EP1399509A1 - Composite contenant de l'abs - Google Patents

Composite contenant de l'abs

Info

Publication number
EP1399509A1
EP1399509A1 EP02743108A EP02743108A EP1399509A1 EP 1399509 A1 EP1399509 A1 EP 1399509A1 EP 02743108 A EP02743108 A EP 02743108A EP 02743108 A EP02743108 A EP 02743108A EP 1399509 A1 EP1399509 A1 EP 1399509A1
Authority
EP
European Patent Office
Prior art keywords
weight
abs
composites according
styrene
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Withdrawn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
EP02743108A
Other languages
German (de)
English (en)
Inventor
Edgar Leitz
Harry Staratschek
Herbert Eichenauer
Wolfgang Siebourg
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.)
Styrolution Jersey Ltd
Original Assignee
Bayer 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 Bayer AG filed Critical Bayer AG
Publication of EP1399509A1 publication Critical patent/EP1399509A1/fr
Withdrawn legal-status Critical Current

Links

Classifications

    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/302—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising aromatic vinyl (co)polymers, e.g. styrenic (co)polymers
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/04—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B15/08—Layered products comprising a layer of metal comprising metal as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/18—Layered products comprising a layer of metal comprising iron or steel
    • 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
    • B32B15/00—Layered products comprising a layer of metal
    • B32B15/20—Layered products comprising a layer of metal comprising aluminium or copper
    • 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
    • B32B21/00—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board
    • B32B21/04—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B21/08—Layered products comprising a layer of wood, e.g. wood board, veneer, wood particle board comprising wood as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/06—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material
    • B32B27/08—Layered products comprising a layer of synthetic resin as the main or only constituent of a layer, which is next to another layer of the same or of a different material of synthetic resin
    • 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
    • B32B27/28—Layered products comprising a layer of synthetic resin comprising synthetic resins not wholly covered by any one of the sub-groups B32B27/30 - B32B27/42
    • 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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers
    • B32B27/304—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl halide (co)polymers, e.g. PVC, PVDC, PVF, PVDF
    • 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
    • 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
    • B32B27/34—Layered products comprising a layer of synthetic resin comprising polyamides
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • 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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • B32B7/00—Layered products characterised by the relation between layers; Layered products characterised by the relative orientation of features between layers, or by the relative values of a measurable parameter between layers, i.e. products comprising layers having different physical, chemical or physicochemical properties; Layered products characterised by the interconnection of layers
    • B32B7/04—Interconnection of layers
    • B32B7/12—Interconnection of layers using interposed adhesives or interposed materials with bonding properties
    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/04—Oxygen-containing compounds
    • C08K5/13—Phenols; Phenolates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L55/00—Compositions of homopolymers or copolymers, obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in groups C08L23/00 - C08L53/00
    • C08L55/02—ABS [Acrylonitrile-Butadiene-Styrene] polymers
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/24—Aluminium
    • 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
    • B32B2311/00—Metals, their alloys or their compounds
    • B32B2311/30—Iron, e.g. steel
    • 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
    • B32B2323/04—Polyethylene
    • 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
    • B32B2323/10—Polypropylene
    • 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
    • B32B2327/00—Polyvinylhalogenides
    • B32B2327/06—PVC, i.e. polyvinylchloride
    • 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
    • B32B2355/00—Specific polymers obtained by polymerisation reactions only involving carbon-to-carbon unsaturated bonds, not provided for in a single one of index codes B32B2323/00 - B32B2333/00
    • B32B2355/02—ABS polymers, i.e. acrylonitrile-butadiene-styrene polymers
    • 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
    • B32B2367/00—Polyesters, e.g. PET, i.e. polyethylene terephthalate
    • 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
    • B32B2369/00—Polycarbonates
    • 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
    • B32B2377/00—Polyamides

