EP2566692A1 - Bauteil umfassend ein einlegeteil und eine kunststoffummantelung sowie verfahren zu seiner herstellung - Google Patents

Bauteil umfassend ein einlegeteil und eine kunststoffummantelung sowie verfahren zu seiner herstellung

Info

Publication number
EP2566692A1
EP2566692A1 EP11718719A EP11718719A EP2566692A1 EP 2566692 A1 EP2566692 A1 EP 2566692A1 EP 11718719 A EP11718719 A EP 11718719A EP 11718719 A EP11718719 A EP 11718719A EP 2566692 A1 EP2566692 A1 EP 2566692A1
Authority
EP
European Patent Office
Prior art keywords
plastic component
component
weight
acid
plastic
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Withdrawn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
EP11718719A
Other languages
German (de)
English (en)
French (fr)
Inventor
Rebekka VON BENTEN
Alireza Talebloo
Harald KRÖGER
Peter Eibeck
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 EP11718719A priority Critical patent/EP2566692A1/de
Publication of EP2566692A1 publication Critical patent/EP2566692A1/de
Withdrawn legal-status Critical Current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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14639—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles for obtaining an insulating effect, e.g. for electrical components
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/16—Making multilayered or multicoloured articles
    • 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
    • B32B15/20—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
    • 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
    • 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
    • B32B27/306—Layered products comprising a layer of synthetic resin comprising vinyl (co)polymers; comprising acrylic (co)polymers comprising vinyl acetate or vinyl alcohol (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
    • B32B27/32—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
    • B32B27/36—Layered products comprising a layer of synthetic resin comprising polyesters
    • B32B27/365—Layered products comprising a layer of synthetic resin comprising polyesters comprising polycarbonates
    • 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
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29C—SHAPING OR JOINING OF PLASTICS; SHAPING OF MATERIAL IN A PLASTIC STATE, NOT OTHERWISE PROVIDED FOR; AFTER-TREATMENT OF THE SHAPED PRODUCTS, e.g. REPAIRING
    • B29C45/00—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor
    • B29C45/14—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles
    • B29C45/14311—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor incorporating preformed parts or layers, e.g. injection moulding around inserts or for coating articles using means for bonding the coating to the articles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
    • B29K—INDEXING SCHEME ASSOCIATED WITH SUBCLASSES B29B, B29C OR B29D, RELATING TO MOULDING MATERIALS OR TO MATERIALS FOR MOULDS, REINFORCEMENTS, FILLERS OR PREFORMED PARTS, e.g. INSERTS
    • B29K2067/00—Use of polyesters or derivatives thereof, as moulding material
    • B29K2067/04—Polyesters derived from hydroxycarboxylic acids
    • B29K2067/046—PLA, i.e. polylactic acid or polylactide
    • 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
    • B32B2262/00—Composition or structural features of fibres which form a fibrous or filamentary layer or are present as additives
    • B32B2262/14—Mixture of at least two fibres made of different materials
    • 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
    • B32B2264/101—Glass
    • 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
    • B32B2264/104—Oxysalt, e.g. carbonate, sulfate, phosphate or nitrate 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
    • B32B2264/12—Mixture of at least two particles made of different materials
    • 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
    • B32B2457/00—Electrical equipment

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 Kunststoffummante- ment of at least two plastic components, wherein the insert is surrounded by a plastic component A and the first plastic component A is surrounded by a second plastic component B.
  • the invention further relates to methods 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.
  • 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 plastic material is eg an unreinforced thermoplastic elastomer.
  • EP-A 1 496 587 a composite component is known, in which a flat cable is led out of a sealed structure made of a plastic material. To seal the gap at which the cable emerges from the plastic material, the opening is filled with a liquid rubber, which is then cured. Also from DE-C 100 53 1 15 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 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 feedthrough in which an electrical contact is guided through a housing and in which the housing leadthrough is sealed against the penetration of undesired substances, is also known from DE-B 10 2005 033 912.
  • the roughness depth of the conductor element in the sealing area is increased by electroplating.
  • Object of the present invention is therefore to provide a component comprising an insert and a plastic sheath, in which the plastic sheath provides sufficient media tightness even with a temperature change storage.
  • a component comprising an insert and a plastic casing made of at least two plastic components, wherein the insert part of a first plastic component A1, wherein the first plastic component A1 is built up from:
  • A1 1 5 to 80 wt .-%, based on the total weight of components A1 1 and A12, of at least one polyester based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds;
  • A12 20 to 95% by weight, based on the total weight of components A1 1 and A12, of at least one homo- or copolyester selected from the group consisting of polylactide (PLA), polycaprolactone, polyhydroxyalkanoates and polyesters of aliphatic dicarboxylic acids and aliphatic diols;
  • A13 0.05 to 15 wt .-%, based on the total weight of components A1 1 and A12, a) of an epoxy group-containing copolymer based on styrene, acrylic ester and / or methacrylic acid ester, b) a bisphenol A epoxide or c ) of an epoxide group-containing natural oil, fatty acid ester or fatty acid amide, or a first plastic component A2, wherein the first plastic component A2 is composed of:
  • A21 10 to 100% by weight, based on the total weight of components A21 and A22, of at least one thermoplastic styrene (co) polymer,
  • A22 0 to 90% by weight, based on the total weight of components A21 and A22, of at least one thermoplastic (co) polyester, A23: 0.05 to 15% by weight, based on the total weight of components A21 and A22 , a) an epoxy group-containing copolymer based on styrene, acrylic ester and / or methacrylic ester, b) a bisphenol A epoxide or c) an epoxide group-containing natural oil, fatty acid ester or fatty acid amide, and the first plastic component A1 or the first Plastic component A2 is enclosed by a second plastic component B, and wherein the second plastic component B is constructed from
  • thermoplastic polyester 10 to 99.99% by weight of at least one thermoplastic polyester
  • B21 at least one highly branched or hyperbranched polycarbonate having an OH number of 1 to 600 mg KOH / g polycarbonate (according to DIN 53249, Part 2) or
  • the first plastic component A1 is composed of the at least one polyester based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds and the at least one homo- or Copolyester selected from the group consisting of polyactide, polycaprolactone, polyhydroxyalkanoates and polyesters of aliphatic dicarboxylic acids and aliphatic diols
  • the first plastic component A2 is composed of the at least one thermoplastic styrene (co) polymer and optionally the at least one thermoplastic ( Copolyester, a significantly improved media tightness compared to the known from the prior art plastic coatings, especially when using the component in temperature changes, achieved the internal encapsulation with the first plastic component A1 or A2 and the external encapsulation with the second plastic component B are achieved.
  • An advantage of using component B is that it has improved adhesion to the first plastic component A1 or A2 by adding the highly branched or hyperbranched polycarbonate or highly branched or hyperbranched polyester, as a result of which the composite obtains a higher density of media. Another advantage is a better flowability and thus better processability. A further advantage is that the use of highly branched or hyperbranched polycarbonates or polyesters does not lead to a decrease in the mechanical properties when the addition amount of the additive is increased.
  • the structures of highly branched or hyperbranched polycarbonates or highly branched or hyperbranched polyesters can also be easily adapted to the requirements of use in thermoplastics.
  • the highly branched or hyperbranched polycarbonates or highly branched or hyperbranched polyesters owing to their defined structure, combine advantageous properties such as high functionality, high reactivity, low viscosity and good solubility.
  • the first plastic component A1 is made up of:
  • A1 1 5 to 80% by weight, based on the total weight of components A1 1 and A12, of at least one partially aromatic polyester based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds;
  • A12 20 to 95% by weight, based on the total weight of components A1 1 and A12, of at least one homo- or copolyester selected from the group consisting of polylactide (PLA), polycaprolactone, polyhydroxyalkanoates and polyesters of aliphatic dicarboxylic acids and aliphatic diols;
  • A13 0.05 to 15 wt .-%, based on the total weight of components A1 1 and A12, a) of an epoxy group-containing copolymer based on styrene, acrylic ester and / or methacrylic acid ester, b) a bisphenol A epoxide or c ) of an epoxide group-containing natural oil, fatty acid ester or fatty acid amide.
  • Particularly preferred partially aromatic polyesters A1 1 include polyesters which are essential components
  • a diol component selected from at least one C 2 to Ci 2 alkanediol and at least one C 5 - to C 0 -Cycloalkandiol or mixtures thereof, and optionally in addition one or more components selected from
  • At least one aminocarboxylic acid selected from the group consisting of the natural amino acids, polyamides obtainable by polycondensation of a dicarboxylic acid having 4 to 6 carbon atoms and a diamine having 4 to 10 carbon atoms, compounds of the formulas (IVa) and (IVb )
  • the acid component 1) of the partially aromatic polyester A1 1 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).
  • aliphatic acids and the corresponding derivatives 1 a) are generally those having 2 to 10 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 as a rule those having 7 to 10 carbon atoms and in particular those having 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-cyclohexanedicarboxylic acid , 1, 3-cyclohexanedicarboxylic acid, diglycolic acid, itaconic acid, maleic acid and 2,5-norbornanedicarboxylic acid.
  • Suitable ester-forming derivatives of the abovementioned aliphatic or cycloaliphatic dicarboxylic acids which are likewise usable are, in particular, the di-C 1 - to C 6 -alkyl esters, such as dimethyl, diethyl, di-n-propyl, diisopropyl, di- n-butyl, di-iso-butyl, di-t-butyl, di-n-pentyl, di-iso-pentyl or di-n-hexyl esters.
  • 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, adipic acid, azelaic acid, sebacic acid, brassylic acid or their respective ester-forming derivatives or mixtures thereof are preferably used.
  • Succinic acid, adipic acid or sebacic acid or their respective ester-forming derivatives or mixtures thereof are particularly preferably used.
  • Particular preference is given to using adipic acid or its ester-forming derivatives, such as their alkyl esters or mixtures thereof.
  • sebacic acid or mixtures of sebacic acid with adipic acid are preferably used when polymer blends with "hard” or “brittle” components A12 such as polyhydroxy butyrate or in particular polylactide are prepared.
  • Succinic acid or mixtures of succinic acid with adipic acid are preferably used as aliphatic dicarboxylic acid when polymer blends with "soft” or “tough” components A12, such as, for example, polyhydroxybuyrate covalerate, are 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-C 1 -C 6 -alkyl esters for example dimethyl, diethyl, di-n-propyl, di-iso-propyl, di-n-butyl, di-iso-butyl, di-t- 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.
  • aromatic dicarboxylic acids 1 b) having a larger number of carbon atoms for example up to 20 carbon atoms.
  • the 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 its ester-forming derivatives such as dimethyl terephthalate used.
  • 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 1) contains 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). According to a further preferred embodiment, the acid component 1) contains from 40 to 59.9 mol% of 1 a), from 40 to 59.9 mol% of 1 b) and from 0.1 to 1 mol% of 1 c), in particular from 40 to 59.8 mole% 1 a), from 40 to 59.8 mole% 1 b) and from 0.2 to 0.5 mole% 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-cyclo
  • 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- Butondrol 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 A used 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 may contain further components.
  • the molecular weight (Mn) 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 their oligomers and polymers such as 3-polyhydroxybutric acid, polyhydroxyvaleric acid, polylactide (for example as NatureWorks® (Fa Cargill) and a mixture of 3-polyhydroxybutyric acid and polyhydroxyvaleric acid (the latter being available under the name Biopol® from Zeneca), particularly preferred for the preparation of partially aromatic polyesters are the low molecular weight and cyclic derivatives thereof.
  • cyclic derivatives thereof such as glycolide (1,4-dioxane-2,5-dione), D -, L-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).
  • 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-aminopenanol, 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").
  • diamino-C 4 -C 6 -alkanes such as 1,4-diaminobutane, 1,5-diaminopentane and 1,6-diaminohexane (hexamethylenediamine, "HMD").
  • 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.
  • Particularly preferred bisoxazolines are 2,2'-bis (2-oxazoline), bis (2-oxazolinyl) methane, 1, 2-bis (2-oxazolinyl) ethane, 1, 3-bis (2-oxazolinyl) propane or 1 , 4-bis (2-oxazolinyl) butane, especially 1, 4-bis (2-oxazolinyl) benzene, 1, 2-bis (2-oxazolinyl) benzene or 1,3-bis (2-oxazolinyl) benzene.
  • the partially aromatic polyester A1 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), respectively based on the sum of the molar amounts of the components 2), 3c), 3d) and 3e) can be used. According to another preferred embodiment, it is possible to use from 0.1 to 5, preferably from 0.2 to 4,% by weight of 3e), based on the total weight of 1) and 2).
  • 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).
  • Further components which may optionally be used to prepare the partially aromatic polyesters include compounds 4a) which contain at least three groups capable of ester formation.
  • the compounds 4a) preferably contain from three to ten functional groups which are capable of forming ester bonds. Particularly preferred compounds 4a) ben 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 0.01 to 15, preferably 0.05 to 10, particularly preferably 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.
  • 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-isocyanophenyl) methane into consideration.
  • the polynuclear aromatic diisocyanates are obtained, for example, in the preparation of mono- or binuclear diisocyanates.
  • component 4b) may also contain urethione groups, for example for capping the isocyanate groups.
  • an aliphatic diisocyanate 4b) is primarily linear or branched alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, for example 1, 6-hexamethylene diisocyanate, isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane ), Understood.
  • Particularly preferred aliphatic diisocyanates 4b) are 1,6-hexamethylene diisocyanate and isophorone diisocyanate.
  • Preferred isocyanurates include the aliphatic isocyanurates derived from alkylene diisocyanates or cycloalkylene diisocyanates having 2 to 20 carbon atoms, preferably 3 to 12 carbon atoms, e.g. Isophorone diisocyanate or methylene bis (4-isocyanatocyclohexane), derived.
  • the alkylene diisocyanates can be both linear and branched. Particular preference is given to isocyanurates based on n-hexamethylene diisocyanate, for example cyclic trimers, pentamers or higher oligomers of n-hexamethylene diisocyanate.
  • the component 4b) in amounts of 0.01 to 5, preferably 0.05 to 4 mol%, particularly preferably 0.1 to 4 mol% based on the sum of the molar amounts of 1) and 2) is used.
  • 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 1), 2), 4a)
  • partially aromatic polyesters which are 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).
