EP2501545A2 - Composant de construction comprenant un insert et un enrobage plastique, et son procédé de fabrication - Google Patents

Composant de construction comprenant un insert et un enrobage plastique, et son procédé de fabrication

Info

Publication number
EP2501545A2
EP2501545A2 EP10778654A EP10778654A EP2501545A2 EP 2501545 A2 EP2501545 A2 EP 2501545A2 EP 10778654 A EP10778654 A EP 10778654A EP 10778654 A EP10778654 A EP 10778654A EP 2501545 A2 EP2501545 A2 EP 2501545A2
Authority
EP
European Patent Office
Prior art keywords
component
plastic component
plastic
acid
insert
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Withdrawn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
EP10778654A
Other languages
German (de)
English (en)
Inventor
Rebekka VON BENTEN
Alireza Talebloo
Harald KRÖGER
Peter Eibeck
Kai Oliver Siegenthaler
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.)
BASF SE
Original Assignee
BASF SE
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 BASF SE filed Critical BASF SE
Priority to EP10778654A priority Critical patent/EP2501545A2/fr
Publication of EP2501545A2 publication Critical patent/EP2501545A2/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Withdrawn legal-status Critical Current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
    • B32B27/06—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
    • B32B27/30—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (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
    • B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
    • B32B19/02—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica the layer of fibres or particles being impregnated or embedded in a plastic substance
    • 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
    • B32B19/00—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica
    • B32B19/08—Layered products comprising a layer of natural mineral fibres or particles, e.g. asbestos, mica comprising asbestos
    • 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
    • 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
    • B32B27/308—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising acrylic (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
    • 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
    • B32B27/38—Layered products comprising a layer of synthetic resin comprising epoxy resins
    • 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
    • B32B3/00—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form
    • B32B3/02—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions
    • B32B3/08—Layered products comprising a layer with external or internal discontinuities or unevennesses, or a layer of non-planar shape; Layered products comprising a layer having particular features of form characterised by features of form at particular places, e.g. in edge regions characterised by added members at particular parts
    • 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
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
    • H02G3/00—Installations of electric cables or lines or protective tubing therefor in or on buildings, equivalent structures or vehicles
    • H02G3/02—Details
    • H02G3/08—Distribution boxes; Connection or junction boxes
    • 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
    • B32B2250/00—Layers arrangement
    • B32B2250/24—All layers being polymeric
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/02—Synthetic macromolecular fibres
    • B32B2262/0261—Polyamide fibres
    • B32B2262/0269—Aromatic polyamide fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/101—Glass fibres
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/10—Inorganic fibres
    • B32B2262/106—Carbon fibres, e.g. graphite fibres
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/06—Vegetal particles
    • B32B2264/062—Cellulose particles, e.g. cotton
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/06—Vegetal particles
    • B32B2264/062—Cellulose particles, e.g. cotton
    • B32B2264/065—Lignocellulosic particles, e.g. jute, sisal, hemp, flax, bamboo
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • 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
    • B32B2264/00—Composition or properties of particles which form a particulate layer or are present as additives
    • B32B2264/10—Inorganic particles
    • B32B2264/102—Oxide or hydroxide
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/50—Properties of the layers or laminate having particular mechanical properties
    • B32B2307/54—Yield strength; Tensile strength
    • 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
    • B32B2307/00—Properties of the layers or laminate
    • B32B2307/70—Other properties
    • B32B2307/704—Crystalline
    • 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
    • B32B2333/00—Polymers of unsaturated acids or derivatives thereof
    • B32B2333/04—Polymers of esters
    • B32B2333/12—Polymers of methacrylic acid esters, e.g. PMMA, i.e. polymethylmethacrylate
    • 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
    • B32B2571/00—Protective equipment
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/08—Cars
    • 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
    • B32B2605/00—Vehicles
    • B32B2605/18—Aircraft
    • H—ELECTRICITY
    • H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
    • H02G—INSTALLATION OF ELECTRIC CABLES OR LINES, OR OF COMBINED OPTICAL AND ELECTRIC CABLES OR LINES
    • H02G15/00—Cable fittings
    • H02G15/013—Sealing means for cable inlets
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31551—Of polyamidoester [polyurethane, polyisocyanate, polycarbamate, etc.]
    • Y10T428/31616—Next to polyester [e.g., alkyd]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31678—Of metal
    • Y10T428/31681—Next to polyester, polyamide or polyimide [e.g., alkyd, glue, or nylon, etc.]
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
    • Y10T428/00—Stock material or miscellaneous articles
    • Y10T428/31504—Composite [nonstructural laminate]
    • Y10T428/31786—Of polyester [e.g., alkyd, etc.]