Definitions

  • the invention relates to composites containing an ABS component and at least one further material and molded parts obtainable from these composites.
  • ABS-type polymers are two-phase plastics
  • thermoplastic copolymer of resin-forming monomers e.g. Styrene and acrylonitrile, the styrene being able to be replaced in whole or in part by methylstyrene or methyl methacrylate; this copolymer, also known as SAN resin or matrix resin, forms the outer phase;
  • graft base butadiene homo- or copolymer
  • This graft polymer (“elastomer phase” or “graft rubber”) forms the disperse phase in the matrix resin.
  • ABS polymers 1) and 2) can be prepared by known processes, such as emulsion
  • ABS polymers are composites by gluing these ABS polymers, in particular those ABS polymers, in which at least one of components 1) and 2) through
  • ABS polymers which contain defined amounts of sterically hindered phenols.
  • the invention thus relates to composites
  • R is CJO-C ig-alkyl
  • Al 5 to 100% by weight, preferably 7.5 to 80% by weight and particularly preferably 10 to 70% by weight of at least one graft polymer obtained by solution, suspension or bulk polymerization or 5 to 80% by weight , preferably 7.5 to 70 wt .-% and particularly preferably 10 to 60 wt .-% of at least one graft polymer obtained by emulsion polymerization and
  • A.2) 95 to 0% by weight, preferably 92.5 to 20% by weight and particularly preferably 90 to 30% by weight (when using a graft polymer obtained by solution, suspension or bulk polymerization) or 95 to 20% by weight, preferably 92.5 to 30% by weight and particularly preferably 90 to 40% by weight (when using one obtained by emulsion polymerization
  • Graft polymer at least one thermoplastic resin.
  • graft polymers are those in which, on a rubber (graft base), monomers or monomer mixtures selected from acrylonitrile, methacrylonitrile, maleic anhydride, N-substituted maleimide,
  • Styrene, methylstyrene, nucleus-substituted styrene, methyl methacrylate are graft-polymerized.
  • Suitable rubbers are practically all rubbers with glass transition temperatures ⁇ 10 ° C., preferably those which contain copolymerized butadiene.
  • Examples are polybutadiene, styrene-butadiene polymers, acrylonitrile-butadiene polymers, acrylic rubbers, optionally with built-in structural units derived from butadiene, acrylate rubbers which comprise a crosslinked rubber such as polybutadiene or a copolymer of butadiene with an ethylenically unsaturated or monomer such as styrene and / Acrylonitrile as the core.
  • the graft polymers contain 3 to 95% by weight, in particular 5 to 70% by weight of rubber and 97 to 5% by weight, in particular 95 to 30% by weight of graft-copolymerized monomers.
  • the rubbers are present in these graft polymers in the form of at least partially crosslinked particles with an average particle diameter (d 50 ) of 0.05 to 20.0 ⁇ m and particularly preferably from 0.1 to 0.8 ⁇ m, the average particle diameter d 50 being measured by means of an ultracentrifuge ( see W. Scholtan, H. Lange: Kolloid.-Z. and Z. Polymer 250 (1972), 782-796).
  • Suitable manufacturing processes are emulsion, solution, bulk or suspension polymerizations; Those graft polymers A) which are prepared by means of emulsion polymerization and / or solution or bulk polymerization are particularly preferred.
  • thermoplastic polymers A.2) can be obtained from the monomers graft-polymerized on the rubber (graft monomers) or similar monomers, in particular from at least two monomers selected from styrene, ⁇ -methylstyrene, p-methylstyrene, halostyrene, acrylonitrile, methacrylonitrile, methyl methacrylate, maleic anhydride , N-substituted maleimides, especially N-phenyl maleimide, or mixtures thereof.
  • thermoplastic resins A.2) are copolymers obtained from 95 to 50% by weight of styrene, ⁇ -methylstyrene or methyl methacrylate or mixtures thereof and 5 to 50% by weight of acrylonitrile, methacrylonitrile, methyl methacrylate or maleic anhydride or mixtures thereof.
  • thermoplastic copolymers contain 20 to 40% by weight of acrylonitrile and 80 to 60% by weight of styrene or ⁇ -methylstyrene in copolymerized form. These copolymers are known. They preferably have molecular weights (M w ) of 15,000 to 200,000 (determined by means of gel permeation chromatography (GPC)).
  • M w molecular weights
  • the thermoplastic polymers A.2) are preferably prepared by solution or bulk polymerization.
  • ABS polymers A are made up of
  • Graft polymer of at least one thermoplastic resin, produced by
  • styrene 2.1 5 to 50 wt .-% acrylonitrile, methacrylonitrile, maleic anhydride or N-substituted maleimide or mixtures thereof and 2.2 95 to 50% by weight of styrene, ⁇ -methylstyrene, nucleus-substituted styrene or methyl methacrylate or mixtures thereof.
  • Compounds with at least one sterically hindered hydroxyl group according to component B) are known or can be prepared in a known manner.
  • suitable compounds B) are the compounds of the formulas (V) to (XXV) known as antioxidants.
  • the compounds of the formulas (V) and (XLX) which are commercially available under the trade names Irganox® 1076 or Irganox® 245 are particularly preferred. These compounds are admixed with the ABS polymer described above at higher temperatures, for example 100 ° to 300 ° C., in conventional mixing units, kneaders, internal mixers, roller mills, screw machines or extruders. The dwell times in the mixing process can vary between 10 seconds and 30 minutes depending on the intensity of the mixing.
  • the usual additives such as pigments, fillers, stabilizers, antistatic agents, lubricants, mold release agents, flame retardants and the like can be added to the ABS component.
  • connection of the ABS component with other materials to the composites according to the invention is preferably carried out by gluing.
  • the adhesives known to the person skilled in the art for bonding to composites are suitable. Epoxy and acrylate adhesives are particularly preferred.
  • the composites according to the invention are suitable for the production of molded parts, foils and plates.
  • molded parts are laminates which are made up of two or more layers, for example foils or plates consisting of metal and plastic layers.
  • graft rubber of 50 wt .-% of polybutadiene having an average particle diameter (d 5 o) of 0.35 microns are graft polymerized to 36.5 wt .-% styrene and 13.5 wt .-% of acrylonitrile in emulsion.
  • Styrene / acrylonitrile (SAN) 72:28 - copolymer with an average molecular weight M w of about 85,000, produced by solution polymerization.
  • Styrene / acrylonitrile (SAN) 72:28 - copolymer with an average molecular weight M w of about 85,000, produced by emulsion polymerization.
  • the parts by weight of the individual polymer components given in Table 1 are mixed with the additives likewise given in Table 1 and 0.5 part by weight of ethylenediamine bisstearylamide in an internal kneader at 200 ° C. to 230 ° C. within 3 to 5 minutes and then granulated. The granules are pressed at approx. 0.5 mm thick sheets at 195 ° C.
  • the foils cut from it are then coated on one side with an aluminum plate (approx. 1 mm) and on the other side with a polyethylene foil using a two-component adhesive (Araldit ® AW 136 H from Ciba, Basel, Switzerland, hardener HY 994 from the company Ciba, Basel, Switzerland). After gluing the
  • Plate-film composite is cured in the press (load 10 t) at 100 ° C within 20 min, after which it is cooled to room temperature under constant load in the press.
  • the adhesive strength is checked 2 days after adhesive curing by manual
  • compositions of the ABS polymers and test results (adhesive strength) of the composites made from them.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Wood Science & Technology (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Adhesives Or Adhesive Processes (AREA)