  • a random copolyester of terephthalic acid (10-40 mol%), 1,4-butanediol (50 mol%) and adipic acid or sebacic acid (10-40 mol%) preference is given to a random copolyester of terephthalic acid (10-40 mol%), 1,4-butanediol (50 mol%) and adipic acid or sebacic acid (10-40 mol%), where the sum of the monomers 100 wt .-% results.
  • 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 A12 is preferably selected from the group consisting of polylactide (PLA), polycaprolactone, polyhydroxyalkanoates, for example PHB or PHB / V, and polyesters of aliphatic dicarboxylic acids and aliphatic diols.
  • PHA polylactide
  • polycaprolactone polyhydroxyalkanoates
  • PHB or PHB / V polyhydroxyalkanoates
  • polyesters of aliphatic dicarboxylic acids and aliphatic diols for example PHB or PHB / V
  • polyesters of aliphatic dicarboxylic acids and aliphatic diols for example PHB or PHB / V
  • at least one of the polyesters contained in the plastic component A1 has a lower melting point than the polyester B1 of the second plastic component B.
  • the lower melting temperature is that by melting the first plastic component A1 when over-molding with the second plastic component B, a particularly dense composite is possible.
  • the first plastic component A1 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, lubricants and antiblocking agents, waxes, emollients, surfactants, antistatic agents and antifogging agents.
  • the proportion of the additives based on the mass of the plastic component A1 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 examples are 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 similar, amorphous silica and similar. powder quartz. Of the fibrous or particulate fillers, the particulate fillers are particularly preferred. Very particular preference is given to minerals and glass beads, in particular glass beads.
  • the proportion of fibrous or particulate fillers based on the mass of the plastic component A1 is preferably in the range from 0 to 50 wt .-%. If the first plastic component A1 contains glass spheres, the proportion of the glass spheres is preferably in the range from 0.1 to 40% by weight, based on the total mass of the first plastic component A1.
  • the fillers may be coated on their surface e.g. be treated with an organic compound or a silane compound.
  • a toughening modifier for the first plastic component A e.g. 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 carbon atoms in the alcohol component.
  • Suitable toughening modifiers are e.g. from WO-A 2007/009930.
  • flame retardants in amounts of 0 to 50 wt .-%, based on the total mass of the first plastic component A1, may be included.
  • Suitable flame retardants are, for example, 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 A13 is contained in the plastic component A1.
  • 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 A1.
  • the compatibilizers used can both improve the incorporation of the component A12 into the matrix of the partly aromatic polyester A1 1 or also serve as adhesion promoters between the first plastic component A1 and the second plastic component B.
  • Suitable compatibilizers are, for example, glycidyl methacrylate-grafted styrene (co) polymers, as used, 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 3000 to 8500 g / mol and a a degree of functionalization of more than two epoxy groups per molecule chain.
  • the first plastic component A2 is made up of:
  • A21 10 to 100% by weight, based on the total weight of components A21 and A22, of at least one thermoplastic styrene (co) polymer,
  • A22 0 to 90% by weight, based on the total weight of components A21 and A22, of at least one thermoplastic (co) polyester,
  • A23 0.05 to 15% by weight, based on the total weight of components A21 and A22, of a) an epoxide group-containing copolymer based on styrene, acrylate and / or methacrylic acid ester, b) a bisphenol A epoxide or c) an epoxy group-containing natural oil, fatty acid ester or fatty acid amide.
  • the first plastic component A2 contains from 50 to 100% by weight of the at least one thermoplastic styrene (co) polymer and in particular from 70 to 100% by weight.
  • the proportion of the at least one thermoplastic see (co) polyester is preferably 0 to 50 wt .-% and in particular 0 to 30 wt .-%.
  • Particularly preferred is an embodiment in which 70 to 90 wt .-% of a thermoplastic styrene (co) polymers and 10 to 30 wt .-% of a thermoplastic (co) polyester are included.
  • thermoplastic styrene (co) polymer A21 is preferably selected from the group consisting of styrene-butadiene copolymers, styrene-acrylonitrile copolymers (SAN), o methylstyrene-styrene-acrylonitrile copolymers, styrene-acrylonitrile copolymers with a particulate rubber phase from diene polymers or alkyl acrylates and o methyl styrene-styrene-acrylonitrile copolymers having a particulate rubber phase from diene polymers or alkyl acrylates, wherein the monomer units other than styrene are each contained in the copolymers in a proportion of 15 to 40% by weight.
  • SAN styrene-acrylonitrile copolymers
  • o methylstyrene-styrene-acrylonitrile copolymers styrene-
  • the component A21 usually contains 15 to 60 wt .-%, preferably 25 to 55 wt .-%, in particular 30 to 50 wt .-%, particulate graft rubber and 40 to 85 wt .-%, preferably from 45 to 75% by weight, in particular from 50 to 70% by weight, of thermoplastic styrene (co) polymer, the percentages by weight being based on the total weight of particulate graft rubber and thermoplastic (co) polymer and together weighing 100% by weight. % result.
  • thermoplastic styrene (co) polymer A21 may contain a-methylstyrene or n-phenylmaleimide in an amount of 0 to 70% by weight.
  • the mass fractions of the monomer units other than styrene or the proportion of o-methylstyrene or n-phenylmaleimide in each case relate to the mass of the thermoplastic styrene (co) polymer A21.
  • the styrene component A21 comprises as the rubber phase a particulate graft rubber based on butadiene and as thermoplastic hard phase copolymers of vinyl aromatic monomers and vinyl cyanides (SAN), in particular of styrene and acrylonitrile, more preferably of styrene, ⁇ -methyl styrene and acrylonitrile.
  • SAN vinyl cyanides
  • ABS Acrylonitrile-butadiene-styrene polymers
  • ABS polymers are generally understood to be impact-modified SAN polymers in which diene polymers, in particular 1,3-polybutadiene, are present in a copolymer matrix of, in particular, styrene and / or ⁇ -methylstyrene and acrylonitrile.
  • ABS polymers and their preparation are known to the person skilled in the art and described in the literature, for example in DIN EN ISO 2580-1 DE of February 2003, WO 02/00745 and WO 2008/020012, as well as in Modern Styrenic Polymers, Edt. J. Scheirs, Wiley & Sons 2003, pp. 305-338.
  • thermoplastic polyester A22 is preferably selected from the group consisting of polyethylene terephthalate, polytrimethylene terephthalate, polybutylene terephthalate and copolyesters of one or more diacids with one or more diols and optionally with one or more lactones and mixtures of at least two of these polyesters.
  • Suitable diacids from which the copolyester is composed are, for example, selected from the group consisting of terephthalic acid, adipic acid, isophthalic acid, 2,6-naphthalenedicarboxylic acid, azelaic acid, sebacic acid, dodecanedioic acids, cyclohexanedicarboxylic acids and mixtures thereof.
  • Suitable diols from which the copolyester is composed are, for example, those which are selected from the group consisting of 1,2-ethanediol, 1,3-propanediol, 1,4-butanediol, pentanediol, 1,6-hexanediol, 1, 4-hexanediol, 1, 4-cyclohexanediol, 1, 4-cyclohexanedimethanol, neopentyl glycol, polytetrahydrofuran and mixtures thereof.
  • lactones are additionally used to form the copolyester, these are preferably selected from the group consisting of ⁇ -caprolactone, hexano-4-lactone, ⁇ -butyrolactone and ⁇ -valerolactone.
  • Preferred thermoplastic polyesters A22 are 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 .-% results.
  • At least one of the polyesters contained in the plastic component A2 has a lower melting point than the polyester B1 of the second plastic component B.
  • the first plastic component A2 may contain one or more additives.
  • the additives are usually 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 fillers are, for example, glass fibers, carbon fibers or aramid fibers.
  • Commonly used particulate fillers are, for example, kaolin, calcined kaolin, talc, chalk, amorphous silica and powdered quartz.
  • the particulate fillers are particularly preferred. Very particular preference is given to minerals and glass beads, in particular glass beads. If the first plastic component A2 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 A2.
  • the fillers may be treated on their surface, for example with an organic compound or a silane compound.
  • Suitable toughening modifiers for the first plastic component A2 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 may be present in amounts of from 0 to 50% by weight, based on the total weight of the first plastic component A2.
  • 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 is contained in the plastic component A2.
  • 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 1 to 3 wt .-%, each based on the total mass of the plastic component A2.
  • the compatibilizers used can both improve the incorporation of component A22 into the matrix of the styrene (co) polymer A21 or also serve as an adhesion promoter between the first plastic component A2 and the second plastic component B.
  • Suitable compatibilizers are, for example, glycidyl methacrylate-grafted styrene (co) polymers, as used, 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 3000 to 8500 g / mol and a degree of functionalization of more than two epoxy groups per molecule chain.
  • Second plastic component B is a molecular weight M w of 5000 to 7000 g / mol and a degree of functionalization of more than four epoxy groups per molecule chain.
  • Second plastic component B is a molecular weight M w of 5000 to 7000 g / mol and a degree of functionalization of more than four epoxy groups per molecule chain.
  • the molding compositions according to the invention contain 10 to 99.99, preferably 30 to 97.99 and in particular 30 to 95 wt .-% of at least one thermoplastic see polyester, which is different from B22.
  • polyesters B1 based on aromatic dicarboxylic acids and an aliphatic or aromatic dihydroxy compound are used.
  • a first group of preferred polyesters are polyalkylene terephthalates, in particular those having 2 to 10 carbon atoms in the alcohol part.
  • 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 and bromine, or by C 1 -C 4 -alkyl groups, such as methyl, ethyl, isopropyl or n-propyl and n, i or t-butyl groups.
  • polyalkylene terephthalates can be prepared by reacting aromatic dicarboxylic acids, their esters or other ester-forming derivatives with aliphatic dihydroxy compounds in a manner known per se.
  • 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 such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and 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 and neopentyl glycol or mixtures thereof.
  • polyesters B1 are polyalkylene terephthalates which are derived from alkanediols having 2 to 6 carbon atoms. Of these, particularly preferred are polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof. Preference is furthermore given to PET and / or PBT which contain up to 1% by weight, preferably up to 0.75% by weight, of 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further monomer units.
  • the viscosity number of the polyester B1 is generally in the range of 50 to 220, preferably from 80 to 160 (measured in a 0.5 wt .-% solution in a phenol / o-Dichlorbenzolgemisch (weight ratio 1: 1 at 25 ° C.) according to ISO 1628.
  • Particular preference is given to polyesters 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 of polyesters DE-A 44 01 055.
  • the carboxyl end group content is usually determined by titration methods (eg potentiometry).
  • Particularly preferred molding compositions contain, as component B1, a mixture of PBT with polyesters which are different from PBT, such as, for example, polyethylene terephthalate (PET).
  • PBT polyethylene terephthalate
  • the proportion e.g. of the polyethylene terephthalate is preferably in the mixture up to 50, in particular 10 to 35 wt .-%, based on 100 wt .-% B1.
  • PET recyclates also termed scrap PET
  • PBT polyalkylene terephthalates
  • Post Industrial Recyclate these are production waste in polycondensation or in processing, e.g. Sprues in injection molding, starting material in injection molding or extrusion, or edge portions of extruded sheets or foils.
  • 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 as regrind present recyclates can be used, wherein the maximum edge length should be at most 10 mm, preferably at most 8 mm. Due to the hydrolytic cleavage of polyesters during processing (due to traces of moisture) it is advisable to pre-dry the recyclate.
  • the residual moisture content after drying is preferably not more than 0.2%, in particular not more than 0.05%.
  • Another group to be mentioned are wholly 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 using mixtures of from 5 to 100 mol% of isophthalic acid and from 0 to 95 mol% of terephthalic acid, in particular mixtures of about 80% of terephthalic acid with 20% of isophthalic acid to approximately equivalent mixtures of these two acids.
  • the aromatic dihydroxy compounds preferably have the general formula (VI)
  • Z represents an alkylene or cycloalkylene group 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 the value 0 to 2 has.
  • the compounds may also carry on the phenylene groups also C 1 -C 6 -alkyl or alkoxy groups and fluorine, chlorine or bromine as substituents.
  • 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 copolyetheresters may also be used.
  • Such products are known per se and are known in the literature, e.g. in US-A-3,651,014. Also in the trade, corresponding products are available, e.g. Hytrel® (DuPont).
  • Suitable halogen-free polycarbonates are, for example, those based on diphenols of the general formula (VII)
  • Q is a single bond, a C to C 8 -alkylene, C 2 - to C 3 -alkylidene, C 3 - to C 6 cycloalkylidene group, a C 6 - to C 2 arylene group and -O-, - S- or -SO 2 - and m is an integer from 0 to 2.
  • the diphenols may on the phenylene radicals also have substituents such as C 6 to C - alkyl or d- to C 6 alkoxy.
  • Preferred diphenols of the formula (VI I) are, for example, hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2-methylbutane , 1,1-bis (4-hydroxyphenyl) cyclohexane.
  • Particular preference is given to 2,2-bis- (4-hydroxyphenyl) -propane and 1,1-bis (4-hydroxyphenyl) -cyclohexane, and also 1,1-bis- (4-hydroxyphenyl) -3,3,5- trimethylcyclohexane.
  • Both homopolycarbonates and copolycarbonates are suitable as component B1; in addition to the bisphenol A homopolymer, the copolycarbonates of bisphenol A are preferred.
  • the suitable polycarbonates may be branched in a known manner, preferably by incorporation of from 0.05 to 2.0 mol%, based on the sum of the diphenols used, of at least trifunctional compounds, for example those containing three or more three phenolic OH groups.
  • the relative viscosities r ⁇ re ⁇ from 1, 10 to 1, 50, in particular from 1, 25 to 1, 40 have. This corresponds to average molecular weights M w (weight average) of 10,000 to 200,000, preferably from 20,000 to 80,000 g / mol.
  • the diphenols of the general formula (VI I) are known per se or can be prepared by known processes.
  • the polycarbonates can be prepared, for example, by reacting the diphenols with phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process), the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators.
  • phosgene by the phase boundary process or with phosgene by the homogeneous phase process (the so-called pyridine process)
  • the molecular weight to be set in each case being achieved in a known manner by a corresponding amount of known chain terminators.