Definitions

  • Component comprising an insert and a plastic casing and method for its production
  • the invention relates to a component, comprising an insert and a plastic sheath of at least two plastic components, wherein the insert is enclosed by a plastic component A and the first plastic component A is surrounded by a second plastic component B.
  • the invention further relates to a method for producing such a component.
  • Components comprising an insert and a plastic jacket are used e.g. when using metal inserts for the integration of electronic components used for example in automotive or aerospace technology.
  • a media-tight or cohesive composite in the component is required to prevent penetration of moisture or liquid and thus damage to the electronic components.
  • the tightness of the component must also be ensured if the component is subject to temperature fluctuations.
  • One reason for defective tightness of the fabric bond in composite structures of a metallic insert with a plastic jacket can e.g. resulting from poor wetting and thus poor adhesion of the metal component by the plastic component.
  • differences in the thermal expansion of the metallic component and the plastic component lead to stresses that can cause cracks.
  • a component in the form of a plug in which a metallic insert is enclosed by a plastic casing is known, for example, from EP-B 0 249 975.
  • a flexible plastic material is introduced between the outer plastic material and the metallic insert.
  • the flexible fuel material is z.
  • a passage of a cable is described from a plastic jacket.
  • the seal is made by a sealant that is adhesive to both the material of the spout and the sheath material of the lines.
  • a suitable sealant for example, fat, wax, resin, bitumen or the like may be mentioned.
  • Another plug connection in which metallic pins are accommodated in a solid casing of a plastic material, is also known from EP-A 0 245 975. A flexible plastic material is inserted between the metal pins and the outer shell to achieve a tight connection.
  • a component in which the insert is encased by a plastic layer is also known from WO-A 2008/099009.
  • the metallic insert is first coated with a plastic compound of low viscosity and in a second step, the envelope is encapsulated with a plastic hard component.
  • Suitable plastics which have the low viscosity are polyamides, aliphatic polyesters or polyesters based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds.
  • a further housing leadthrough, in which an electrical contact is guided through a housing, is known from DE-B 10 2005 033 912.
  • the housing passage is sealed against the ingress of undesirable substances.
  • the roughness depth of the conductor element in the sealing area is increased by electroplating.
  • a component comprising an insert and a plastic sheath of at least two plastic components, wherein the insert is enclosed by a first plastic component A and the first plastic component A is surrounded by a second plastic component B, wherein the first plastic component A is constructed :
  • A1 5 to 80 wt .-%, based on the total weight of the components A1 and A2, of at least one polyester based on aliphatic and aromatic
  • A2 20 to 95% by weight, based on the total weight of components A1 and A2, of at least one homo- or copolyester selected from the group consisting of polylactide (PLA), polycaprolactone, polyhydroxyalkanoates (eg PHB or PHB / V) and polyesters of aliphatic dicarboxylic acids and aliphatic diols;
  • PLA polylactide
  • PHB polycaprolactone
  • PHB or PHB / V polyhydroxyalkanoates
  • polyesters of aliphatic dicarboxylic acids and aliphatic diols polyesters of aliphatic dicarboxylic acids and aliphatic diols
  • A3 from 0.05 to 15% by weight, based on the total weight of components A1 and A2, of a) of an epoxide group-containing copolymer based on styrene, acrylic ester and / or methacrylic ester, b) of a bisphenol A epoxide or c) one
  • thermoplastic styrene (co) polymer each based on the polymer content of the second plastic component B.
  • the first plastic component A which is composed of the at least one polyester based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds A1 (hereinafter referred to as partially aromatic polyesters) and the at least one homo- or copolyester A2 and as Compatibility Agent used component A3, a significantly improved compared to the known from the prior art plastic sheathing media density is achieved, especially when using the component in temperature changes.
  • Particularly preferred partially aromatic polyesters A1 include polyesters which, as essential components 1), are an acid component
  • a diol component selected from at least one C 2 to Ci 2 alkanediol, at least one C 5 - to C 0 -Cycloalkandiol or mixtures thereof, and optionally in addition one or more components selected from
  • the acid component 1) of the partly aromatic polyester A1 contains from 30 to 70, in particular from 40 to 60, mol% of 1 a) and from 30 to 70, in particular from 40 to 60, mol% of 1 b).
  • aliphatic acids and the corresponding derivatives 1 a) are generally those having 2 to 1 0 carbon atoms, preferably 4 to 6 carbon atoms, into consideration. They can be both linear and branched.
  • the cycloaliphatic dicarboxylic acids which can be used in the context of the present invention are generally those having 7 to 10 carbon atoms and, in particular, those containing 8 carbon atoms. In principle, however, it is also possible to use dicarboxylic acids having a larger number of carbon atoms, for example having up to 30 carbon atoms.
  • malonic acid succinic acid, glutaric acid, 2-methylglutaric acid, 3-methylglutaric acid, adipic acid, pimelic acid, azelaic acid, sebacic acid, fumaric acid, 2,2-dimethylglutaric acid, suberic acid, 1,3-cyclopentanedicarboxylic acid, 1,4-cycl oh exa ndi ca rbo n se u re, 1, 3-cyclohexane icarboxylic acid, diglycols, itaconic acid, maleic acid and 2,5-norbornane dicarboxylic acid.
  • ester-forming derivatives of the abovementioned aliphatic or cycloaliphatic dicarboxylic acids which are also useful, in particular the di-Ci- to C 6 - alkyl esters, such as dimethyl, diethyl, D in-propyl, D i-isopropyl, D in butyl, di-isobutyl, di-t-butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl ester.
  • Anhydrides of dicarboxylic acids can also be used.
  • the dicarboxylic acids or their ester-forming derivatives can be used individually or as a mixture of two or more thereof.
  • succinic acid Preference is given to using succinic acid, adipic acid, azelaic acid, sebacic acid, brassylic acid or their respective ester-forming derivatives or mixtures thereof.
  • Succinic acid, adipic acid or sebacic acid or their respective ester-forming derivatives or mixtures thereof are particularly preferably used.
  • aliphatic dicarboxylic acid sebacic acid or mixtures of sebacic acid with adipic acid are preferably used when polymer blends with "hard” or "brittle" components A2 such as polyhydroxy butyrate or in particular polylactide are prepared.
  • succinic acid or mixtures of succinic acid with adipic acid are preferably used when polymer blends with "white Chen “or” tough "components A2 such as Polyhydroxybuyratcovaleriat be prepared.
  • Succinic acid, azelaic acid, sebacic acid and brassylic acid also have the advantage that they are available as renewable raw materials.
  • aromatic dicarboxylic acid 1 b there are generally mentioned those having 8 to 12 carbon atoms, and preferably those having 8 carbon atoms. Examples include terephthalic acid, isophthalic acid, 2,6-naphthoic acid and 1, 5-naphthoic acid and ester-forming derivatives thereof.
  • di-CrC 6 - alkyl esters for example dimethyl, diethyl, di-n-propyl, di-iso-propyl, di-n-butyl, di-isobutyl, Di-t-butyl butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl ester.
  • the anhydrides of dicarboxylic acids 1 b) are also suitable ester-forming derivatives. In principle, however, it is also possible to use aromatic dicarboxylic acids 1 b) having a larger number of carbon atoms, for example up to 20 carbon atoms.
  • aromatic dicarboxylic acids or their ester-forming derivatives 1 b) can be used individually or as a mixture of two or more thereof. Particularly preferred are terephthalic acid or d e r e r e d e r e d e d e derivatives used dimethyl terephthalate.
  • the sulfonate group-containing compound is usually an alkali metal or alkaline earth metal salt of a sulfonate-containing dicarboxylic acid or its ester-forming derivatives, preferably alkali metal salts of 5-sulfoisophthalic acid or mixtures thereof, particularly preferably the sodium salt.
  • the acid component contains 1) from 40 to 60 mol% of 1 a), from 40 to 60 mol% of 1 b) and from 0 to 2 mol% of 1 c).