Abstract

L'invention concerne des composites qui contiennent : I) un constituant ABS, contenant A) un polymère ABS et B) 0,05 à 5 % en poids d'au moins un phénol contenant au moins un groupe hydroxyle à encombrement stérique, sélectionné dans des unités structurelles de formules générales (I) à (IV) dans lesquelles R représente alkyle C>10<-C>18<, et II) au moins une autre matière sélectionnée parmi des métaux, d'autres plastiques ou d'autres matières.
EP02743108A 2001-06-07 2002-05-27 Composite contenant de l'abs Withdrawn EP1399509A1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10127748A DE10127748A1 (de) 2001-06-07 2001-06-07 Verbund enthaltend ABS
DE10127748 2001-06-07
PCT/EP2002/005783 WO2002098978A1 (fr) 2001-06-07 2002-05-27 Composite contenant de l'abs

Publications (1)

Publication Number Publication Date
EP1399509A1 true EP1399509A1 (fr) 2004-03-24

Family

ID=7687572

Family Applications (1)

Application Number Title Priority Date Filing Date
EP02743108A Withdrawn EP1399509A1 (fr) 2001-06-07 2002-05-27 Composite contenant de l'abs

Country Status (8)

Country Link
US (1) US20030008948A1 (fr)
EP (1) EP1399509A1 (fr)
JP (1) JP2004527645A (fr)
KR (1) KR20040010685A (fr)
CN (1) CN100354366C (fr)
DE (1) DE10127748A1 (fr)
MX (1) MXPA03011241A (fr)
WO (1) WO2002098978A1 (fr)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB201313849D0 (en) * 2013-08-02 2013-09-18 Castings Technology Internat Producing a metal object

Family Cites Families (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5883187A (en) * 1995-05-16 1999-03-16 Bayer Antwerpen S.A./N.V. Polymer composition with improved toughness
US5698622A (en) * 1996-03-14 1997-12-16 Bayer Ag Stabilisation of ABS graft polymers using dithiodipropionic acid
DE19715595A1 (de) * 1997-04-15 1998-10-22 Bayer Ag Emulsionsfrei hergestellte ABS-Formmassen mit sehr hohrer Kerbschlagzähigkeit

Non-Patent Citations (1)

* Cited by examiner, † Cited by third party
Title
See references of WO02098978A1 *

Also Published As

Publication number Publication date
MXPA03011241A (es) 2004-03-18
JP2004527645A (ja) 2004-09-09
DE10127748A1 (de) 2002-12-12
CN1541250A (zh) 2004-10-27
CN100354366C (zh) 2007-12-12
KR20040010685A (ko) 2004-01-31
WO2002098978A1 (fr) 2002-12-12
US20030008948A1 (en) 2003-01-09

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