  • Suitable chain terminators include phenol, pt-butylphenol but also long-chain alkylphenols such as 4- (1, 3-tetramethyl-butyl) -phenol, according to DE-OS 28 42 005 or monoalkylphenols or dialkylphenols having a total of 8 to 20 carbon atoms in the alkyl - Substituents according to DE-A 35 06 472, such as p-nonylphenyl, 3,5-di-t-butylphenol, pt-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) -phenol and 4- ( 3,5-dimethylheptyl) phenol.
  • Halogen-free polycarbonates in the context of the present invention means that the polycarbonates are composed of halogen-free diphenols, halogen-free chain terminators and optionally halogen-free branching agents, the content of minor ppm amounts of saponifiable chlorine, resulting, for example, from the preparation of the polycarbonates with phosgene by the interfacial process, is not to be regarded as halo-containing within the meaning of the invention.
  • Such polycarbonates with ppm contents of saponifiable chlorine are halogen-free polycarbonates in the context of the present invention.
  • Suitable components B1 which may be mentioned are amorphous polyester carbonates, with phosgene being replaced by aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units during the preparation.
  • aromatic dicarboxylic acid units such as isophthalic acid and / or terephthalic acid units during the preparation.
  • EP-A 71 1 810 Further suitable copolycarbonates with cycloalkyl radicals as monomer units are described in EP-A 365 916.
  • bisphenol A can be replaced by bisphenol TMC.
  • polycarbonates are available under the trademark APEC HT® from Bayer.
  • the molding compositions according to the invention contain 0.01 to 50, preferably 0.5 to 20 and in particular 0.7 to 10 wt .-% of at least one highly branched or hyperbranched polycarbonate, having an OH number of 1 to 600, preferably 10 to 550 and in particular from 50 to 550 mg KOH / g polycarbonate (according to DIN 53240, Part 2) as component B21 or at least one hyperbranched polyester as component B22 or mixtures thereof as explained below.
  • Hyperbranched polycarbonates B21 in the context of this invention are understood to mean uncrosslinked macromolecules having hydroxyl and carbonate groups which are structurally as well as molecularly nonuniform. They can be constructed on the one hand, starting from a central molecule analogous to dendrimers, but with uneven chain length of the branches. On the other hand, they can also be constructed linearly with functional side groups or, as a combination of the two extremes, they can have linear and branched molecular parts. For the definition of dendrimeric and hyperbranched polymers see also P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.
  • hyperbranched means that the degree of branching (DB), that is to say the mean number dendritic linkages plus average number of end groups per molecule, 10 to 99.9%, preferably 20 to 99%, particularly preferably 20 to 95%.
  • DB degree of branching
  • dendrimer in the context of the present invention is meant that the degree of branching is 99.9-100% For definition of the "degree of branching” see H. Frey et al., Acta Polym. 1997, 48, 30.
  • degree of branching see H. Frey et al., Acta Polym. 1997, 48, 30.
  • hyperbranched is used in the context of the present invention synonymously with “dendrimer”.
  • component B21 has a number average molecular weight M n of from 100 to 15,000, preferably from 200 to 12,000 and in particular from 500 to 10,000 g / mol (GPC, standard PMMA).
  • the glass transition temperature Tg is in particular from -80 ° C to -140 ° C, preferably from -60 to 120 ° C (according to DSC, DIN 53765).
  • the viscosity (mPas) at 23 ° C. is from 50 to 200,000, in particular from 100 to 150,000 and very particularly preferably from 200 to 100,000.
  • Component B21 is preferably obtainable by a process which comprises at least the following steps comprising: a) reacting at least one organic carbonate (BA) of the general formula RO (CO) OR with at least one aliphatic alcohol (BB) which has at least 3 OH groups, with elimination of alcohols ROH to give one or more condensation products (BK) where each R independently of one another is a straight-chain or branched aliphatic, araliphatic or aromatic hydrocarbon radical having 1 to 20 C atoms, and b) intermolecular conversion of the condensation products (BK) to a highly functional, highly branched or hyperbranched polycarbonate , Wherein the quantitative ratio of the OH groups to the carbonates in the reaction mixture is selected so that the condensation products (BK) on average either a carbonate group and more
  • radicals R of the organic carbonates (BA) of the general formula RO (CO) OR used as starting material are each, independently of one another, a straight-chain or branched aliphatic, araliphatic or aromatic carbonyl radical. hydrogen radical with 1 to 20 C atoms.
  • the two radicals R can also be linked together to form a ring. It is preferably an aliphatic hydrocarbon radical and more preferably a straight-chain or branched alkyl radical having 1 to 5 carbon atoms.
  • Dialkyl or diaryl carbonates can be prepared, for example, from the reaction of aliphatic, araliphatic or aromatic alcohols, preferably monoalko get with phosgene. Furthermore, they can also be prepared via oxidative carbonylation of the alcohols or phenols by means of CO in the presence of noble metals, oxygen or NO x .
  • diaryl or dialkyl carbonates see also "Ullmann 's Encyclopedia of Industrial Chemistry", 6th Edition, 2000 Electronic Release, published by Wiley-VCH.
  • suitable carbonates include aliphatic or aromatic carbonates, such as ethylene carbonate, 1, 2 or 1, 3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethylphenyl carbonate, dibenzyl carbonate, dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate, diisobutyl carbonate, dipentyl carbonate, dihexyl carbonate, dicyclohexyl carbonate, Diheptyl carbonate, dioctyl carbonate, didecylacarbonate or didodecyl carbonate.
  • aliphatic or aromatic carbonates such as ethylene carbonate, 1, 2 or 1, 3-propylene carbonate, diphenyl carbonate, ditolyl carbonate, dixylyl carbonate, dinaphthyl carbonate, ethylphenyl carbonate, dibenzyl carbonate, dimethyl carbon
  • Aliphatic carbonates are preferably used, in particular those in which the radicals comprise 1 to 5 C atoms, for example dimethyl carbonate, diethyl carbonate, dipropyl carbonate, dibutyl carbonate or diisobutyl carbonate.
  • the organic carbonates are reacted with at least one aliphatic alcohol (BB) which has at least 3 OH groups or mixtures of two or more different alcohols.
  • BB aliphatic alcohol
  • Examples of compounds having at least three OH groups include glycerol, trimethylolmethane, trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, tris (hydroxymethyl) amine, tris (hydroxyethyl) amine, tris (hydroxypropyl) amine, pentaerythritol, bis ( trimethylolpropane) or sugars, such as, for example, glucose, trifunctional or higher-functional polyetherols based on trifunctional or higher-functional alcohols and ethylene oxide, propylene oxide or butylene oxide, or polyesterols.
  • glycerol trimethylolethane, trimethylolpropane, 1, 2,4-butanetriol, pentaerythritol, and their polyetherols based on ethylene oxide or propylene oxide are particularly preferred.
  • polyhydric alcohols can also be used in mixture with difunctional alcohols ( ⁇ ' ), with the proviso that the mean OH functionality of all the alcohols used together is greater than 2.
  • suitable compounds with two OH groups include ethylene glycol, diethylene glycol, triethylene glycol, 1, 2 and 1, 3-propanediol, dipropylene glycol, tripropylene glycol, neopentyl glycol, 1, 2, 1, 3 and 1, 4-butanediol, 1, 2, 1, 3- and 1,5-pentanediol, hexanediol, cyclopentanediol, cyclohexanediol, cyclohexanedimethanol, difunctional polyether or polyesterols.
  • the reaction of the carbonate with the alcohol or alcohol mixture to form the highly functional highly branched polycarbonate according to the invention is generally carried out with elimination of the monofunctional alcohol or phenol from the carbonate molecule.
  • the highly functional highly branched polycarbonates formed by the process according to the invention are terminated after the reaction, ie without further modification, with hydroxyl groups and / or with carbonate groups.
  • alcohols such as methanol, ethanol, butanol, alcohol / water mixtures, acetone, 2-butanone, ethyl acetate, butyl acetate, methoxypropyl acetate, methoxyethyl acetate, tetrahydrofuran, dimethylformamide, dimethylacetamide, N-methylpyrrolidone, ethylene carbonate or propylene carbonate.
  • a high-functionality polycarbonate is to be understood as meaning a product which, in addition to the carbonate groups which form the polymer backbone, also has at least three, preferably at least six, more preferably at least ten functional groups.
  • the functional groups are carbonate groups and / or OH groups.
  • the number of terminal or pendant functional groups is not limited to the top, but products having a very large number of functional groups may have undesirable properties such as high viscosity or poor solubility.
  • the high-functionality polycarbonates of the present invention generally have not more than 500 terminal or pendant functional groups, preferably not more than 100 terminal or pendant functional groups.
  • condensation product (BK) In the preparation of the high-functionality polycarbonates B21, it is necessary to adjust the ratio of the OH group-containing compounds to the carbonate so that the resulting simplest condensation product (referred to below as the condensation product (BK)) has on average either one carbonate group and more than one OH Group or an OH group and more than one carbonate group.
  • the simplest structure of the condensation product (BK) of a carbonate (BA) and a di- or polyalcohol (BB) results in the arrangement XY n or Y n X, where X is a carbonate group, Y is a hydroxyl group and n usually one Number between 1 and 6, preferably between 1 and 4, particularly preferably between 1 and 3 represents.
  • the reactive group which thereby results as a single group, is generally referred to below as the "focal group". If, for example, in the preparation of the simplest condensation product (BK) from a carbonate and a dihydric alcohol, the reaction ratio is 1: 1, the average results in a molecule of the type XY, illustrated by the general formula 1
  • R has the meaning defined above for the organic carbonates (BA) and R 1 is an aliphatic radical.
  • the preparation of the condensation product (BK) can also be carried out, for example, from a carbonate and a trihydric alcohol, illustrated by the general formula 4, take place, wherein the reaction ratio is at molar 2: 1. This results in the average molecule of type X 2 Y, focal group here is an OH group.
  • R and R 1 have the same meaning as in the formulas 1 to 3.
  • difunctional compounds for example a dicarbonate or a diol
  • this causes an extension of the chains, as illustrated, for example, in general formula (5).
  • the result is again on average a molecule of the type XY 2 , focal group is a carbonate group.
  • R 2 is an organic, preferably aliphatic radical
  • R and R 1 are defined as described above.
  • the simple condensation products (BK) described by way of example in the formulas 1 to 5 preferably react according to the invention intermolecularly to form highly functional polycondensation products, referred to hereinafter as polycondensation products (BP).
  • the conversion to the condensation product (K) and the polycondensation product (BP) is usually carried out at a temperature of 0 to 250 ° C, preferably at 60 to 160 ° C in bulk or in solution. In general, all solvents can be used which are inert to the respective starting materials.
  • condensation reaction is carried out in bulk.
  • the monofunctional alcohol ROH or phenol liberated in the reaction can be removed from the reaction equilibrium by distillation, optionally under reduced pressure, to accelerate the reaction.
  • Suitable catalysts are compounds which catalyze esterification or transesterification reactions, for example alkali metal hydroxides, alkali metal carbonates, alkali metal hydrogencarbonates, preferably of sodium, potassium or cesium, tertiary amines, guanidines, ammonium compounds, phosphonium compounds, aluminum, tin, zinc, titanium, Zirconium or bismuth organic compounds, furthermore so-called double metal cyanide (DMC) catalysts, as described, for example, in DE 10138216 or in DE 10147712.
  • DMC double metal cyanide
  • potassium hydroxide potassium carbonate, potassium bicarbonate, diazabicyclooctane (DABCO), diazabicyclononene (DBN), diazabicycloundecene (DBU), imidazoles, such as imidazole, 1-methylimidazole or 1, 2-dimethylimidazole, titanium tetrabutylate, titanium tetraisopropylate, dibutyltin oxide, dibutyltin dilaurate, Tin dioctoate, Zirkonacetylacetonat or mixtures thereof used.
  • DABCO diazabicyclooctane
  • DBN diazabicyclononene
  • DBU diazabicycloundecene
  • imidazoles such as imidazole, 1-methylimidazole or 1, 2-dimethylimidazole, titanium tetrabutylate, titanium tetraisopropylate, dibutyltin oxide, dibutyltin
  • the addition of the catalyst is generally carried out in an amount of 50 to 10,000, preferably from 100 to 5000 ppm by weight, based on the amount of the alcohol or alcohol mixture used. Furthermore, it is also possible to control the intermolecular polycondensation reaction both by adding the appropriate catalyst and by selecting a suitable temperature. Furthermore, the average molecular weight of the polymer (BP) can be adjusted via the composition of the starting components and over the residence time.
  • the condensation products (BK) and the polycondensation products (BP), which were prepared at elevated temperature, are usually stable at room temperature over a longer period.
  • condensation reaction may result in polycondensation products (BP) having different structures that have branches but no crosslinks.
  • the polycondensation products (BP) ideally have either a carbonate group as a focal group and more than two OH groups or an OH group as a focal group and more than two carbonate groups.
  • the number of reactive groups results from the nature of the condensation products used (BK) and the degree of polycondensation.
  • a condensation product (BK) according to the general formula 2 can be prepared by three-fold intermolecular condensation to form two different polycondensation Products (BP), which are represented in the general formulas 6 and 7, react.
  • BP polycondensation Products
  • R and R 1 are as defined above in Formulas 1 to 5.
  • the temperature can be lowered to a range in which the reaction comes to a standstill and the product (BK) or the polycondensation product (BP) is storage-stable.
  • a product having groups which are reactive toward the focal group of (BP) can be added to the product (BP) to terminate the reaction .
  • a carbonate group as the focal group for example, a mono-, di- or polyamine may be added.
  • a hydroxyl group as a focal group for example, a mono-, di- or polyisocyanate, an epoxy group-containing compound or an OH group-reactive acid derivative may be added to the product (BP).
  • the preparation of the high-functionality polycarbonates according to the invention is usually carried out in a pressure range from 0.1 mbar to 20 bar, preferably at 1 mbar to 5 bar, in reactors or reactor cascades which are operated batchwise, semicontinuously or continuously.
  • the products according to the invention can be further processed after preparation without further purification.
  • the polycarbonates according to the invention can be given, in addition to the functional groups already obtained by the reaction, further functional groups.
  • the functionalization can be carried out during the molecular weight build-up or else subsequently, ie after the end of the actual polycondensation.