  • the acid component contains 1) from 40 to 59.9 mol% 1 a), from 40 to 59.9 mol% 1 b) and from 0, 1 to 1 mol% 1 c), in particular from 40 to 59.8 mol% of 1 a), from 40 to 59.8 mol% of 1 b) and from 0.2 to 0.5 mol% of 1 c).
  • the diols 2) are selected from branched or linear alkanediols having 2 to 12 carbon atoms, preferably 4 to 6 carbon atoms, or cycloalkanediols having 5 to 10 carbon atoms.
  • alkanediols examples include ethylene glycol, 1, 2-propanediol, 1, 3-propanediol, 1, 2-butanediol, 1, 4-butanediol, 1, 5-pentanediol, 2,4-dimethyl-2-ethylhexane-1, 3 diol, 2,2- Dimethyl 1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-isobutyl-1,3-propanediol, 2,2,4-trimethyl-1,6-hexanediol, in particular, ethylene glycol, 1, 3-propanediol, 1, 4-butanediol and 2,2-dimethyl-1,3-propanediol (neopentyl glycol); Cyclopentanediol, 1,4-cyclohexanediol, 1,2-cyclohex
  • 1,4-butanediol in particular in combination with adipic acid as component a1) and 1,3-propanediol, in particular in combination with sebacic acid as component a1).
  • 1, 3-Propanediol and 1, 4-butanediol also have the advantage that they are available as renewable raw materials. It is also possible to use mixtures of different alkanediols.
  • component A or component B can be used in excess.
  • the molar ratio of the components used A to B in the range of 0.4: 1 to 1, 5: 1, preferably in the range of 0.6: 1 to 1, 1: 1.
  • the polyesters on which the polyester mixtures according to the invention are based can contain further components.
  • dihydroxy compounds 3a) are preferably used diethylene glycol, triethylene glycol, polyethylene glycol, polypropylene glycol and polytetrahydrofuran (poly-THF), more preferably diethylene glycol, triethylene glycol and polyethylene glycol, wherein also mixtures thereof or compounds having different variables n (see formula I) ,
  • the molecular weight (M n ) of the polyethylene glycol is usually selected in the range from 250 to 8000, preferably from 600 to 3000 g / mol.
  • from 15 to 98, preferably 60 to 99.5 mol% of the diols 2) and 0.2 to 85, preferably 0.5 to 30 mol% of the dihydroxy compounds 3a), based on the molar Amount of 2) and 3a) can be used for the preparation of partially aromatic polyesters.
  • the hydroxycarboxylic acid 3b) used is glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid, cyclic derivatives thereof such as glycolide (1,4-dioxane-2,5-dione), D L-dilactide (3,6-dimethyl-1,4-dioxane-2,5-dione), p- Hydroxybenzoic acid and its oligomers and polymers such as 3-polyhydroxybutyric acid, polyhydroxyvaleric acid, polylactide (obtained, for example, as NatureWorks® (from Ca rg ill)), as well as a mixture of 3-polyhydroxybutyric acid and polyhydroxyvaleric acid (the latter is under the name Biopol ® by Zeneca Avail- lent), particularly preferably for the preparation of partly aromatic polyesters are the low molecular weight and cyclic derivatives thereof.
  • cyclic derivatives thereof such as glycolide (1,4-diox
  • the hydroxycarboxylic acids may be used, for example, in amounts of from 0.01 to 50, preferably from 0.1 to 40,% by weight, based on the amount of 1) and 2).
  • the amino-C 2 -Ci2-alkanol or amino-C 5 -C 0 cycloalkanol (component 3c), wherein here also include 4-aminomethylcyclohexanemethanol, are preferably used are amino-C 2 -C 6 alkanols such as 2-aminoethanol, 3-aminopropanol, 4-aminobutanol, 5-aminopentanol, 6-aminohexanol and amino C 5 -C 6 cycloalkanols such as aminocyclopentanol and aminocyclohexanol, or mixtures thereof.
  • the diamino-C 1 -C 5 -alkane (component 3d) used is preferably diamino-C 4 -C 6 -alkanes, such as 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane (hexamethylenediamine, "HMD").
  • HMD hexamethylenediamine
  • from 0.5 to 99.5 mol%, preferably 0.5 to 50 mol%, 3c), based on the molar amount of 2), and from 0 to 50, preferably from 0 to 35 mol -%, 3d), based on the molar amount of 2) are used for the preparation of partially aromatic polyesters.
  • the 2,2'-bisoxazolines 3e) of general formula III are generally obtainable by the process of Angew. Chem. Int. Edit, Vol. 1 1 (1972), pp. 287-288.
  • partially aromatic polyesters for example, from 70 to 98 mol% 2), to 30 mol% 3c) and 0.5 to 30 mol% 3d) and 0.5 to 30 mol% 3e), in each case based on the sum of the molar amounts of the components 2), 3c), 3d) and 3e) can be used.
  • natural aminocarboxylic acids can be used. These include valine, leucine, isoleucine, threonine, methionine, phenylalanine, tryptophan, lysine, alanine, arginine, aspartic acid, cysteine, glutamic acid, glycine, histidine, proline, serine, tyrosine, asparagine or glutamine.
  • Preferred aminocarboxylic acids of the general formulas IVa and IVb are those in which s is an integer from 1 to 1000 and t is an integer from 1 to 4, preferably 1 or 2, and T is selected from the group consisting of phenylene and - (CH 2 ) U -, where u is 1, 5 or 12.
  • 3f) may also be a polyoxazoline of the general formula V.
  • 3f) can also be a mixture of different aminocarboxylic acids and / or polyoxazolines. According to a preferred embodiment, 3f) can be used in amounts of from 0.01 to 50, preferably from 0.1 to 40,% by weight, based on the total amount of components 1) and 2).
  • the compounds 4a) preferably contain from three to ten functional groups which are capable of forming ester bonds.
  • Particularly preferred compounds 4a) have three to six functional groups of this kind in the molecule, in particular three to six hydroxyl groups and / or carboxyl groups. Examples include:
  • Trimethylolpropane trimethylolethane
  • the compounds 4a) are generally used in amounts of from 0.01 to 15, preferably from 0.05 to 10, particularly preferably from 0.1 to 4, mol%, based on the component 1).
  • component 4b) one or a mixture of different isocyanates are used. It is possible to use aromatic or aliphatic diisocyanates. However, it is also possible to use higher functional isocyanates. Among an aromatic diisocyanate 4b) are in the context of the present invention, especially
  • 2,2'-, 2,4'- and 4,4'-diphenylmethane diisocyanate as component 4b) are particularly preferred.
  • the latter diisocyanates are used as a mixture.
  • trinuclear isocyanate 4b) is also tri (4-isocyanatophenyl) methane into consideration.
  • the polynuclear aromatic diisocyanates are obtained, for example, in the preparation of mono- or binuclear diisocyanates.
  • component 4b) may also contain uretdione groups, for example for capping the isocyanate groups.
  • an aliphatic diisocyanate 4b) is preferably an alkylene or a difunctional alkenylcyclodiene diisocyanate having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, e.g. 1, 6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclo-hexane) understood.
  • Particularly preferred aliphatic diisocyanates 4b) are 1,6-hexamethylene diisocyanate and isophorone diisocyanate.
  • component 4b) is used in amounts of from 0.01 to 5, preferably from 0.05 to 4, mol%, particularly preferably from 0.1 to 4, mol%, based on the sum of the molar amounts of 1) and 2).
  • divinyl ether 4c) can be used in general all conventional and commercially available divinyl ether. Preference is given to using 1,4-butanediol divinyl ether, 1,6-hexanediol divinyl ether or 1,4-cyclohexanedimethanol divinyl ether or mixtures thereof.
  • the divinyl ethers are preferably used in amounts of from 0.01 to 5, in particular from 0.2 to 4,% by weight, based on the total weight of 1) and 2).
  • Examples of preferred partially aromatic polyesters are based on the following components
  • partially aromatic polyesters based on 1), 2), 4a) or 1), 2), 4b) or on 1), 2), 4a), 4b) are particularly preferred.
  • the partially aromatic polyesters are based on 1), 2), 3c), 3d), 3e) or 1), 2), 4a), 3c), 3e).
  • at least one of the polyesters contained in the plastic component A has a lower melting point than the polyester B1 of the second plastic component B.
  • Preferred thermoplastic polyester A1 is a random copolyester of terephthalic acid (10-40 mol%), 1,4-butanediol (50 mol%) and adipic acid or Sebacic acid (10-40 mol%), the sum of the monomers being 100 wt%.
  • Particularly preferred is a random copolyester of terephthalic acid (15-35 mol%), 1,4-butanediol (50 mol%) and adipic acid (15-35 mol%), the sum of the monomers being 100 wt% ,
  • the homo- or copolyester A2 is preferably selected from the group consisting of polylactide (PLA), polycaprolactone, polyhydroxyalkanoates, for example PHB or PH B / V, and polyesters of aliphatic dicarboxylic acids and aliphatic diols.
  • PLA polylactide
  • polycaprolactone polycaprolactone
  • polyhydroxyalkanoates for example PHB or PH B / V
  • polyesters of aliphatic dicarboxylic acids and aliphatic diols polyesters of aliphatic dicarboxylic acids and aliphatic diols.
  • the first plastic component A may contain one or more additives.
