the parameters mentioned for Example A.
  • the composition of the translucent 50 ⁇ m thick film was 97% by weight of a TPU from Shore-A-Harte 92 with a polyadipate-based soft segment phase and 1% by weight of low molecular weight amide waxes and 2% by weight of silica.
  • the processing parameters corresponded to Example B The modification was carried out analogously to Example A
  • a 50 ⁇ m thick ester amide copolymer film was made using 98% by weight
  • Copolyesteramide with a Shore A hardness of large 95, 1% by weight of silicate and 1% by weight of amide wax was produced.
  • the processing parameters corresponded to Example A.
  • the modification was carried out analogously to Example A.
  • the evaluation of the films produced in the examples and comparative examples was partly carried out with regard to application-relevant properties such as skin / skin friendliness or haptics and biodegradability.
  • the evaluation of these relevant properties was obtained by subjective evaluation by several independent persons and the evaluations given in Table 1 as far as possible - The subjective assessments were verified through standardized test procedures
  • the haptics were assessed manually on the finished film webs before and after the finishing step.
  • the coefficients of friction or numbers were determined in accordance with DIN 53 375.
  • the gloss was determined in accordance with DIN 67530 at a measuring angle of 20 °
  • the table below shows characteristic data of the films produced in the examples and comparative examples
  • the films shown in the examples are the films known from the prior art from the comparative examples, in particular with regard to the controlled biodegradability. are clearly superior to the pure films of ester-amide copolymers as described in Comparative Example 2, the films not yet modified according to the invention do not yet offer advantages in terms of wearing comfort and elasticity

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Biological Depolymerization Polymers (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne un procédé de modification d'objets et/ou de produits semi-finis en matières de moulage à base de polymère et de résine. Selon ce procédé, les objets et/ou les produits semi-finis en matières de moulage comprenant des mélanges de polymérisats thermoplastiques à bonne biodégradabilité et des polymérisats thermoplastiques à biodégradabilité difficile, sont soumis à une biodégradation.
EP98908050A 1997-02-17 1998-02-04 Procede de modification de produits ou de produits semi-finis en matieres de moulage comprenant des melanges de matieres thermoplastiques Withdrawn EP0960156A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE19706024A DE19706024A1 (de) 1997-02-17 1997-02-17 Verfahren zur Modifizierung von Produkten oder Halbzeugen aus Formmassen bestehend aus Mischungen thermoplastischer Kunststoffe
DE19706024 1997-02-17
PCT/EP1998/000586 WO1998036019A1 (fr) 1997-02-17 1998-02-04 Procede de modification de produits ou de produits semi-finis en matieres de moulage comprenant des melanges de matieres thermoplastiques

Publications (1)

Publication Number Publication Date
EP0960156A1 true EP0960156A1 (fr) 1999-12-01

Family

ID=7820483

Family Applications (1)

Application Number Title Priority Date Filing Date
EP98908050A Withdrawn EP0960156A1 (fr) 1997-02-17 1998-02-04 Procede de modification de produits ou de produits semi-finis en matieres de moulage comprenant des melanges de matieres thermoplastiques

Country Status (6)

Country Link
US (1) US6251968B1 (fr)
EP (1) EP0960156A1 (fr)
JP (1) JP2001512505A (fr)
AU (1) AU6619698A (fr)
DE (1) DE19706024A1 (fr)
WO (1) WO1998036019A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US7309252B2 (en) * 2005-02-22 2007-12-18 Tyco Electronics Corporation Low profile surface mount connector
JP2007106783A (ja) * 2005-10-11 2007-04-26 Fujitsu Ltd 樹脂成型体およびこれを用いた電子機器、樹脂成型体の処理方法
KR100960402B1 (ko) * 2005-10-17 2010-05-28 폴리원 코포레이션 열가소성 폴리우레탄 분말 조성물 및 용도

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS54119593A (en) * 1978-03-09 1979-09-17 Agency Of Ind Science & Technol Biodegradation of copolyester-amide
JP3194792B2 (ja) * 1992-06-12 2001-08-06 天野エンザイム株式会社 酵素を用いた脂肪族ポリエステルの分解法
BR9405651A (pt) * 1993-01-08 1995-11-14 Novon International Inc Composição de mistura de polímeros termoplásticos biodegradáveis; processo de preparar a mesma; artigo formado; filme e fibra
DE19619236A1 (de) * 1996-05-13 1997-11-20 Bayer Ag Abbau von biologisch abbaubaren Polyesteramiden mit Enzymen

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO9836019A1 *

Also Published As

Publication number Publication date
AU6619698A (en) 1998-09-08
DE19706024A1 (de) 1998-08-20
US6251968B1 (en) 2001-06-26
WO1998036019A1 (fr) 1998-08-20
JP2001512505A (ja) 2001-08-21

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