  • Such effects can be achieved, for example, by addition of compounds during the polycondensation, in addition to hydroxyl groups or carbonate groups further functional groups or functional elements, such as mercapto, primary, secondary or tertiary amino groups, ether groups, derivatives of carboxylic acids, derivatives of sulfonic acids, derivatives of phosphonic acids , Silane groups, siloxane groups, aryl radicals or long-chain alkyl radicals.
  • carbamate groups for example, ethanolamine, propanolamine, isopropanolamine,
  • Mercaptoethanol can be used, for example, for the modification with mercapto groups.
  • Tertiary amino groups can be produced, for example, by incorporation of N-methyldiethanolamine, N-methyldipropanolamine or N, N-dimethylethanolamine.
  • Ether groups can be generated, for example, by condensation of di- or higher-functional polyetherols.
  • Long-chain alkyl radicals can be introduced by reaction with long-chain alkanediols, the reaction with alkyl or aryl diisocyanates generates polycarbonates having alkyl, aryl and urethane groups.
  • Subsequent functionalization can be obtained by reacting the resulting highly functional, highly branched or hyperbranched polycarbonate in an additional process step (step c) with a suitable functionalizing reagent which can react with the OH and / or carbonate groups of the polycarbonate .
  • Hydroxyl-containing high-functionality, highly or hyperbranched polycarbonates can be modified, for example, by addition of molecules containing acid groups or isocyanate groups.
  • polycarbonates containing acid groups can be obtained by reaction with compounds containing anhydride groups.
  • hydroxyl-containing high-functionality polycarbonates can also be converted into highly functional polycarbonate-polyether polyols by reaction with alkylene oxides, for example ethylene oxide, propylene oxide or butylene oxide.
  • a big advantage of the method lies in its economy. Both the conversion to a condensation product (BK) or polycondensation product (BP) and the reaction of (BK) or (BP) to polycarbonates with other functional groups or elements can be carried out in a reaction apparatus, which is technically and economically advantageous.
  • the molding compositions according to the invention may comprise at least one hyperbranched polyester of the type A x B y , where x is at least 1, preferably at least 1, 3, in particular at least 2
  • y is at least 2.1, preferably at least 2.5, in particular at least 3. Of course, mixtures may also be used as units A and B, respectively.
  • a polyester of the type A x B y is understood to mean a condensate which is composed of an x-functional molecule A and a y-functional molecule B.
  • Hyperbranched polyesters B22 in the context of this invention are understood as meaning uncrosslinked macromolecules having hydroxyl and carboxyl groups which are structurally as well as molecularly nonuniform. They can be constructed on the one hand, starting from a central molecule analogous to dendrimers, but with uneven chain length of the branches. On the other hand, they can also be constructed linearly with functional side groups or, as a combination of the two extremes, they can have linear and branched molecular parts. For the definition of dendrimeric and hyperbranched polymers see also PJ Flory, J. Am. Chem. Soc. 1952, 74, 2718 and H. Frey et al., Chem. Eur. J. 2000, 6, no. 14, 2499.
  • DB degree of branching
  • dendrimer in the context of the present invention is meant that the degree of branching is 99.9-100% For definition of the "degree of branching” see H. Frey et al., Acta Polym. 1997, 48, 30.
  • degree of branching see H. Frey et al., Acta Polym. 1997, 48, 30.
  • hyperbranched is used in the context of the present invention synonymously with “dendrimer”.
  • the component B22 preferably has a M n of 300 to 30,000, in particular from 400 to 25,000 and very particularly from 500 to 20,000 g / mol, determined by means of GPC, standard PMMA, eluent dimethylacetamide.
  • B22 has an OH number of 0 to 600, preferably 1 to 500, in particular from 20 to 500 mg KOH / g polyester according to DIN 53240 and preferably a COOH number of 0 to 600, preferably from 1 to 500 and in particular of 2 to 500 mg KOH / g polyester.
  • the T g is preferably from -50 ° C to 140 ° C and in particular from -50 to 100 ° C (by DSC, according to DIN 53765).
  • those components B22 are preferred in which at least one OH or COOH number is greater than 0, preferably greater than 0.1 and in particular greater than 0.5.
  • the dicarboxylic acids which can be reacted according to variant (a) include, for example, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, undecane- ⁇ , oo-dicarboxylic acid, dodecane- ⁇ , oo-dicarboxylic acid, cis- and trans- Cyclohexane-1, 2-dicarboxylic acid, cis- and trans-cyclohexane-1, 3-dicarboxylic acid, cis- and trans-cyclohexane-1, 4-dicarboxylic acid, cis- and trans-cyclopentane-1, 2-dicarboxylic acid and cis- and trans-cyclopentane-1,3-dicarboxylic acid, wherein the abovementioned dicarboxylic acids may be substituted by one or more radicals selected from C 1 -C 10
  • C 3 -C 12 cycloalkyl groups for example, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl; Alkylene groups such as methylene or ethylidene or
  • C 6 -C 4 -aryl groups such as, for example, phenyl, 1-naphthyl, 2-naphthyl, 1-anthryl, 2
  • dicarboxylic acids which can be reacted according to variant (a) include ethylenically unsaturated acids, such as, for example, maleic acid and fumaric acid, and also aromatic dicarboxylic acids, for example phthalic acid, isophthalic acid or terephthalic acid.
  • dicarboxylic acids can be used either as such or in the form of derivatives.
  • Mono- or dialkyl esters preferably mono- or dimethyl esters or the corresponding mono- or diethyl esters, but also those of higher alcohols such as n-propanol, iso-propanol, n-butanol, isobutanol, tert-butanol, n-pentanol, n Hexanol-derived mono- and dialkyl esters, furthermore mono- and divinyl esters and mixed esters, preferably methyl ethyl ester.
  • Succinic acid, glutaric acid, adipic acid, phthalic acid, isophthalic acid, terephthalic acid or their mono- or dimethyl esters are particularly preferably used. Most preferably, adipic acid is used.
  • adipic acid is used.
  • trifunctional alcohols for example, can be implemented: glycerol, BuTan-1, 2,4-triol, n-pentane-1, 2,5-triol, n-pentane-1, 3,5-triol, n-hexane -1, 2,6-triol, n-hexane-1, 2,5-triol, n-hexane-1, 3,6-triol, trimethylolbutane, trimethylolpropane or di-trimethylolpropane, trimethylolethane, pentaerythritol or dipentaerythritol; Sugar alcohols such as mesoerythritol, threitol, sorbito
  • convertible tricarboxylic acids or polycarboxylic acids are, for example, 1, 2,4-benzenetricarboxylic acid, 1, 3,5-benzenetricarboxylic acid, 1, 2,4,5-Benzoltetracarbonklare and mellitic acid.
  • Tricarboxylic acids or polycarboxylic acids can be used in the reaction according to the invention either as such or in the form of derivatives.
  • Derivatives are preferably understood the relevant anhydrides in monomeric or polymeric form,
  • Mono-, di- or trialkyl preferably mono-, di- or trimethyl esters or the corresponding mono-, di- or triethyl esters, but also those of higher alcohols such as n-propanol, iso-propanol, n-butanol, isobutanol, tert Butanol, n-
  • diols for variant (b) of the present invention include ethylene glycol, propane-1,2-diol, propane-1,3-diol, butane-1,2-diol, butane-1,3-diol, butane-1 , 4-diol, butane-2,3-diol, pentane-1, 2-diol, pentane-1, 3-diol, pentane-1, 4-diol, pentane-1, 5-diol, pentane-2 , 3-diol, pentane-2,4-diol, hexane-1,2-diol, hexane-1,3-diol, hexane-1,4-diol, hexane-1,5-diol, hexane-1, 6 -diol, hexane-2,5-diol, heptane-1, 2-dio
  • one or both hydroxyl groups in the abovementioned diols can also be substituted by SH groups.
  • the molar ratio of molecules A to molecules B in the A x B y polyester in variants (a) and (b) is 4: 1 to 1: 4, in particular 2: 1 to 1: 2.
  • the at least trifunctional alcohols reacted according to variant (a) of the process may each have hydroxyl groups of the same reactivity. Also preferred here are at least trifunctional alcohols whose OH groups are initially identically reactive, but in which a drop in reactivity, owing to steric or electronic influences, due to reaction with at least one acid group, is induced in the remaining OH groups. let adorn. This is the case, for example, when using trimethylolpropane or pentaerythritol.
  • the at least trifunctional alcohols reacted according to variant (a) can also have hydroxyl groups with at least two chemically different reactivities.
  • the different reactivity of the functional groups can be based either on chemical (for example primary / secondary / tertiary OH group) or on steric causes.
  • the triol may be a triol having primary and secondary hydroxyl groups, preferred example being glycerin.
  • Suitable are, for example, hydrocarbons such as paraffins or aromatics. Particularly suitable paraffins are n-heptane and cyclohexane. Particularly suitable aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as a mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene.
  • solvents in the absence of acidic catalysts are particularly suitable: ethers such as dioxane or tetrahydrofuran and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the amount of solvent added is according to the invention at least 0.1 wt .-%, based on the mass of the starting materials to be reacted, preferably at least 1 wt .-% and particularly preferably at least 10 wt .-%. It is also possible to use excesses of solvent, based on the mass of reacted starting materials to be reacted, for example 1:01 to 10 times. Solvent amounts of more than 100 times, based on the mass of reacted starting materials to be reacted, are not advantageous because significantly lower concentrations of the reactants, the reaction rate decreases significantly, resulting in uneconomical long reaction times.
  • a dehydrating agent which is added at the beginning of the reaction.
  • Suitable examples are molecular sieves, in particular molecular sieve 4A, MgS0 4 and Na 2 S0 4 . It is also possible during the reaction to add further de-watering agent or to replace de-watering agent with fresh de-watering agent. It is also possible to distill off water or alcohol formed during the reaction and to use, for example, a water separator.
  • the process can be carried out in the absence of acidic catalysts.
  • alumium compounds of the general formula Al (OR) 3 and titanates of the general formula Ti (OR) 4 can be used as acidic inorganic catalysts, where the radicals R can be identical or different and are selected independently of one another
  • C 1 -C 10 -alkyl radicals for example methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl, tert-butyl, n-pentyl, isopentyl, sec-pentyl, neo Pentyl, 1,2-dimethylpropyl, iso-amyl, n-hexyl, iso-hexyl, sec-hexyl, n-heptyl, iso-heptyl, n-octyl, 2-ethylhexyl, n-nonyl or n-decyl,
  • C 3 -C 12 cycloalkyl radicals for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl and cyclododecyl; preferred are cyclopentyl, cyclohexyl and cycloheptyl.
  • radicals R in Al (OR) 3 or Ti (OR) 4 are preferably identical and selected from isopropyl or 2-ethylhexyl.
  • Preferred acidic organometallic catalysts are, for example, selected from dialkyltin oxides R 2 SnO, where R is as defined above.
  • a particularly preferred representative of acidic organometallic catalysts is di-n-butyltin oxide, which is commercially available as so-called oxo-tin, or di-n-butyltin dilaurate.
  • Preferred acidic organic catalysts are acidic organic compounds with, for example, phosphate groups, sulfonic acid groups, sulfate groups or phosphonic acid groups. Particularly preferred are sulfonic acids such as para-toluenesulfonic acid. It is also possible to use acid ion exchangers as acidic organic catalysts. use, for example, sulfonic acid-containing polystyrene resins, which are crosslinked with about 2 mol% divinylbenzene.
  • the process according to the invention is carried out under an inert gas atmosphere, that is to say, for example, under carbon dioxide, nitrogen or noble gas, of which argon in particular may be mentioned.
  • the inventive method is carried out at temperatures of 60 to 200 ° C.
  • the pressure conditions of the method according to the invention are not critical per se. You can work at significantly reduced pressure, for example at 10 to 500 mbar.
  • the process according to the invention can also be carried out at pressures above 500 mbar.
  • the reaction is preferably at atmospheric pressure; but it is also possible to carry out at slightly elevated pressure, for example up to 1200 mbar. You can also work under significantly elevated pressure, for example, at pressures up to 10 bar.
  • the reaction is preferably at atmospheric pressure.
  • the reaction time of the process according to the invention is usually 10 minutes to 25 hours, preferably 30 minutes to 10 hours and particularly preferably one to 8 hours.
  • component B22 can be prepared in the presence of enzymes or decomposition products of enzymes (according to DE-A 101 63163).
  • the dicarboxylic acids reacted according to the invention do not belong to the acidic organic catalysts in the sense of the present invention.
  • lipases or esterases are Candida cylindracea, Candida lipolytica, Candida rugosa, Candida antarctica, Candida utilis, Chromobacterium viscosum, Geotrichum viscosum, Geotrichum candidum, Mucor javanicus, Mucor miehei, pig pancreas, Pseudomonas spp., Pseudomonas fluorescens, Pseudomonas cepacia, Rhizopus arrhizus, Rhizopus delemar, Rhizopus niveus, Rhizopus oryzae, Aspergillus niger, Penicillium roquefortii, Penicillium camembertii or Esterase from Bacillus spp. and Bacillus thermoglucosidase.
  • Candida antarctica lipase B The enzymes listed are commercially available, for example from Novozy
  • the enzyme is preferably used in immobilized form, for example on silica gel or Lewatit®.
  • Processes for the immobilization of enzymes are known per se, for example from Kurt Faber, "Biotransformations in Organic Chemistry", 3rd edition 1997, Springer Verlag, Chapter 3.2 "Immobilization” page 345-356. Immobilized enzymes are commercially available, for example from Novozymes Biotech Inc., Denmark.
  • the amount of immobilized enzyme used is 0.1 to 20 wt .-%, in particular 10 to 15 wt .-%, based on the mass of the total starting materials to be reacted.
  • the inventive method is carried out at temperatures above 60 ° C.
  • Suitable are, for example, hydrocarbons such as paraffins or aromatics.
  • paraffins are n-heptane and cyclohexane.
  • aromatics are toluene, ortho-xylene, meta-xylene, para-xylene, xylene as a mixture of isomers, ethylbenzene, chlorobenzene and ortho- and meta-dichlorobenzene.
  • ethers such as dioxane or tetrahydrofuran and ketones such as methyl ethyl ketone and methyl isobutyl ketone.