  • the additives are usually selected from the group consisting of toughener, flame retardant, nucleating agent, carbon black, pigments, colorants, mold release agents, heat aging stabilizers, antioxidants, processing stabilizers, G and antiblocking agents, waxes, plasticizers, surfactants, antistatic agents and antifogging agents.
  • the proportion of the additives based on the mass of the plastic component A is preferably in the range of 0 to 15 wt .-%.
  • fibrous or particulate fillers may also be included.
  • Suitable fibrous or particulate fillers may be inorganic or organic. Suitable are e.g. Glass fibers, carbon fibers, aramid fibers, kaolin, calcined kaolin, talc, chalk, silicates, mica, wollastonites, montmorillonites, cellulosic fibers such as cotton, flax, hemp, nettle fibers or the like, amorphous silica and powdered quartz.
  • the particulate fillers are particularly preferred. Very particular preference is given to minerals and glass spheres, in particular glass spheres.
  • the proportion of fibrous or particulate fillers based on the mass of the plastic component A is preferably in the range of 0 to 50 wt .-%. If the first plastic component A contains glass beads, then the proportion of the glass beads is preferably in the range of 0.1 to 40 wt .-%, based on the total mass of the first plastic component A.
  • the fillers on their surface can e z. B. be treated with an organic compound or a silane compound.
  • Suitable toughening modifiers for the first plastic component A are, for example, copolymers which are composed of at least two monomer units selected from ethylene, propylene, butadiene, isobutene, isoprene, chloroprene, vinyl acetate, styrene, acrylonitrile and acrylic or methacrylic acid esters having 1 to 18 C atoms in the alcohol component.
  • Suitable toughening modifiers are known, for example, from WO-A 2007/009930.
  • flame retardants in amounts of 0 to 50 wt .-%, based on the total mass of the first plastic component A, be included.
  • Suitable flame retardants are e.g. halogen-containing flame retardants, halogen-free flame retardants, melamine cyanurate-based flame retardants, phosphorus-containing flame retardants or expanded graphite-containing flame retardants.
  • At least one compatibilizer A3 is contained in the plastic component A.
  • the proportion of the at least one compatibilizer is preferably in the range of 0.05 to 5 wt .-%, in particular in the range of 0.1 to 3 wt .-%, each based on the total mass of the plastic component A.
  • compatibilizers used can both improve the incorporation of component A2 into the matrix of semiaromatic polyester A1 or also serve as adhesion promoters between first plastic component A and second plastic component B.
  • Suitable compatibilizers are e.g. grafted with glycidyl methacrylates styrene (co) polymers, as described for example in Macromol. Symp. 2006, 233, pages 17-25 are described.
  • Styrene (co) polymers grafted with isocyanate groups, poly [methylene (phenylene isocyanate)], bisoxazolines, styrene copolymers grafted with oxazoline groups or styrene copolymers grafted with maleic anhydride are also suitable.
  • epoxy-functionalized styrene copolymers with a methacrylic acid moiety Preference is given to random, epoxy-functionalized styrene-acrylic acid copolymers having a molecular weight M w of from 3000 to 8500 g / mol and a degree of functionalization of more than two epoxy groups per molecule chain. Particularly preferred are random, epoxy-functionalized styrene-acrylic acid copolymer having a molecular weight Mw of 5000 to 7000 g / mol and a degree of functionalization of more than four epoxy groups per molecule chain.
  • the at least one semicrystalline, thermoplastic polyester B1 based on aromatic dicarboxylic acid n and aliphatic or aromatic dihydroxy compounds of the second plastic component B is preferably a polyalkylene terephthalate or a mixture of at least two different polyalkylene terephthalates.
  • the at least one polyalkylene terephthalate preferably has 2 to 10 C atoms in the alcohol portion.
  • Such polyalkylene terephthalates are known per se and described in the literature. They contain an aromatic ring in the main chain derived from the aromatic dicarboxylic acid.
  • the aromatic ring may also be substituted, for example by halogen, such as chlorine or bromine, or by C 1 -C 4 -alkyl groups, such as methyl, ethyl, i-propyl, n-propyl or n-butyl, i-butyl or t-butyl. butyl groups.
  • halogen such as chlorine or bromine
  • C 1 -C 4 -alkyl groups such as methyl, ethyl, i-propyl, n-propyl or n-butyl, i-butyl or t-butyl. butyl groups.
  • the polyalkylene terephthalates can be prepared in a known manner by means of dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds.
  • Preferred dicarboxylic acids are 2,6-naphthalenedicarboxylic acid, terephthalic acid and isophthalic acid or mixtures thereof. Up to 30 mol%, preferably not more than 10 mol% of the aromatic dicarboxylic acids can be replaced by aliphatic or cycloaliphatic dicarboxylic acids, for example adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and / or cyclohexanedicarboxylic acids.
  • aliphatic dihydroxy compounds are diols having 2 to 6 carbon atoms, in particular 1, 2-ethanediol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1 , 4-cyclohexanedimethanol, neopentyl glycol or mixtures thereof.
  • the semicrystalline, thermoplastic polyester B1 of the second plastic component B formed as polyalkylene terephthalate is particularly preferably a polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate or a mixture of at least two of these polyalkylene terephthalates.
  • formed as a polyalkylene terephthalate partially crystalline thermoplastic polyester B1 of the second plastic component B is a polybutylene terephthalate or a mixture of polybutylene terephthalate (60 to 90 wt .-%) and polyethylene terephthalate (10 to 40 wt .-%), wherein the sum of PBT and PET is 100% by weight.
  • the viscosity number of the polyesters A2, B1 is generally in the range from 50 to 220 ml / g, preferably in the range from 80 to 160 ml / g (measured in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture (Weight ratio 1: 1) at 250 ° C according to ISO 1628).
  • polyesters A2, B1 whose carboxyl end group content is up to 100 meq / kg, preferably up to 50 meq / kg and in particular up to 40 meq / kg polyester.
  • Such polyesters may, for example, according to the in DE-A 44 01 055 described methods are prepared.
  • the carboxyl end group content is usually determined by titration methods, for example potentiometry.
  • polyethylene terephthalate recyclates also called scrap PET
  • polyalkylene terephthalates such as polybutylene terephthalate
  • Recyclates are generally understood as so-called Post Industrial Recyclates or Post Consumer Recyclates.
  • Post Industrial Recyclate is production waste during polycondensation or processing, such as injection molding, injection molded or extruded parts, or edge sections of extruded sheets or foils.
  • Post Consumer Recyclate is usually plastic that is collected and processed after use by the end user.
  • plastic that is collected and processed after use by the end user.
  • blow-molded polyethylene terephthalate bottles which are used, for example, for mineral water, soft drinks and juices.
  • Both types of recycled material can be present either as regrind or in the form of granules. In the latter case, the slag cyclates after separation and purification are melted in an extruder and granulated. This usually facilitates the handling, the flowability and the metering for further processing steps.
  • Both granulated and regrind recyclates can be used, with the maximum edge length being 10 mm, preferably 8 mm.
  • the residual moisture content after drying is preferably less than 0.2%, in particular less than 0.05%.
  • polyesters are fully aromatic polyesters derived from aromatic dicarboxylic acids and aromatic dihydroxy compounds.
  • Suitable aromatic dicarboxylic acids are the compounds already described for the polyalkylene terephthalates. Preference is given to mixtures of 5 to 100 mol% of isophthalic acid and 0 to 95 mol% of terephthalic acid, in particular mixtures of about 80% terephthalic acid with 20% isophthalic acid to about equivalen te mixtures of these two acids are used.
  • the aromatic dihydroxy compounds preferably have the general formula
  • Z represents an alkylene or Cylcloalkylenolize having up to 8 C-atoms, an arylene group having up to 12 C atoms, a carbonyl group, a sulfonyl group, an oxygen or sulfur atom or a chemical bond and in the m is 0 to 2 Has.
  • the compounds can also carry C 1 -C 8 -alkyl or alkoxy groups or fluorine, chlorine or bromine as substituents on the phenylene groups.
  • Suitable parent compounds of these compounds are dihydroxydiphenyl, di (hydroxyphenyl) alkane, di (hydroxyphenyl) cycloalkane, di (hydroxyphenyl) sulfide, di (hydroxyphenyl) ether, di (hydroxyphenyl) ketone, di (hydroxyphenyl) sulfoxide, ⁇ , ⁇ '-di- (hydroxyphenyl) -dialkylbenzene, di- (hydroxyphenyl) sulfone, di- (hydroxybenzoyl) benzene, resorcinol and hydroquinone and their kemalkyltechnischtechnische, etc.
  • Dihydroxydiphenylsulfone and 2,2-di- (3 ', 5'-dimethyl-4'-hydroxyphenyl) propane or mixtures thereof are preferred.
  • mixtures of polyalkylene terephthalates and wholly aromatic polyesters These generally contain from 20 to 98% by weight of the polyalkylene terephthalate and from 2 to 80% by weight of the wholly aromatic polyester.
  • polyester block copolymers such as copolyether esters can also be used.
  • Such products are known per se and are known in the literature, e.g. in US 3,651,014. Also in the trade, corresponding products are available, e.g. under the name Hytrel® from DuPont.
  • Polyalkylene terephthalates B1 with styrene copolymers B2 can also be used. These preferably contain 60 to 90 wt .-% Polyalkylene terephthalate and 10 to 40 wt .-% of the styrene copolymer. Particularly preferred are mixtures with 60 to 80 wt .-% polyalkylene terephthalate and 20 to 40 wt .-% styrene copolymer.
  • the second plastic component B contains at least one thermoplastic styrene (co) polymer B2, this is preferably selected from the group consisting of acrylonitrile-styrene-acrylic ester (ASA), acrylonitrile-butadiene-styrene copolymers (ABS), styrene Acrylonitrile copolymers (SAN) and mixtures thereof.
  • ASA acrylonitrile-styrene-acrylic ester
  • ABS acrylonitrile-butadiene-styrene copolymers
  • SAN styrene Acrylonitrile copolymers
  • a preferred embodiment contains, as styrene copolymer B2, a styrene-acrylonitrile-acrylic acid copolymer (ASA) having the composition styrene 20-40% by weight, acrylonitrile 20-40% by weight, acrylic acid 20-40% by weight, wherein the sum of the individual monomers gives 100 wt .-%.
  • ASA styrene-acrylonitrile-acrylic acid copolymer
  • the polyalkylene terephthalate B 1 is polybutylene terephthalate and the styrene copolymer B2 is a styrene-acrylonitrile-acrylic acid copolymer (ASA) having the composition styrene 20-40% by weight, acrylonitrile 20-40% by weight, acrylic acid 20 -40 wt .-%, wherein the sum of the individual monomers 100 wt .-% results.
  • the proportion of B1 is 60 to 80 wt .-%, the proportion of B2 20 to 40 wt .-%, the proportions add up to 100 wt .-% based on the total plastic composition of the polymer component B.
  • the second plastic component B may contain one or more additives in addition to the at least one semicrystalline, thermoplastic polyester B1 and optionally the at least one thermoplastic styrene (co) polymer B2.
  • the additives are selected from the group consisting of fibrous or particulate fillers, tougheners, flame retardants, nucleating agents, carbon black, pigments, colorants, mold release agents, heat aging stabilizers, antioxidants, processing stabilizers and compatibilizers.
  • Suitable fibrous or particulate fillers are, for example, carbon fibers, glass fibers, glass beads, amorphous silicic acid, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, calcium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar.
  • the fillers are preferably used in amounts of 0, 1 to 50 wt .-%, particularly preferably in amounts of 10 to 40 wt .-%.
  • Particularly preferred are fibrous fillers, and particularly preferred are glass fibers.
  • the proportion of fillers is based on the total mass of the second plastic component B. For better compatibility, the fillers may be treated with an organic compound or a silane compound on their surface.
  • Flame retardants which may be contained in the second plastic component B, are preferably the same as they may be included in the first plastic component A.
  • the abovementioned additives may also be present in stabilizers, oxidation inhibitors, agents against thermal decomposition and decomposition by UV radiation, lubricants and mold release agents, colorants, for example dyes and pigments (including carbon blacks), nucleating agents, plasticizers, etc. ,
  • 0 to 2 wt .-%, based on the total mass of the second plastic component B fluorine-containing ethylene polymers may be included.
  • the component is e.g. a plastic part as used in electrical engineering, a mechatronic component or a plastic housing with plug contacts.
  • the insert which is enclosed by the plastic jacket is e.g. a punched grid.
  • the component can be e.g. as a connector use.
  • the insert can also be a wire, a round conductor, a flat conductor, a flexible foil or a printed circuit board.
  • the insert may also be a tether, a door latch, a lock, a threaded bushing, a rolling bearing, a plate, a wire for stabilizers or a zinc diecast or die-cast aluminum component for a door locking unit.
  • the component is a blade for a knife, a pair of scissors, a scalpel or even for a screwdriver.
  • the insert is preferably made of a metal. Suitable metals from which the insert is made are e.g.
  • Copper and copper-containing alloys for example CuSn6, CuSnO, 15, CuBe, CuFe, CuZn37, CuSn4Zn6Pb3-C-GC (gunmetal) or CuZn39Pb3 (brass), aluminum and aluminum-containing alloys, for example AISi12Cu1, AISM OMg, titanium, stainless steel, lead-free metals and Metal alloys or materials with a tin coating.
  • the invention further relates to a method for producing a component, which comprises an insert and a plastic casing of at least two plastic components, wherein the method comprises the following steps.
  • At least one homo- or copolyester selected from the group consisting of polylactide (P LA), polycapro la cto n, Polyhydroxyalkanoates (eg PHB or PHB / V) and polyesters of aliphatic dicarboxylic acids and aliphatic diols;
  • A3 0.05 to 15% by weight, based on the total weight of components A1 to A2, of a) an epoxide-group-containing copolymer based on styrene, acrylate and / or methacrylic acid ester, b) a bisphenol A epoxide or c) an epoxide group-containing natural oil, fatty acid ester or fatty acid amide; and
  • B1 50 to 100 wt .-% of at least one partially crystalline, thermoplastic polyester based on aromatic dicarboxylic acids and aliphatic or aromatic dihydroxy compounds and
  • thermoplastic styrene (co) polymer each based on the polymer content of the second plastic component B, wherein either first the insert with the first plastic component A wrapped and then the second plastic component B is applied or first the outer envelope B is formed, and then a cavity formed between the outer envelope of the second plastic component B and the insert is filled with the first plastic component A to form the envelope of the insert.
  • Particularly preferred partially aromatic polyesters include polyesters which, as essential components 1), are an acid component 1 a) 30 to 99 mol% of at least one aliphatic or at least one cycloaliphatic dicarboxylic acid or its ester-forming derivatives or mixtures thereof 1 b) 1 to 70 mol% of at least one aromatic dicarboxylic acid or its ester-forming derivative or mixtures thereof and
  • a diol component selected from at least one C 2 to Ci 2 alkanediol, at least one C 5 - to C 0 -Cycloalkandiol or mixtures thereof and if desired, in addition, one or more Components selected from
  • the acid component 1) of the partly aromatic polyesters contains from 30 to 70, in particular from 40 to 60, mol% 1 a) and from 30 to 70, in particular from 40 to 60, mol% 1 b).
  • the hydroxycarboxylic acid 3b) used is glycolic acid, D-, L-, D, L-lactic acid, 6-hydroxyhexanoic acid, cyclic derivatives thereof such as glycolide (1,4-dioxane-2,5-dione), D -, L-dilactide (3,6-dimethyl-1, 4-dioxane-2,5-dione), p-hydroxybenzoic acid and their oligomers and polymers such as 3-polyhydroxybutric acid, polyhydroxyvaleric acid, polylactide (for example as NatureWorks® (Fa Ca rg ill) er Scholltl chch) as well as a Mi schsch from 3-polyhydroxybutyric acid and polyhydroxy-valeric acid (the latter is under the name Biopol® Zeneca available), particularly preferred for the production of partially aromatic polyesters are the low molecular weight and cyclic Derivatives thereof.
  • cyclic derivatives thereof such as glycolide (1,4-d
  • the hydroxycarboxylic acids may be used, for example, in amounts of from 0.01 to 50, preferably from 0.1 to 40,% by weight, based on the amount of 1) and 2).
  • the wrapping of the insert part with the first plastic component A takes place in step (a) by an injection molding process.
  • the insert is inserted into an injection mold.
  • the tool is closed and the plastic molding compound injected into the tool.
  • the plastic molding compound envelops the insert at least partially and forms an adhesive connection with the insert. The result is a media-tight connection between the insert and the plastic component A.