  • the amount of solvent added is at least 5 parts by weight, based on the mass of the starting materials to be used, preferably at least 50 parts by weight, and more preferably at least 100 parts by weight. Amounts of more than 10,000 parts by weight of solvent are not desirable because at significantly lower concentrations, the reaction rate drops significantly, resulting in uneconomical long reaction times.
  • the process according to the invention is carried out at pressures above 500 mbar.
  • the reaction is at atmospheric pressure or slightly elevated pressure, for example up to 1200 mbar. You can also work under significantly elevated pressure, for example, at pressures up to 10 bar.
  • the reaction is preferably at atmospheric pressure.
  • the reaction time of the method according to the invention is usually 4 hours to 6 days, preferably 5 hours to 5 days and more preferably 8 hours to 4 days.
  • the highly functional hyperbranched polyester can be isolated, for example by filtering off the enzyme and concentration, wherein the concentration is usually carried out at reduced pressure. Further suitable work-up methods are precipitation after addition of water and subsequent washing and drying.
  • high-functionality, hyperbranched polyesters obtainable by the process according to the invention are distinguished by particularly low levels of discoloration and resinification.
  • hyperbranched polymers see also: P.J. Flory, J. Am. Chem. Soc. 1952, 74, 2718 and A. Sunder et al., Chem. Eur. J. 2000, 6, No.1, 1-8.
  • "highly functional hyperbranched” means that the degree of branching, that is to say the average number of dendritic linkages plus the average number of end groups per molecule, is 10 - 99.9%, preferably 20 - 99%, more preferably 30-90% (see H. Frey et al., Acta Polym., 1997, 48, 30).
  • the polyesters of the invention have a molecular weight M w of from 500 to 50,000 g / mol, preferably from 1,000 to 20,000, particularly preferably from 1,000 to 19,000.
  • the polydispersity is from 1, 2 to 50, preferably 1, 4 to 40, particularly preferably 1, 5 to 30 and most preferably 1, 5 to 10. They are usually readily soluble, that is, clear solutions of up to 50 wt .-%, in some cases even up to 80 wt .-%, of the polyester according to the invention in tetrahydrofuran (THF), n-butyl acetate, ethanol and many other solvents without the naked eye gel particles are detectable.
  • THF tetrahydrofuran
  • the high-functionality hyperbranched polyesters according to the invention are carboxy-terminated, carboxy- and hydroxyl-terminated and are preferably terminated by hydroxyl groups.
  • the ratios of the components B21 to B22 are preferably from 1:20 to 20: 1, in particular from 1:15 to 15: 1 and very particularly from 1: 5 to 5: 1, when used in admixture.
  • the hyperbranched polycarbonates B21 / polyesters B22 used are particles with a size of 20-500 nm. These nanoparticles are finely distributed in the polymer blend, and the size of the particles in the compound is from 20 to 500 nm, preferably 50-300 nm ,
  • the plastic component B may contain from 1 to 40, preferably from 1 to 20,% by weight of an impact-modifying polymer (often also referred to as a rubber-elastic polymer or elastomer).
  • Preferred rubber-elastic polymers are polymers based on olefins which are composed of the following components: D1 40-100% by weight, preferably 55-79.5% by weight, of at least one ⁇ -olefin having 2 to 8 C atoms,
  • wt .-% preferably 0.5 to 20 wt .-% of an ethylenically unsaturated mono- or dicarboxylic acid or a functional derivative of such an acid
  • the first preferred group to be mentioned are the so-called ethylene-propylene (EPM) or ethylene-propylene-diene (EPDM) rubbers, which preferably have a ratio of ethylene to propylene units in the range from 40:60 to 90:10 exhibit.
  • EPM ethylene-propylene
  • EPDM ethylene-propylene-diene
  • the Mooney viscosities (MLI + 4/100 ° C.) of such, preferably uncrosslinked, EPM or EPDM rubbers are preferably in the range from 25 to 100, in particular 35 to 90 (measured on the large rotor after 4 minutes running at 100 ° C according to DIN 53 523).
  • EPM rubbers generally have practically no double bonds, while EPDM rubbers can have 1 to 20 double bonds / 100 carbon atoms.
  • suitable diene monomers D2 for EPDM rubbers include conjugated dienes such as isoprene and butadiene, non-conjugated dienes having 5 to 25 carbon atoms, such as penta-1,4-diene, hexa-1,4-diene, hexa-1, 5-diene, 2,5-dimethylhexa-1,5-diene and octa-1,4-diene, cyclic dienes such as cyclopentadiene, cyclohexadienes, cyclooctadienes and dicyclopentadiene and alkenylnorbornenes such as 5-ethylidene-2-norbornene, 5-butylidene 2-norbornene, 2-methallyl-5-norbornene, 2-isopropenyl-5-norbornene and tricyclodienes such as 3-methyl-tricyclo (5.2.1.0.2.6) - 3,8-decadiene or mixtures thereof.
  • the diene content of the EPDM rubbers is preferably from 0.5 to 50, especially 2 to 20 percent, and more preferably 3 to 15. "° / o, based on the total weight of the olefin polymer.
  • EPM or EPDM rubbers may preferably also be grafted with reactive carboxylic acids or their derivatives.
  • Acrylic acid, methacrylic acid and their derivatives as well as maleic anhydride may be mentioned here in particular.
  • Particularly preferred components D are, for example, MBS rubbers composed of:
  • D2 90 to 100 wt .-% of a diene, 0 to 10 wt .-% of further crosslinkable monomers and 1 to 35 wt .-% of a shell of
  • D7 1 to 30 wt .-% of styrene or unsaturated styrenes or mixtures thereof and D8 70 to 100 wt .-% of at least one unsaturated nitrile.
  • Suitable monomers D7 are styrenes or substituted styrenes of the general formula (VIII)
  • R is a d- to C 8 alkyl, preferably methyl or ethyl, or hydrogen
  • R 1 is a d- to C 8 alkyl radical, preferably methyl or ethyl
  • n is 1, 2 or 3, or mixtures thereof.
  • Another group of preferred olefin polymers are copolymers of ⁇ -olefins having 2 to 8 C atoms, in particular of ethylene, with C 1 -C 8 -alkyl esters of acrylic acid and / or methacrylic acid.
  • esters having 1 to 12 C atoms in particular having 2 to 10 C atoms.
  • Examples thereof are methyl, ethyl, propyl, n-, i-butyl and t-butyl, 2-ethylhexyl, octyl and decyl acrylates or the corresponding esters of methacrylic acid. Of these, n-butyl acrylate and 2-ethylhexyl acrylate are particularly preferred.
  • the proportion of methacrylic acid esters and acrylic esters D3 in the olefin polymers is 0-60, preferably 10-50 and in particular 30-45 wt .-%.
  • acid-functional and / or latent acid-functional monomers of ethylenically unsaturated mono- or dicarboxylic acids D4 or monomers D5 containing epoxy groups may also be present in the olefin polymers.
  • monomers D4 are acrylic acid, methacrylic acid, tertiary alkyl esters of these acids, in particular tert-butyl acrylate and.
  • Dicarboxylic acids such as maleic acid and fumaric acid or derivatives of these acids and their monoesters called.
  • Suitable latent acid-functional monomers are those compounds which form free acid groups under the polymerization conditions or during the incorporation of the olefin polymers into the molding compositions.
  • Examples of these are anhydrides of dicarboxylic acids having up to 20 carbon atoms, in particular maleic anhydride and tertiary C 1 -C 2 -alkyl esters of the abovementioned acids, in particular tert-butyl acrylate and tert-butyl methacrylate.
  • the acid-functional or latent acid-functional monomers and the epoxy group-containing monomers are preferably incorporated into the olefin polymers by addition of compounds of the general formulas (XI) - (XII) to the monomer mixture.
  • H 2 C CR- COO- (CH 2 ) n - -c -CHR (XI I)
  • radicals R 1 - R 9 represent hydrogen or alkyl groups having 1 to 6 carbon atoms and m is an integer from 0 to 20 and n is an integer from 0 to 10.
  • R 1 - R 7 is hydrogen, for m the value 0 or 1 and for n the value 1.
  • the corresponding compounds are maleic acid, fumaric acid, maleic anhydride, D4 or alkenyl glycidyl ether or vinyl glycidyl ether D5.
  • Preferred compounds of the formulas (IX), (X), (XI) and (XII) are maleic acid and maleic anhydride as component D4 and epoxy group-containing esters of acrylic acid and / or methacrylic acid, with glycidyl acrylate and glycidyl methacrylate (as component D5) being especially to be favoured.
  • the proportion of components D4 or D5 is in each case from 0.07 to 40% by weight, in particular from 0.1 to 20 and particularly preferably from 0.15 to 15% by weight, based on the total weight of the olefin polymers. Particular preference is given to olefin polymers
  • esters of acrylic and / or methacrylic acid are the methyl, ethyl, propyl and i- or t-butyl esters.
  • Olefinpolymerisate whose proportion is preferably 0 to 20, in particular 4 to 18 and very particularly 5 to 15 wt .-%, based on the total weight of all components.
  • the preparation of the ethylene copolymers described above can be carried out by processes known per se, preferably by random copolymerization under high pressure and elevated temperature.
  • the melt index of the ethylene copolymers is generally in the range of 1 to 80 g / 10 min (measured at 190 ° C and 2.16 kg load).
  • acrylate rubbers D composed of: a) 70 to 90% by weight, and preferably 75 to 85% by weight, of crosslinked elastomeric core composed of:
  • a seed-grafted shell consisting of an alkyl methacrylate polymer whose alkyl group has 1 to 4 carbon atoms or a random copolymer of an alkyl methacrylate whose alkyl group is 1 to 4 carbon atoms and an alkyl acrylate whose alkyl group has 1 to 8 carbon atoms, the alkyl acrylate being contained in a molar amount of 5 to 40%, and preferably in the range of 10 to 20%.
  • n-alkyl acrylates usable for forming the copolymer (I) according to the present invention
  • n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate and especially n-octyl acrylate can be used for illustration.
  • n-alkyl acrylates useful in forming the copolymer (II) according to the invention include n-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, n-heptyl acrylate, and especially n-octyl acrylate.
  • the n-alkyl acrylates which can be used to form the copolymers (I) and / or (II) may be identical or different.
  • alkyl acrylates which can be used according to the invention to form the mixtures of alkyl acrylates in the copolymers (I) and / or (II), ethyl acrylate, n-propyl acrylate, n-butyl acrylate, amyl acrylate, 2-methylbutyl acrylate , 2-ethylhexyl acrylate, n-hexyl acrylate, n-octyl acrylate, n-decyl acrylate, n-dodecyl acrylate and 3,5,5-trimethylhexyl acrylate.
  • the n-alkyl acrylate should be present in a proportion by weight of at least 10% by weight. of the mixture of alkyl acrylates, this amount preferably being in the range of 20 to 80%.
  • n-alkyl acrylates and especially n-octyl acrylate are preferably used for the preparation of the copolymers (I) and (II).
  • a mixture of alkyl acrylates is used to form the copolymers (I) and / or (II)
  • preferably 20 to 80% by weight of n-octyl acrylate and preferably 80 to 20% by weight of n-butyl acrylate are used.
  • alkyl methacrylates which can be used to form the shell grafted onto the crosslinked elastomeric core according to the present invention are, for example, ethyl methacrylate, n-propyl methacrylate, isopropyl methacrylate; n-butyl methacrylate, isobutyl acrylate and especially methyl methacrylate.
  • the crosslinking agent used to form the copolymer (I) can be selected according to the present invention particularly from the derivatives having at least two vinyl-type double bonds or one or more vinyl-type double bonds and at least one allyl-type double bond.
  • compounds are used which contain in their molecules mainly double bonds of the vinyl type.
  • crosslinking agents may be the divinylbenzenes, (meth) acrylates of polyalcohols such as trimethylolpropane triacrylate, trimethylolpropane trimethacrylate, allyl acrylate, allyl methacrylate, diacrylates or methacrylates of alkylene glycols having 2 to 10 carbon atoms in the alkylene chain, and especially ethylene glycol diacrylate, ethylene glycol dimethacrylate, butane-1,4 diol diacrylate, butane-1, 4-dimethacrylate, hexene-1, 6-diol diacrylate, hexane-1, 6-dimethacrylate, the diacrylate or dimethacrylate of polyoxyalkylene glycol of the following formula:
  • the grafting agent used to prepare the copolymer (II) can be selected according to the present invention particularly among the derivatives containing at least two allyl type double bonds or one or more allyl type double bonds and at least one vinyl type double bond.
  • grafting agents are, for example, diallyl maleate, diallyl itaconate, allyl acrylate, allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, diallyl terephthalate and triallyl trimesate.
  • the preferred amount of impact modifier incorporated into the thermoplastic polymer is in the range of from 1 to 30 weight percent, and preferably from 5 to 10 weight percent, to 100 weight percent of the thermoplastic polymer used.
  • a viscosity in the molten state can be defined which changes to the same extent.
  • the viscosity in the molten state may be in a fairly wide range, with the proviso that good dispersion of the impact modifier is ensured in the operations of using the resin composition with the modifier.
  • the value of the resisting torque of a Brabender rheometer containing 50 g of impact modifier and operated at a temperature of 200 ° C with a rotation speed of the rotors of 40 rpm is suitable Torque after 20 min at 200 ° C is performed.
  • Suitable values for the viscosity in the molten state of the impact modifier correspond to values of the above-mentioned torque in the range of 600 to 4000 ns.
  • the preferred Values for the viscosity of the impact modifier in the molten state Torque values in the range of 800 to 3000 Nm and in particular in the range of 1000 to 2500 Nm.
  • one or a mixture of different graft copolymers is used as component E in amounts of from 1 to 60% by weight, based on the sum of all components.
  • Preferred inventive Molding compositions contain from 2 to 50, more preferably from 3 to 40 wt .-%, of at least one graft copolymer E, which is different from rubbery polymers, which are used as impact modifier D.
  • the graft polymers E are composed of
  • E2 from 20 to 80% by weight, preferably from 30 to 50% by weight, of a grafting pad
  • R is a Ci to C 8 alkyl, preferably methyl or ethyl, or hydrogen and R 1 is a Ci to C 8 alkyl, preferably methyl or ethyl, and n is 1, 2 or 3 or mixtures thereof and
  • unsaturated nitrile preferably acrylonitrile or methacrylonitrile or mixtures thereof.
  • graft base E1 polymers are considered, whose glass transition temperature is below 10 ° C, preferably below 0 ° C, more preferably below -20 ° C. These are, for example, elastomers based on C 1 -C 8 -alkyl esters of acrylic acid, which may optionally contain further comonomers.
  • Graft bases E1 which are constructed from are preferred
  • E12 0 to 30 wt .-%, in particular 20 to 30 wt .-% of a further copolymerizable monoethylenically unsaturated monomers, such as butadiene, iso pren, styrene, acrylonitrile, methyl methacrylate or vinyl methyl ether or mixtures thereof
  • a further copolymerizable monoethylenically unsaturated monomers such as butadiene, iso pren, styrene, acrylonitrile, methyl methacrylate or vinyl methyl ether or mixtures thereof
  • bi- or polyfunctional crosslinking monomers E13 are monomers which preferably contain two, optionally also three or more, capable of copolymerizing ethylenic double bonds, which are not conjugated in the 1, 3-positions.
  • Suitable crosslinking monomers are, for example, divinylbenzene, diallyl maleate, diallyl fumarate, diallyl phthalate, triallyl cyanurate or triallyl isocyanurate.
  • the acrylic acid ester of tricyclodecenyl alcohol has proven to be a particularly advantageous crosslinking monomer (cf DE-A 12 60 135).
  • Preferred grafting layers E2 are those in which E21 is styrene or ⁇ -methylstyrene or mixtures thereof and E22 is acrylonitrile or methacrylonitrile.
  • the preferred monomer mixtures used are, in particular, styrene and acrylonitrile or ⁇ -methylstyrene and acrylonitrile.
  • the grafting pads are obtainable by copolymerization of components E21 and E22.
  • the graft base E1 of the graft polymers E which is composed of the components E1 1, optionally E12, and E13, is also referred to as ASA rubber.
  • Their preparation is known per se and described for example in DE-A 28 26 925, DE-A 31 49 358 and DE-A 3414 1 18.
  • the preparation of the graft polymers E can be carried out, for example, by the method described in DE-PS 12 60 135.
  • the structure of the graft (graft) of the graft polymers can be one or two-stage.
  • the 1st stage generally constitutes from 20 to 70% by weight, preferably from 25 to 50% by weight, based on E2.
  • styrene or substituted styrenes or mixtures thereof (E1 1) are used.
  • the second stage of the graft shell generally accounts for 30 to 80 wt .-%, in particular 50 to 75 wt .-%, each based on E2, from.
  • the conditions of the graft polymerization are preferably chosen such that particle sizes of 50 to 700 nm (d 50 value of the integral mass distribution) result. Measures for this purpose are known and described for example in DE-OS 2826925.
  • the seed latex process can be used to directly produce a coarse-particle rubber dispersion.
  • the particles of the rubber in a known manner, for example by agglomeration, increased so that the latex is bimodal (50 to 180 nm and 200 to 700 nm) is constructed.
  • a mixture of two graft polymers having particle diameters (d 50 value of the integral mass distribution) of from 50 to 180 nm or from 200 to 700 nm in a weight ratio of from 70:30 to 30:70 is used.
  • the chemical structure of the two graft polymers is preferably the same, although the shell of the coarse-particulate graft polymer can be constructed in two stages in particular.
  • Mixtures of the components, the latter having a coarse and fine graft polymer, are e.g. described in DE-OS 36 15 607.
  • Mixtures of the components, the latter having a two-stage graft shell, are known from EP-A 1 1 1 260.
  • the molding compositions of the invention 0 to 60 wt .-%, based on the sum of all components, of at least one copolymer based on styrene or substituted styrenes and unsaturated nitriles.
  • Preferred inventive Corresponding molding compositions contain the component F in proportions of 1 to 45, in particular from 2 to 40 wt .-%, based on the sum of all components.
  • copolymers F are according to the invention.
  • F1 60 to 95 wt .-%, preferably 70 to 85 wt .-% of styrene or substituted styrenes of the general formula (XIII) or mixtures thereof and
  • the copolymers F are resinous, thermoplastic and rubber-free. Particularly preferred copolymers F are those of styrene and acrylonitrile, of ⁇ -methylstyrene and acrylonitrile or of styrene, ⁇ -methylstyrene and acrylonitrile. It is also possible to use several of the copolymers described at the same time.
  • the Copolmerisate F are known per se and can be prepared by free-radical polymerization, in particular by emulsion, suspension, solution and bulk polymerization. They have viscosity numbers in the range of 40 to 160, which corresponds to average molecular weights M w (weight average) of 40,000 to 2,000,000.
  • G2 1 to 80 wt .-%, preferably 15 to 50 wt .-% of an antimony oxide.
  • Preferred oxides G2 are antimony trioxide and antimony pentoxide.
  • the oxide G2 can be incorporated into the polymer A1, A2 or B in so-called batches (concentrates), it being possible for example to use polymers in the concentrate which correspond to component A1, A2 or B or different of the respective component A1, A2 or B are.
  • Suitable flame retardants G1 are preferably brominated compounds such as brominated diphenyl ethers, brominated trimethylphenylindanes (FR 1808 from DSB), tetrabromobisphenol-A and hexabromocyclododecane.
  • Suitable flame retardants G1 are preferably brominated compounds, such as brominated oligocarbonates (BC 52 or BC 58 from Great Lakes) of the structural formula:
  • polypentabromobenzyl acrylates with n> 4 for example FR 1025 from Dead Sea Bromine (DSB) of the formula:
  • Preferred brominated compounds are furthermore oligomeric reaction products (n> 3) of tetrabromo-bis-phenol-A with epoxides (eg FR 2300 and 2400 from DSB) of the formula:
  • the brominated oligostyrenes preferably used as flame retardants have a mean degree of polymerization (number average) between 3 and 90, preferably between 5 and 60, measured by vapor pressure osmometry in toluene. Cyclic oligomers are also suitable. According to a preferred embodiment of the invention, the brominated oligomeric styrenes to be employed have the following formula (XIV) in which R is hydrogen or an aliphatic radical, in particular an alkyl radical such as. B. CH 2 or C 2 H 5 and n represent the number of repeating chain units. R 'may be both H and bromine as well as a fragment of a common radical generator:
  • n can be 1-88, preferably 3-58.
  • the brominated oligostyrenes contain from 40 to 80% by weight, preferably from 55 to 70% by weight, of bromine. Preference is given to a product which consists predominantly of polydibromostyrene. The substances are melted undecomposed and z.
  • the preparation of the flame retardant can also be carried out by ionic oligomerization of styrene and subsequent bromination.
  • the amount of brominated oligostyrene necessary for the flameproofing of the polyamides depends on the bromine content.
  • the bromine content in the molding compositions according to the invention is from 2 to 20 wt .-%, preferably from 5 to 12 wt .-%.
  • the brominated polystyrenes according to the invention are usually obtained by the process described in EP-A 47 549:
  • n '(see XVI) generally has values of from 125 to 1500, which corresponds to a molecular weight of from 42,500 to 235,000, preferably from 130,000 to 135,000.
  • the bromine content (based on the content of nucleus-substituted bromine) is generally at least 50, preferably at least 60 and in particular 65% by weight.
  • the commercially available powdery products generally have a glass transition temperature of 160 to 200 ° C and are available, for example, under the names HP 7010 from Albemarle and Pyrocheck or PB 68 from Ferro Corporation. It is also possible to use mixtures of the brominated oligostyrenes with brominated polystyrenes in the molding compositions according to the invention, the mixing ratio being arbitrary.
  • chlorine-containing flame retardants D1 are suitable, with Deklorane® plus from Oxychem being preferred.
  • the plastic components A1, A2 and / or B can be 1 to 40, preferably 2 to 30 and in particular 5 to 20 wt .-% of a halogen-free flame retardant selected from the group of nitrogen-containing or phosphorus-containing compounds or PN condensates or their mixtures, included.
  • the melamine cyanurate which is suitable according to the invention as halogen-free flame retardant H is a reaction product of preferably equimolar amounts of melamine (formula (XVI)) and cyanuric acid or isocyanuric acid (formulas (XVIa) and (XVIb))
  • the commercially available product is a white powder with a mean particle size d 50 of 1, 5 - 7 ⁇ .
  • melamine melamine borate
  • oxalate phosphate prim.
  • pyrophosphate sec neopentyl glycol boronic acid melamine and polymeric melamine phosphate (CAS No. 56386-64-2) ,
  • Suitable guanidine salts are
  • Melon 32518-77-7 Compounds in the context of the present invention are understood to mean, for example, benzoguanamine itself and its adducts or salts as well as the nitrogen-substituted derivatives and its adducts or salts. Also suitable are ammonium polyphosphate (NH 4 PO 3 ) n with n about 200 to 1000, preferably 600 to 800, and tris (hydroxyethyl) isocyanurate (THEIC) of the formula (XVII)
  • Ar aromatic carboxylic acids
  • Suitable carboxylic acids are, for example, phthalic acid, isophthalic acid, terephthalic acid, 1,3,5-benzenetricarboxylic acid, 1,2,4-benzenetricarboxylic acid, pyromellitic acid, mellophanic acid, prehnitic acid, 1-naphthoic acid, 2-naphthoic acid, naphthalenedicarboxylic acids and anthracene carboxylic acids.
  • the preparation is carried out by reacting the tris (hydroxyethyl) isocyanurate with the acids, their alkyl esters or their halides according to the processes of EP-A 584 567.
  • reaction products are a mixture of monomeric and oligomeric esters, which may also be crosslinked.
  • the degree of oligomerization is usually 2 to about 100, preferably 2 to 20.
  • the mixing ratio, for example, of (NH 4 P0 3 ) n to THEIC is preferably 90 to 50 to 10 to 50, in particular 80 to 50 to 50 to 20 wt .-%, based on the mixture of such components H.
  • R, R ' are straight-chain or branched alkyl radicals having 1 to 10 C atoms, preferably hydrogen, and in particular their adducts with phosphoric acid, boric acid and / or pyrophosphoric acid. Also preferred are allantoin compounds of the formula (XIX)
  • R, R ' have the meaning given in formula (XVIII) and their salts with phosphoric acid, boric acid and / or pyrophosphoric acid and glycolurils of the formula (XX) or its salts with the abovementioned acids
  • Suitable products are commercially available or according to DE-A 196 14 424.
  • the cyanoguanidine (formula (XXI)) which can be used according to the invention is obtained e.g. by reaction of calcium cyanamide with carbonic acid, wherein the resulting cyanamide dimerizes at pH 9 to 10 to cyanguanidine.
  • the commercially available product is a white powder with a melting point of 209 ° C to 21 1 ° C.
  • Phosphoric acid salts of the formula (XXII) and / or diphosphinic acid salts of the formula (XXIII) and / or their polymers are preferred as phosphorus-containing inorganic compounds,
  • R 1 is hydrogen, C 1 -C 6 -alkyl, preferably C 1 -C 4 -alkyl, linear or branched, for example methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl ; phenyl; wherein preferably at least one radical R 1 or R 2 , in particular R 1 and R 2 is hydrogen;
  • R Cr to Cio-alkylene linear or branched, e.g. Methylene, ethylene, n-propylene, iso-propylene, n-butylene, tert-butylene, n-pentylene, n-octylene, n-dodecylene; Arylene, e.g. Phenylene, naphthylene;
  • Alkylarylene e.g. Methyl-phenylene, ethyl-phenylene, tert-butyl-phenylene, methyl-naphthylene, ethyl-naphthylene, tert-butyl-naphthylene;
  • Arylalkylene e.g. Phenylmethylene, phenylethylene, phenylpropylene, phenylbutylene;
  • M is an alkaline earth, alkali metal, Al, Zn, Fe, boron; m is an integer of 1 to 3; n is an integer from 1 to 3 and x is 1 or 2.
  • R 1 and R 2 are hydrogen, where M is preferably Zn or Al and calcium phosphinate is very particularly preferred.
  • Such products are commercially available, for example, as calcium phosphinate.
  • Suitable salts of the formula (XXII) or (XXIII) in which only one radical R 1 or R 2 is hydrogen are, for example, salts of phenylphosphinic acid, their Na and / or Ca salts being preferred.
  • the phosphorus-containing compounds of component H are preferably organic and inorganic phosphorus-containing compounds in which the phosphorus has the valence state -3 to +5.
  • level of oxidation is understood to mean the term "oxidation state” as used in the textbook of inorganic chemistry by A.F. Hollemann and E. Wiberg, Walter des Gruyter and Co. (1964, 57th to 70th edition), pages 166 to 177, is reproduced.
  • Phosphorus compounds of valence levels -3 to +5 are derived from phosphine (-3), diphosphine (-2), phosphine oxide (-1), elemental phosphorus (+0), hypophosphorous acid (+1), phosphorous acid (+3), Hypodiphosphoric acid (+4) and phosphoric acid (+5).
  • Examples of phosphorus compounds of the phosphine class which have the valence state -3 are aromatic phosphines such as triphenylphosphine, tritolylphosphine, trinonylphosphine, trinaphthylphosphine and trisnonylphenylphosphine and the like. Particularly suitable is triphenylphosphine.
  • Examples of phosphorus compounds of the diphosphine class which have the valence state -2 are tetraphenyldiphosphine, tetranaphthyldiphosphine and the like. Particularly suitable is tetranaphthyldiphosphine.
  • Phosphorus compounds of valence state -1 are derived from the phosphine oxide.
  • R 1 , R 2 and R 3 are the same or different alkyl, aryl, alkylaryl or cycloalkyl groups having 8 to 40 carbon atoms.
  • phosphine oxides are triphenylphosphine oxide, tritolylphosphine oxide, trisnonylphenylphosphine oxide, tricyclohexylphosphine oxide, tris (n-butyl) phosphine oxide, tris (n-hexyl) phosphine oxide, tris (n-octyl) phosphine oxide, tris (cyanoethyl) phosphine oxide, Benzyl bis (cyclohexyl) phosphine oxide, benzyl bisphenyl phosphine oxide, phenyl bis (n-hexyl) phosphine oxide.