  • the injection molding of the plastic molding material is generally carried out at the pressures for injection molding. Wen n however z. B.
  • the injection of the component A should preferably take place at a maximum pressure in the Tool of less than 900 bar, more preferably less than 600 bar, takes place.
  • the low injection pressure prevents the insert from deforming during encapsulation.
  • the first plastic component A solidifies and becomes solid. Another advantage of overmolding the insert with the first plastic component A is that the insert is stabilized by this plastic wrap.
  • Transitions between the surfaces of the encapsulation made of the first plastic component A can be obtuse-angled, acute-angled or rounded. Also, enamel lips may be pronounced, i. thin, protruding portions of the first plastic component A. These are then melted and deformed by the over-sharpening with the second plastic component B. In this way, a cohesive connection is generated.
  • protruding areas may be formed on the encapsulation of the insert made of the first plastic component A.
  • the first plastic component A may be the insert, e.g. enclose with a cross section in the form of a double-T. Due to the projecting regions of such an encapsulation with the first synthetic material component A, a positive connection can be achieved. Since the first plastic component A is generally melted by the overspill with the second plastic component B, the geometry of the pre-extrusion of the first plastic component A can generally change if the processing temperature of the second plastic component B is above the melting temperature or the er The first fuel component is listed. Also, the pre-injection from the first plastic component A can not be deformed by the pressure of the injected melt during the encapsulation with the second plastic component B. So z. B. sharp edges of the pre-injection of the first plastic component A are rounded.
  • the so wrapped insert is covered with the second plastic component B.
  • the wrapping with the second plastic component B is preferably also carried out by an injection-molded process.
  • the injection molding process is generally carried out with the usual pressures for injection molding. If the plastic molding compound contains When injection pressure has been injected, the pressure in the tool is generally higher than the maximum pressure in the tool in step (a).
  • the hardened first plastic component A is preferably fused on its surface, so that a particularly good adhesion between the first plastic component A and the second plastic component B is formed.
  • the wrapping of the insert with the first plastic component A in step (a) and the molding of the outer casing of the second plastic component B in step (b) can be carried out in the same injection mold.
  • the injection mold initially encloses a cavity which corresponds to the shape of the insert with the envelope of the first plastic component A. Then the tool must open so that the free form corresponds to the shape of the finished component.
  • Corresponding tools are known to the person skilled in the art.
  • the wrapping of the insert with the first plastic component A in step (a) takes place in a first tool and the molding of the outer casing of the second plastic component B in step (b) in a second tool.
  • the insert part wrapped with the first plastic component A it is necessary for the insert part wrapped with the first plastic component A to be removed from the first tool and to be inserted into the second tool before the insert molding with the second plastic component B.
  • the first plastic component A of the inflowing melt of the second plastic component B provide sufficient mechanical resistance.
  • a sufficient rigidity and strength is necessary, which depend on the degree of solidification of the first plastic component A and the injection pressure of the second plastic component B.
  • the injection molding machine In order to avoid that the injection molding machine must be cleaned after each injection process in order to change the material, it is preferred that two different injection molding or plasticizing units are used for the first plastic component A and the second plastic component B. If the wrapping in step (a) and the forming of the outer wrapping in step (b) are done with the same tool, it is possible that the mold is connected to both injection molding machines at the same time. Alternatively, it is also possible to first connect the tool to the injection molding machine, with which the first plastic component A is injected, and then with the injection molding machine, with which the second plastic component B is encapsulated around the insert with the envelope of the first plastic component A. , Conventional injection molding machines used for this purpose are, for example, injection molding machines with a turntable tool.
  • the cylinders are arranged opposite one another and the tool is respectively rotated to the cylinder from which is injected next.
  • these are preferably each connected to an injection molding machine.
  • injection molding machine any, known in the art injection molding machine is suitable.
  • step (b) only parts of the insert wrapped in the first plastic component A are coated with the second plastic component B.
  • the areas are encapsulated with the second plastic component B, which have an outer surface, since the envelope with the second plastic component B, the molding dimensional accuracy is ensured.
  • the entire insert is coated with the envelope of the first plastic component A with the second plastic component B.
  • the wrapping of the insert takes place preferably with the second plastic component B in such a way that this component envelops the insert in the areas in which outer surfaces are present.
  • the areas which are potted with the first plastic component A preferably have no outwardly facing surfaces. In this way, it is ensured that the component produced in this way is dimensionally stable and dimensionally stable.
  • the wrapping of the insert with the second plastic component B is preferably carried out by an injection molding process. For this purpose, the insert is inserted into an injection mold and then encapsulated with the second plastic component B.
  • the tool is in these areas on the insert. After wrapping the insert with the second plastic component B, the areas that are to be wrapped with the first plastic component A, released.
  • movable parts are provided in the tool, which first form the recesses and then release the recesses for casting with the first plastic component A or the insert, which is encapsulated with the second plastic component B, is removed from the tool and in a second tool is inserted, in which the areas which are to be wrapped with the first plastic component A, are kept free.
  • the wrapping with the first plastic component A is preferably also carried out by an injection molding process. This is generally carried out at the usual pressures for injection molding processes.
  • the injection molding process for the first plastic component is Preferably, component A is carried out at a lower pressure than the injection molding process with which the second plastic component B is extrusion-coated around the insert.
  • the pressure for wrapping the insert with the first plastic component A is then preferably below 900 bar, preferably below 600 bar.
  • a compound density connection between the first plastic component A and the second plastic component B is preferably achieved by melting the plastic component B by the melt of the first plastic component A on its surface, so that, for example, by interdiffusion a particularly good adhesion between the first plastic component A and the second plastic component B is formed.
  • first plastic component A and the second plastic component B can combine chemically and / or mechanically.
  • a chemical compound can be formed, for example, by reaction of the polymer components of the first plastic component A and the second plastic component B, for example by covalent bonds between the first plastic component A or a component of the first plastic component A and the second plastic component B or a component of the second plastic component B are knotted ,
  • the method can be designed at any time so that there is not only a good adhesion but also a form fit between the first plastic component A and the second plastic component B.
  • the melt temperature of the first plastic component A during the first encapsulation of the insert preferably lies in the range of the processing temperature of the underlying polymer which is customary in injection molding. If the first plastic component A is a mixture of two polymers, the melt temperature is chosen so high that both components are in the liquid state.