  • oxidized reaction products of phosphine with aldehydes especially from t-butylphosphine with glyoxal.
  • Particular preference is given to using triphenylphosphine oxide, tricyclohexlyphosphine oxide, tris (n-octyl) phosphine oxide and tris (cyanoethyl) phosphine oxide.
  • triphenylphosphine sulfide and its derivatives of phosphine oxides as described above.
  • Phosphorus of the valence state +0 is the elemental phosphorus. Eligible are red and black phosphorus. Preference is given to red phosphorus.
  • Phosphorus compounds of the "oxidation state" +1 are e.g. Hypophosphites of purely organic nature, e.g. organic hypophosphites, such as cellulose hypophosphite esters, esters of hypophosphorous acids with diols, e.g. of 1, 10-dodecyldiol. Also substituted phosphinic acids and their anhydrides, e.g. Diphenylphosphinic can be used.
  • diphenylphosphinic acid di-p-tolylphosphinic acid, di-cresylphosphinic anhydride
  • compounds such as hydroquinone, ethylene glycol, propylene glycol bis (diphenylphosphinic) esters u.a. in question.
  • aryl (alkyl) phosphinic acid amides e.g. Diphenylphosphinic acid dimethylamide and sulfonamidoaryl (alkyl) phosphinic acid derivatives, e.g. p-
  • Tolylsulfonamidodiphenylphosphin yarn Hydroquinone and ethylene glycol bis (diphenylphosphinic) esters and the bis-diphenylphosphinate of hydroquinone are preferably used.
  • Phosphorus compounds of the oxidation state +3 are derived from the phosphorous acid.
  • R is a Ci to C 4 alkyl radical, preferably methyl radical
  • phosphorus of the valence state +3 in triaryl (alkyl) phosphites such as triphenyl phosphite, tris (4-decylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite or Phenyldidecylphosphit include.
  • diphosphites such as propylene glycol-1, 2-bis (diphosphite) or cyclic phosphites, which are derived from pentaerythritol, neopentyl glycol or pyrocatechol, in question.
  • methyl neopentyl glycol phosphonate and phosphite and dimethyl pentaerythritol diphosphonate and phosphite are particularly preferred.
  • hypodiphosphates As phosphorus compounds of oxidation state +4 are mainly hypodiphosphates, such. Tetraphenyl hypodiphosphate or Bisneopentylhypodiphosphat into consideration.
  • Suitable phosphorus compounds of the oxidation state +5 are, in particular, alkyl- and aryl-substituted phosphates.
  • Examples are phenylbisdodecylphosphate, phenylethylhydrogenphosphate, phenylbis (3,5,5-trimethylhexyl) phosphate, ethyldiphenylphosphate, 2-ethylhexyldi (tolyl) phosphate, diphenylhydrogenphosphate, bis (2-ethylhexyl) -p-tolylphosphate, tritolylphosphate, bis (2-ethylhexyl) phenyl phosphate, di (nonyl) phenyl phosphate, phenylmethyl hydrogen phosphate, di (dodecyl) p-tolyl phosphate, p-tolylbis (2,5,5-trimethylhexyl) phosphate or 2-ethylhexy
  • Triphenyl phosphate and resorcinol bis (diphenyl phosphate) and its ring-substituted derivatives of the general formula (XXVI) (RDP) are very particularly suitable:
  • the substituents have the following meaning an aromatic radical having 6 to 20 C atoms, preferably a phenyl radical which may be substituted by alkyl groups having 1 to 4 C atoms, preferably methyl, a divalent phenol radical, preferably
  • n an average value between 0.1 to 100, preferably 0.5 to 50, in particular 0.8 to 10 and very particularly 1 to 5.
  • cyclic phosphates can also be used. Particularly suitable here is diphenylpentaerythritol diphosphate and phenylneopentyl phosphate.
  • Such polymeric, halogen-free organic phosphorus compounds containing phosphorus in the polymer chain are formed, for example, in the preparation of pentacyclic, unsaturated phosphine dihalides, as described, for example, in DE-A 20 36 173.
  • the molecular weight measured by vapor pressure osmometry in dimethylformamide, the Polyphospholinoxide should be in the range of 500 to 7000, preferably in the range of 700 to 2000.
  • the phosphorus here has the oxidation state -1.
  • inorganic coordination polymers of aryl (alkyl) phosphinic acids such as poly-ß-sodium (l) -methylphenylphosphinat be used. Their preparation is given in DE-A 31 40 520. The phosphorus has the oxidation number +1.
  • halogen-free polymeric phosphorus compounds by the reaction of a phosphonic acid chloride, such as phenyl, methyl, propyl, styryl and vinylphosphonic dichloride with bifunctional phenols, such as hydroquinone, resorcinol, 2,3,5-trimethylhydroquinone, bisphenol-A, tetramethylbiphenol -A arise.
  • polymeric phosphorus compounds which may be present in the molding compositions according to the invention are prepared by reaction of phosphorus oxytrichloride or phosphoric ester dichlorides with a mixture of mono-, bi- and trifunctional phenols and other compounds bearing hydroxyl groups (see Houben-Weyl-Muller, Thieme et al. Verlag Stuttgart, Organic Phosphorus Compounds Part II (1963)).
  • polymeric phosphonates can be prepared by transesterification reactions of phosphonic acid esters with bifunctional phenols (cf., DE-A 29 25 208) or by reactions of phosphonic acid esters with diamines or diamides or hydrazides (compare US Pat. No. 4,403,075).
  • inorganic poly ammonium phosphate
  • R 1 to R 20 are independently hydrogen, a linear or branched alkyl group up to 6 C atoms n an average value of 0.5 to 50 and
  • X is a single bond
  • C O, S, S0 2 , C (CH 3 ) 2
  • Preferred compounds H are those in which R 1 to R 20 independently of one another are hydrogen and / or a methyl radical. In the event that R 1 to R 20 independently of one another are methyl, those compounds H are preferred in which the radicals R 1 , R 5 , R 6 , R 10 , R 11 , R 15 , R 16 , R 20 in ortho-position to the oxygen of the phosphate group represent at least one methyl radical. Further preferred are connections fertilize H, in which per aromatic ring, a methyl group, preferably in the ortho position, is present and the other radicals are hydrogen.
  • n is preferably 0.5 to 5, in particular 0.7 to 2 and in particular ⁇ 1 as an average value.
  • the value of n as an average value is given by the preparation of the compounds listed above, so that the degree of oligomerization is usually less than 10 and small amounts ( usually ⁇ 5 wt .-%) of triphenyl phosphate, this being different from batch to batch.
  • the compounds H are commercially available as CR-741 from Daihachi.
  • P-N condensates are suitable, in particular those as described in WO 2002/96976.
  • Particularly preferred combinations H are mixtures of phosphorus- and nitrogen-containing compounds, wherein mixing ratios of 1:10 to 10: 1, preferably 1: 9 to 9: 1 are preferred.
  • the plastic components A1, A2 and / or B can contain 0 to 60, in particular up to 50% by weight of further additives and processing aids which are different from D, E, F, G and H.
  • the molding compositions of the invention 0 to 5, preferably 0.05 to 3 and in particular 0.1 to 2 wt .-% of at least one ester or amide of saturated or unsaturated aliphatic carboxylic acids having 10 to 40, preferably 16 to 22 carbon atoms with aliphatic saturated alcohols or amines having 2 to 40, preferably 2 to 6 carbon atoms.
  • the carboxylic acids can be 1- or 2-valent. Examples which may be mentioned are pelargonic acid, palmitic acid, lauric acid, margaric acid, dodecanedioic acid, behenic acid and particularly preferably stearic acid, capric acid and montanic acid (mixture of fatty acids having 30 to 40 carbon atoms).
  • the aliphatic alcohols can be 1 - to 4-valent.
  • examples of alcohols are n-butanol, n-octanol, stearyl alcohol, ethylene glycol, propylene glycol, neopentyl glycol, pentaerythritol, with glycerol and pentaerythritol being preferred.
  • the aliphatic amines can be 1 - to 3-valent. Examples of these are stearylamine, ethylenediamine, propylenediamine, hexamethylenediamine, di (6-aminohexyl) amine, with ethylenediamine and hexamethylenediamine being particularly preferred.
  • esters or amides are glycerol distearate, glycerol tristearate, ethylenediamine distearate, glycerol monopalmitate, glycerol trilaurate, glycerol monobehenate and pentaerythritol tetrastearate.
  • fibrous or particulate fillers C are carbon fibers, glass fibers, glass spheres, amorphous silica, asbestos, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, chalk, powdered quartz, mica, barium sulfate and feldspar called in amounts up to 50 wt. %, in particular up to 40%.
  • Preferred fibrous fillers are carbon fibers, aramid fibers and potassium titanate fibers, glass fibers being particularly preferred as E glass. These can be used as rovings or cut glass in the commercial forms.
  • the fibrous fillers can be surface-pretreated for better compatibility with the thermoplastic with a silane compound.
  • Suitable silane compounds are those of the general formula (X- (CH 2 ) n ) k -Si- (O-C m H 2m + 1 ) 2 _ k in which the substituents have the following meanings:
  • X is NH 2 -, CH 2 -CH-, HO-,
  • O n is an integer from 2 to 10, preferably 3 to 4
  • n is an integer from 1 to 5, preferably 1 to 2
  • k is an integer from 1 to 3, preferably 1 Preferred silane compounds are aminopropyltrimethoxysilane,
  • silane compounds are generally used in amounts of 0.05 to 5, preferably 0.5 to 1, 5 and in particular 0.8 to 1 wt .-% (based on C) for surface coating.
  • acicular mineral fillers are also suitable.
  • the term "needle-shaped mineral fillers” is understood to mean a mineral filler with a pronounced, needle-like character.
  • An example is acicular wollastonite.
  • the mineral has an L / D (length to diameter) ratio of 8: 1 to 35: 1, preferably 8: 1 to 1: 1: 1.
  • the mineral filler may optionally be pretreated with the aforementioned silane compounds; however, pretreatment is not essential.
  • Kaolin, calcined kaolin, wollastonite, talc and chalk are mentioned as further fillers.
  • thermoplastic molding compositions according to the invention may contain conventional processing aids such as stabilizers, antioxidants, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • processing aids such as stabilizers, antioxidants, agents against thermal decomposition and decomposition by ultraviolet light, lubricants and mold release agents, colorants such as dyes and pigments, nucleating agents, plasticizers, etc.
  • antioxidants and heat stabilizers sterically hindered phenols and / or phosphites, hydroquinones, aromatic secondary amines such as diphenylamines, various substituted representatives of these groups and mixtures thereof in concentrations up to 1 wt .-%, based on the weight of the thermoplastic molding compositions mentioned.
  • UV stabilizers which are generally used in amounts of up to 2 wt .-%, based on the molding composition, various substituted resorcinols, salicylates, benzotriazoles and benzophenones may be mentioned.
  • inorganic pigments such as titanium dioxide, ultramarine blue, iron oxide and carbon black, furthermore organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and anthraquinones as colorants.
  • organic pigments such as phthalocyanines, quinacridones, perylenes and also dyes such as nigrosine and anthraquinones
  • nucleating agents sodium phenylphosphinate, alumina, silica and preferably talc may be used.
  • lubricants and mold release agents are usually used in amounts of up to 1 wt .-%.
  • Preferred are long-chain fatty acids (eg stearic acid or behenic acid), their salts (eg Ca or Zn stearate) or montan waxes (mixtures of straight-chain, saturated carboxylic acids with chain lengths of 28 to 32 C atoms) and Ca or Na montanate and also low molecular weight polyethylene or polypropylene waxes.
  • plasticizers are dioctyl phthalate, dibenzyl phthalate, butyl benzyl phthalate, hydrocarbon oils, N- (n-butyl) benzenesulfonamide.
  • the novel molding materials may contain from 0 to 2% by weight of fluorine-containing ethylene polymers. These are polymers of ethylene with a fluorine content of 55 to 76 wt .-%, preferably 70 to 76 wt .-%.
  • PTFE polytetrafluoroethylene
  • tetrafluoroethylene-hexafluoro-propylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers.
  • PTFE polytetrafluoroethylene
  • tetrafluoroethylene-hexafluoro-propylene copolymers or tetrafluoroethylene copolymers with smaller proportions (generally up to 50% by weight) of copolymerizable ethylenically unsaturated monomers.
  • fluorine-containing ethylene polymers are homogeneously distributed in the molding compositions and preferably have a particle size d 50 (number average) in the range of 0.05 to ⁇ ⁇ ⁇ , in particular from 0.1 to 5 ⁇ on. These small particle sizes can be achieved particularly preferably by using aqueous dispersions of fluorine-containing ethylene polymers and incorporating them into a polyester melt.
  • thermoplastic molding compositions according to the invention can be prepared by processes known per se, in which mixing the starting components in conventional mixing devices such as screw extruders, Brabender mills or Banbury mills and then extruded. After extrusion, the extrudate can be cooled and comminuted. It is also possible to premix individual components and then to add the remaining starting materials individually and / or likewise mixed.
  • the mixing temperatures are usually 230 to 290 ° C Component and manufacturing process
  • 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 may 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 roller bearing, a plate, a wire for stabilizers, or a zinc die-cast 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.
  • 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 part as well as a plastic casing of at least two plastic components, the method comprising the following steps.
  • A1 1 5 to 80 wt .-%, based on the total weight of components A1 1 and A12, of at least one polyester based on aliphatic and aromatic dicarboxylic acids and aliphatic dihydroxy compounds; A12: 20 to 95 wt .-%, based on the total weight of the components A1 1 and
  • A12 at least one homo- or copolyester selected from the group consisting of polylactide (PLA), polycaprolactone, polyhydroxyalkanoates and polyesters of aliphatic dicarboxylic acids and aliphatic diols; A13: 0.05 to 15 wt .-%, based on the total weight of the components A1 1 and A12, a) of an epoxy group-containing copolymer based on styrene, acrylic acid ester 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, or with a first plastic component A2, the first plastic component A2 being composed of:
  • A21 10 to 100% by weight, based on the total weight of components A21 and A22, of at least one thermoplastic styrene (co) polymer,
  • A22 0 to 90% by weight, based on the total weight of components A21 and A22, of at least one thermoplastic (co) polyester,
  • A23 0.05 to 15 wt .-%, based on the total weight of the components A21 and A22, a) of an epoxy group-containing copolymer based on styrene, acrylic acid ester 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,
  • thermoplastic polyester 10 to 99.99% by weight of at least one thermoplastic polyester
  • B21 at least one highly branched or hyperbranched polycarbonate having an OH number of 1 to 600 mg KOH / g polycarbonate (according to DIN 53249, Part 2) or
  • B22 at least one highly branched or hyperbranched polyester of A x B y where x is at least 1, 1, and y is at least 2.1 or mixtures thereof, wherein the first plastic component A1 or the first plastic component A2 and / or the second plastic component B can continue to be included:
  • first plastic component A1 first plastic component A2 and second plastic component B have already been described above.