  • a higher processing temperature leads to a more easily flowing melt, which can better wet the surface of the insert, whereby a higher bond strength between the material of the insert and the first plastic component A can be achieved.
  • a melt temperature At too high a melt temperature, however, thermal degradation of the first plastic component A or one of its components A1 or A2 may occur.
  • the melt temperature of the second plastic component B is preferably in the range of the processing temperature of the underlying polymer customary in injection molding. If the second plastic component B is a mixture of two polymers, the melt temperature is chosen so high that both components are in the liquid state.
  • a higher processing temperature leads to a more easily flowing melt, which can better wet and / or melt the surface of the coating of the first plastic component A, whereby a higher bond strength between the second plastic component B and the first plastic component A can be achieved.
  • the melt temperature of the second plastic component B is not set so high that the envelope of the first plastic component A is completely melted and washed away.
  • the injection pressure for the second plastic component B is preferably chosen so that excessive deformation of the envelope of the first plastic component A, in the worst case, floating away, is avoided.
  • the component according to the invention is e.g. a plastic part as used in electrical engineering. It is also possible that the component is a mechatronic component or a plastic housing with plug contacts. Use find such components, e.g. as sensors, such as oil sensors, wheel speed sensors, pressure sensors, etc., as electronics housings, as control housings, e.g. in the field of ABS, ESP, transmission, airbag or engine control in motor vehicles. Also, the components may e.g. be used as a window regulator modules or for headlight control. Even outside the automotive industry, the components of the invention may be e.g. be used as sensors, as level sensors or as piping units. Further suitable uses for the components according to the invention are e.g. Electronic components in home appliances. Suitable components are e.g. Relays, bobbins, switch parts, solenoid valves, electrical hand tools, connectors or connectors.
  • the component of the invention from the insert with the envelope of the first plastic component A and the outer envelope of the second plastic component B is characterized in that it along both interfaces, ie the interface between the insert and wrapping of the first plastic component A and the interface between the first plastic component A and the second plastic component B, is media-tight.
  • Media density connection means that the leak rate after a climate change test with at least 200 cycles, in which the component to be tested is alternately subjected to a temperature of -40 ° C and + 150 ° C, less than 0.5 cm 3 / min.
  • the leak rate is usually determined by a differential pressure method at a test pressure of 0.5 bar. Examples
  • Test specimens are produced from an insert of CuSn6, which is enveloped by a first plastic component A and a second plastic component B.
  • the insert is first punched out of strip-cut CuSn6 using a punching tool.
  • the insert has a rectangular frame, in which the opposite short sides are additionally lent by a web in the middle connected to each other.
  • the manufactured insert has a length of 30 mm, a width of 10.5 mm and a height of 0.5 mm.
  • the length of the slots between the outer frame bars and the middle bar is 25 mm and the width of the slots is 3 mm.
  • the stampings are cleaned with acetone of oils and impurities.
  • an injection molding machine with a screw diameter of 18 mm is used (Allrounder 270S from Arburg).
  • the closing force of the tool is 500 kN, the injection pressure 1500 bar.
  • a cuboid coating is generated, wherein the envelope of the second plastic component B, the first plastic component A completely encloses.
  • the envelope of the first plastic component A has a length of 15 mm, a width of 4.5 mm and a thickness of 1, 5 mm, the envelope of the second plastic component B, which completely encloses the first plastic component A, a length of 20 mm, a width of 13 mm and a thickness of 4.5 mm.
  • the components with the envelope of the first plastic component A and the envelope of the second plastic component B are subjected to a thermal shock stress of up to 500 cycles.
  • the following protocol was used for a thermal shock cycle: 15 minutes storage at 150 ° C, temperature change to -40 ° C within 10 seconds, 15 minutes storage at -40 ° C, temperature change to 150 ° C within 10 seconds.
  • the thermal shock treatment is carried out in a temperature shock chamber VT 7030S2 from Vötsch.
  • the measurement of the tightness by differential pressure method was carried out before the stress and after 100, 200 and possibly 500 cycles. For the differential pressure measurement, two volumes, a test volume and a reference volume are subjected to the same pressure.
  • test volume leaks, a pressure difference arises which can be measured directly.
  • the pressure drop per time can be measured.
  • the specimen was tightly clamped at its outer periphery in a holder and pressurized from the underside.
  • the seal was made by a rubber sealing ring. Only occurring in the direction of the insert leaks between insert and the envelope of the first plastic component A or the envelope of the first plastic component A and the envelope of the second plastic component B lead to a leakage of the test volume, as in the blank test with a solid specimen of component B1.
  • the test medium used was air.
  • the test volume V test was 36 ml.
  • the filling time of the volumes with a test pressure of 0.5 bar was 5 seconds.
  • the results are summarized in Table 1.
  • the components A1 -4 represent different total compositions of component A, not the individual components thereof.
  • Component A1 is a blend consisting of 55% of a random aliphatic-aromatic copolyester prepared from terephthalic acid (25%), adipic acid (25%) and butanediol (45%) with 45% polylactide (PLA).
  • This blend has two melting points of 1 10-120 ° C and 140-155 as determined by DSC, a Vicat softening temperature (VST A / 50) of 68 ° C measured according to ISO 306: 2004, a Shore D hardness of 59 measured ISO 868 and an E modulus of 750 MPa determined according to ISO 527 on blown films of a thickness of 50 ⁇ .
  • Component A2 is a random copolyester of terephthalic acid (25 mol%), 1, 4-butanediol (50 mol%) and adipic acid (25 mol%) with melting point 1 10-120 ° C (DSC measurement according to ISO 1 1357th -3) and Shore D hardness of 32, determined according to ISO 868.
  • the Vicat softening temperature is 91 ° C, measured according to EN ISO 306: 2004.
  • Component A3 is a polybutylene terephthalate with a viscosity number of 130 ml / g, measured in 0.5% solution in phenol / o-dichlorobenzene (1: 1) according to ISO 1628.
  • the material has an E modulus of 2500 MPa (ISO 527-2 ) and a melting range of 220-225 ° C (DSC measurement according to ISO 1 1357-3).
  • Component A4 is a polybutylene terephthalate with 30% by weight of solid glass beads.
  • the material has a viscosity number of 1 13 ml / g, measured in 0.5% solution in phenol / o-dichlorobenzene (1: 1) according to ISO 1628, an E modulus of 4000 MPa (ISO 527-2) and a Melting range of 220-225 ° C (DSC measurement according to ISO 1 1357-3).
  • Component B is a polybutylene terephthalate with 30 wt .-% glass fibers having a viscosity number of 102 g / ml, measured in 0.5% solution in phenol / o-dichlorobenzene (1: 1) according to ISO 1628. It also contains 0.1 wt. % of a furnace carbon black having a mean particle size between 10 and 35 nm (CI LAS) and a BET surface area of 1 10-120 m 2 / g (ISO 9277), and 0.5% by weight of pentaerythritol tetrastearate as lubricant.
  • CI LAS mean particle size between 10 and 35 nm
  • ISO 9277 BET surface area
  • the material has an E-modulus of 10000 MPa (ISO 527-2) and a melting range of 220-225 ° C (DSC measurement according to ISO 1 1357-3).
  • the glass fibers have a diameter of ⁇ ⁇ .
  • STAB in Table 1 stands for standard deviation.
  • the example shows the improvement of the properties of a component made of a metallic insert, which is covered with a first plastic component A and a second plastic component B when described polyester mixtures are used as the first plastic component A.
  • Pre-encapsulations with pure polyesters or copolyesters as component A have been used in Comparative Examples 1 to 3, the corresponding injection-molded parts either could not be produced (Comparative Experiment 1) or showed high leaks directly after injection molding (Comparative Example 2) or after only 100 thermal shock cycles (See 3).