  • the wrapping of the insert part with the first plastic component A1 or A2 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 A1 or A2.
  • the injection of the plastic molding compound is generally carried out at the customary for injection molding pressures. However, if e.g.
  • the injection of the component A1 or A2 preferably 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 A1 or A2 solidifies and becomes solid.
  • Another advantage of overmolding the insert with the first plastic component A1 or A2 is that the insert is stabilized by this plastic covering.
  • a wide variety of geometries can be realized.
  • a rectangular, diamond-shaped, pentagonal, octagonal, circular or elliptical cross-section can be realized.
  • the plastic covering of the first plastic component A1 or A2 may also be rounded. Transitions between the surfaces of the encapsulation made of the first plastic component A1 or A2 can be obtuse-angled, acute-angled or rounded. Melting lips may also be pronounced, ie thin, projecting regions of the first plastic component A1 or A2. These are then melted and deformed by 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 from the first plastic component A1 or A2.
  • the first plastic component A1 or A2 may be the insert, e.g. enclose with a cross section in the form of a double-T. Due to the projecting areas of such an encapsulation with the first plastic component A1 or A2, a positive connection can be achieved. Since the first plastic component A1 or A2 is generally melted by the overspill with the second plastic component B, the geometry of the pre-extrusion of the first plastic component A1 or A2 can generally change if the processing temperature of the second plastic component B above the melting temperature or the softening point of the first plastic component A1 or A2 is located.
  • the pre-extrusion of the first plastic component A1 or A2 can be deformed by the pressure of the injected melt in the encapsulation with the second plastic component B.
  • sharp edges of the pre-injection of the first plastic component A1 or A2 are rounded.
  • the insert part thus enveloped is enveloped with the second plastic component B.
  • the wrapping with the second plastic component B preferably also takes place by means of a pointed casting process.
  • the injection molding process is generally carried out with the usual pressures for injection molding.
  • the pressure in the tool is generally higher than the maximum pressure in the tool in step (a).
  • the hardened first plastic component A1 or A2 is preferably fused on its surface, so that a particularly good adhesion between the first plastic component A1 or A2 and the second plastic component B is formed.
  • the wrapping of the insert with the first plastic component A1 or A2 in step (a) and the forming 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 A1 or A2.
  • the tool must open so that the free form corresponds to the shape of the finished part.
  • Corresponding tools are known to the person skilled in the art.
  • the wrapping of the insert with the first plastic component A1 or A2 in step (a) takes place in a first tool and the forming of the outer casing of the second plastic component B in step (b) in a second tool.
  • the insert part covered with the first plastic component A1 or A2 it is necessary for the insert part covered with the first plastic component A1 or A2 to be removed from the first tool and to be inserted into the second tool before being encapsulated with the second plastic component B. If it is desired that deformation of the sheath of the insert from the first plastic component A1 or A2 is avoided, it is necessary for the first plastic component A1 or A2 of the inflowing melt of the second plastic component B to oppose a sufficient mechanical resistance. For this purpose, a sufficient rigidity and strength is necessary, which depend on the degree of solidification of the first plastic component A1 or A2 and the injection pressure of the second plastic component B.
  • the first plastic component A1 or A2 and the second plastic component B two different injection molding or plasticizing units are used. 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 A1 or A2 is injected and then with the injection molding machine, with the second plastic component B to the insert with the enclosure of the first plastic component A1 or A2 is overmoulded. Conventional injection molding machines used for this purpose are, for example, injection molding machines with rotary table tools.
  • the cylinders are arranged opposite each other 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 part covered with the first plastic component A1 or A2 are enveloped 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 wrapped with the envelope of the first plastic component A1 or A2 with the second plastic component B.
  • first the outer envelope is formed from the second plastic component B, wherein portions of the insert are not wrapped, and in a second step, the non-enveloped portions of the insert are coated with the first plastic component A1 or A2, the enveloping takes place the insert with the second plastic component B preferably such 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 A1 or A2 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.
  • the insert is inserted into an injection mold and then encapsulated with the second plastic component B.
  • the tool is located 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 A1 or A2, released.
  • movable parts are provided in the tool, which first form the recesses and then release the recesses for the purpose of casting with the first plastic component A1 or A2 or the insert which is encapsulated with the second plastic component B, is the Tool removed and placed in a second tool in which the areas to be wrapped with the first plastic component A1 or A2, are kept free.
  • the wrapping with the first plastic component A1 or A2 preferably also takes place by means of 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 A1 or A2 is preferably 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 A1 or A2 is then preferably below 900 bar, preferably below 600 bar.
  • a media-tight connection between the first plastic component A1 or A2 and the second plastic component B is preferably achieved in that the plastic component B is melted by the melt of the first plastic component A1 or A2 on its surface, so that for example by interdiffusion a particularly good adhesion between the first plastic component A1 or A2 and the second plastic component B is formed.
  • first Plastic component A1 or A2 and the second plastic component B chemically and / or mechanically connect.
  • a chemical compound can be formed, for example, by reaction of the polymer components of the first plastic component A1 or A2 and the second plastic component B, for example by covalent bonds between the first plastic component A1 or A2 or a component of the first plastic component A1 or A2 and the second plastic component B or a component the second plastic component B are knotted.
  • the method can also be designed at any time so that there is not only a good adhesion but also a positive connection between the first plastic component A1 or A2 and the second plastic component B.
  • the melt temperature of the first plastic component A1 or A2 in the first extrusion coating of the insert part is preferably in the range of the processing temperature of the underlying polymer customary in injection molding. If the first plastic component A1 or A2 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 results in a more easily flowing melt that can better wet the surface of the insert, allowing a higher bond strength to be achieved between the insert material and the first plastic component A1 or A2.
  • thermal degradation of the first plastic component A1 or A2 or one of its components A1 1 or A12 or A21 or A22 may occur.
  • the melt temperature of the second plastic component B is preferably in the range of the customary in injection molding processing temperature of the underlying polymer. If the second plastic component B is a mixture of two polymers, the melting temperature is selected to be 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 casing made of the first plastic component A1 or A2, thereby achieving a higher bond strength between the second plastic component B and the first plastic component A1 or A2 can.
  • there may be a more or less thick boundary layer which represents a cohesive connection of the plastic components A1 or A2 and the second plastic component B, which improves the media tightness by interdiffusion.
  • the melt temperature of the second plastic component B is not set so high that the envelope of the first plastic component A1 or A2 is completely melted and washed away.
  • the injection pressure for the second plastic component B is preferably selected so that excessive deformation of the envelope of the first plastic component A1 or A2, 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 according to the invention consisting of the insert part with the cover made of the first plastic component A1 or A2 and the outer cover made of the second plastic component B is characterized in that it extends along both boundary surfaces, ie the interface between the insert part and the cover made of the first plastic component A1 or A2 and the interface between the first plastic component A1 or A2 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.
  • Test specimens are produced from an insert of CuSn 6 , which is enveloped by a first plastic component A and a second plastic component B, wherein the first plastic component A is the above-described plastic component A1 or A2.
  • the insert part is first punched out of strip-cut CuSn 6 using a punching tool.
  • the insert has a rectangular shaped frame, in which the opposite short sides are additionally connected by a web in the middle.
  • 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 gating of the insert with the first plastic component A and the wrapped with the first plastic component A insert with the second plastic component B takes place almost at the parting plane.
  • 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.
  • test volume For the differential pressure measurement, two volumes, a test volume and a reference volume are subjected to the same pressure. If the test volume leaks, a pressure difference arises which can be measured directly. Alternatively, 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 the Component B1 was shown.
  • the test medium used was air.
  • the test volume Vp ref was 36 ml.
  • the filling time of the volumes with a test pressure of 0.5 bar was 5 seconds. After a settling time of 10 seconds, the pressure drop was measured for at least 5 seconds. Subsequently, the volumes were emptied within 2 seconds. From the differential pressure drop, the leak rates were calculated according to Boyle-Marriotte: r [m il // m ⁇ in i] - ⁇ riW ' ⁇
  • the table shows the components A1 to A4 for different total compositions of component A.
  • Component B1 or B2 are different encapsulation, wherein component B1 is an outer casing according to the prior art and B2 for the component B GE measure of the invention is.
  • TSZ means thermal shock cycles.
  • Component A1 is a copolymer of the monomers styrene (40% by weight), o methylstyrene (30% by weight) and acrylonitrile (20% by weight) comprising a butadiene phase (10 Wt .-%) with an elastic modulus of 2400 MPa and a Vicat softening temperature of 1 15 ° C.
  • Component A2 is a blend of 90% by weight of component A1 and 10% by weight of a random copolyester of terephthalic acid (25 mol%), 1,4-butanediol (50 mol%) and adipic acid (25 mol%). ) with melting point 1 10 to 120 ° C (DSC measurement according to ISO 1 1357-3) 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 mixture of 97 wt .-% of component A1 and 3 wt .-% of an epoxy-functionalized styrene-acrylic acid copolymer having molecular weight M w of 6800 g / mol and a degree of functionalization of more than 4 epoxy groups per molecular chain. The glass transition is 54 ° C.
  • Component A4 is a blend consisting of 45% by weight of a random aliphatic-aromatic copolyester prepared from terephthalic acid (25 mol%), adipic acid (25 mol%) and butanediol (45 mol%) with 45 wt% Polylactide (PLA).
  • This blend has 2 melting points of 1 10 to 120 ° C and 140 to 155 ° C, determined by means of DSC, a Vicat softening temperature (VST A 50) of 68 ° C, measured according to ISO 306: 2004, a Shore D Hardness of 59, measured according to ISO 868, and an E modulus of 750 MPa, determined according to ISO 527 on blown films of a thickness of 50 ⁇ on.
  • VST A 50 Vicat softening temperature
  • Component B1 is a polybutylene terephthalate with 30 wt .-% glass fiber having a viscosity number 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 an average particle size between 10 and 35 nm (CILAS) and a BET surface area of 1 10-120 m 2 / g (ISO 9277) and 0.5 wt .-% Pentaerithritoltetrastearat as a lubricant.
  • 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 10 ⁇ m.
  • Component B2 is a mixture containing 99.5% by weight of component B1 and 0.5% by weight of a hyperbranched polycarbonate.
  • a hyperbranched polycarbonate trimethylolpropane x 3 ethylene oxide as polyhydric alcohol was equimolarly mixed with diethyl carbonate in a three-necked flask equipped with stirrer, reflux condenser and internal thermometer and 250 ppm K 2 C0 3 (based on the amount of alcohol) was added as catalyst. The mixture was then heated with stirring to 100 ° C and stirred for 2 h at this temperature. As the reaction progressed, the temperature of the reaction mixture was reduced due to the incipient boiling cooling of the liberated monoalcohol. Now, the reflux condenser has been exchanged a Abstäbenden kuhnler, ethanol distilled off and the temperature of the reaction mixture slowly increased to 160 ° C.
  • the distilled ethanol was collected in a cooled round bottomed flask, weighed and determined the percentage of sales so compared to the theoretically possible full conversion.
  • the amount of ethanol in the distillate based on full conversion is 90 mol%.
  • reaction products were then analyzed by gel permeation chromatography, eluent was dimethylacetamide, polymethylmethacrylate (PMMA) was used as standard.
  • PMMA polymethylmethacrylate
  • the hyperbranched polycarbonate has a number average molecular weight M n of 2500 g / mol and a weight average molecular weight M w of 4100 g / mol.
  • the viscosity at 23 ° C is 4020 mPas and the OH number according to DIN 53240, Part 2 is 310 mg KOH / g.

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  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Mechanical Engineering (AREA)
  • Architecture (AREA)
  • Civil Engineering (AREA)
  • Structural Engineering (AREA)
  • Laminated Bodies (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Injection Moulding Of Plastics Or The Like (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
EP11718719A 2010-05-05 2011-05-05 Bauteil umfassend ein einlegeteil und eine kunststoffummantelung sowie verfahren zu seiner herstellung Withdrawn EP2566692A1 (de)

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EP11718719A EP2566692A1 (de) 2010-05-05 2011-05-05 Bauteil umfassend ein einlegeteil und eine kunststoffummantelung sowie verfahren zu seiner herstellung

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EP10161980 2010-05-05
PCT/EP2011/057176 WO2011138384A1 (de) 2010-05-05 2011-05-05 Bauteil umfassend ein einlegeteil und eine kunststoffummantelung sowie verfahren zu seiner herstellung
EP11718719A EP2566692A1 (de) 2010-05-05 2011-05-05 Bauteil umfassend ein einlegeteil und eine kunststoffummantelung sowie verfahren zu seiner herstellung

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EP2566692A1 true EP2566692A1 (de) 2013-03-13

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EP (1) EP2566692A1 (enExample)
JP (1) JP5808394B2 (enExample)
KR (1) KR20130100912A (enExample)
CN (1) CN102985256B (enExample)
BR (1) BR112012028309A2 (enExample)
MY (1) MY163063A (enExample)
WO (1) WO2011138384A1 (enExample)

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KR102106548B1 (ko) * 2018-12-12 2020-05-04 주식회사 세프라 덴드리머를 포함하는 에어백 슈트용 올레핀계 탄성체 복합수지 조성물

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JP5808394B2 (ja) 2015-11-10
WO2011138384A1 (de) 2011-11-10
BR112012028309A2 (pt) 2016-11-01
CN102985256B (zh) 2015-08-12
CN102985256A (zh) 2013-03-20
KR20130100912A (ko) 2013-09-12
MY163063A (en) 2017-08-15
JP2013530851A (ja) 2013-08-01

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