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  • Engineering & Computer Science (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Laminated Bodies (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Developing Agents For Electrophotography (AREA)

Abstract

L'invention concerne un composant de construction, qui comprend un insert et un enrobage plastique constitué d'au moins deux composants plastiques, l'insert étant entouré par un premier composant plastique A et le premier composant plastique A étant entouré par un second composant plastique B. Selon l'invention, le premier composant plastique A est formé à partir de : A1 : 5 à 80 % en poids, par rapport au poids total des composants A1 et A2, d'au moins un polyester à base d'acides dicarboxyliques aliphatiques et aromatiques et de composés dihydroxy aliphatiques; A2 : 20 à 95 % en poids, par rapport au poids total des composants A1 et A2, d'au moins un homo- ou copolyester choisi dans le groupe constitué par le polylactide (PLA), la polycaprolactone, les polyhydroxyalcanoates et les polyesters d'acides dicarboxyliques aliphatiques et de diols aliphatiques; A3 : 0,05 à 15 % en poids, par rapport au poids total des composants A1 et A2, de a) un copolymère contenant des groupes époxyde à base de styrène, d'un ester de l'acide acrylique et/ou d'un ester de l'acide méthacrylique, b) un époxyde de bisphénol A ou c) une huile naturelle, un ester d'acide gras ou un amide d'acide gras contenant des groupes époxyde; et le second composant plastique B est formé à partir de B1 : 50 à 100 % en poids d'au moins un polyester thermoplastique partiellement cristallin à base d'acides dicarboxyliques aromatiques et de composés dihydroxy aliphatiques ou aromatiques et B2 : 0 à 50 % en poids d'au moins un (co)polymère de styrène thermoplastique, à chaque fois par rapport à la fraction polymère du second composant plastique B.
EP10778654A 2009-11-18 2010-11-16 Composant de construction comprenant un insert et un enrobage plastique, et son procédé de fabrication Withdrawn EP2501545A2 (fr)

Priority Applications (1)

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EP10778654A EP2501545A2 (fr) 2009-11-18 2010-11-16 Composant de construction comprenant un insert et un enrobage plastique, et son procédé de fabrication

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EP09176360 2009-11-18
EP10778654A EP2501545A2 (fr) 2009-11-18 2010-11-16 Composant de construction comprenant un insert et un enrobage plastique, et son procédé de fabrication
PCT/EP2010/067521 WO2011061162A2 (fr) 2009-11-18 2010-11-16 Composant de construction comprenant un insert et un enrobage plastique, et son procédé de fabrication

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US (1) US20120231280A1 (fr)
EP (1) EP2501545A2 (fr)
JP (1) JP5730320B2 (fr)
KR (1) KR20120099467A (fr)
CN (1) CN102712177B (fr)
BR (1) BR112012012027A2 (fr)
MY (1) MY160739A (fr)
WO (1) WO2011061162A2 (fr)

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Publication number Priority date Publication date Assignee Title
MY163063A (en) * 2010-05-05 2017-08-15 Basf Se Component comprising an insert part and plastics jacketing, and process for production of the component
US20110274932A1 (en) * 2010-05-05 2011-11-10 Basf Se Component comprising an insert part and plastics jacketing, and process for production of the component

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Also Published As

Publication number Publication date
BR112012012027A2 (pt) 2016-05-17
CN102712177A (zh) 2012-10-03
CN102712177B (zh) 2015-10-14
KR20120099467A (ko) 2012-09-10
WO2011061162A2 (fr) 2011-05-26
US20120231280A1 (en) 2012-09-13
MY160739A (en) 2017-03-15
JP2013511402A (ja) 2013-04-04
JP5730320B2 (ja) 2015-06-10
WO2011061162A3 (fr) 2011-07-14

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