Classifications

• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
  • C08L67/03—Polyesters derived from dicarboxylic acids and dihydroxy compounds the dicarboxylic acids and dihydroxy compounds having the carboxyl- and the hydroxy groups directly linked to aromatic rings
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L67/00—Compositions of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Compositions of derivatives of such polymers
  • C08L67/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
  • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
  • C08L25/02—Homopolymers or copolymers of hydrocarbons
  • C08L25/04—Homopolymers or copolymers of styrene
  • C08L25/08—Copolymers of styrene
  • C08L25/12—Copolymers of styrene with unsaturated nitriles
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2205/00—Polymer mixtures characterised by other features
  • C08L2205/03—Polymer mixtures characterised by other features containing three or more polymers in a blend
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L25/00—Compositions of, homopolymers or copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by an aromatic carbocyclic ring; Compositions of derivatives of such polymers
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L2666/00—Composition of polymers characterized by a further compound in the blend, being organic macromolecular compounds, natural resins, waxes or and bituminous materials, non-macromolecular organic substances, inorganic substances or characterized by their function in the composition
  • C08L2666/02—Organic macromolecular compounds, natural resins, waxes or and bituminous materials
• • C—CHEMISTRY; METALLURGY
  • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
  • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
  • C08L51/00—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers
  • C08L51/04—Compositions of graft polymers in which the grafted component is obtained by reactions only involving carbon-to-carbon unsaturated bonds; Compositions of derivatives of such polymers grafted on to rubbers

Definitions

• the invention relates to molding compositions, moldings, structures, recyclates and laminates and their use.
• Molded parts made of polymeric materials which are used in particular in the interior of motor vehicles, have to meet high requirements, particularly with regard to their mechanical properties, their surface properties, their aging and their emission and / or odor behavior.
• ABS ABS. This material has poor UV resistance, poor heat aging resistance and poor
• ABS / PC polymer blend made of acrylonitrile / butadiene / styrene copolymer and polycarbonate.
• ABS / PC polymer blend made of acrylonitrile / butadiene / styrene copolymer and polycarbonate.
• this material has only insufficient UV resistance, poor heat aging behavior (toughness and elongation at break after heat storage), poor stress crack resistance, for example against plasticizers, poor flowability, and in particular poor emission properties and poor odor behavior.
• Odor behavior is the inclination of materials after a temperature and climate storage of specified Continuous release of volatile components that have a noticeable smell.
• ABS / PA polymer blend made of ABS and polyamide
• ABS / PA also has poor UV resistance, poor
• PPE / HTPS polymer blend made of polyphenylene oxide and impact-modified polystyrene. Disadvantages of this material are its poor flowability, poor UV resistance. Foam adhesion and heat aging resistance, as well as its bad smell behavior.
• PET / PC polymer blend of polyethylene terephthalate and polycarbonate
• Disadvantages of this material are its low resistance to stress cracking, for example against plasticizers, and its poor flowability.
• PBT / PC also has poor flowability and stress crack resistance as another material used.
• the abovementioned materials predominantly have only poor heat resistance, which is expressed in only a low Vicat B softening temperature (Vicat B ⁇ 130 ° C.), and poor heat aging resistance.
• a good heat resistance and heat aging resistance of the materials used is essential, however, since the interior of the motor vehicle can heat up considerably, particularly when exposed to solar radiation.
• polymer materials based on PBT / ASA / PSAN polymer blends made of polybutylene terephthalate. Acrylonitrile / styrene / acrylic acid ester copolymer and polystyrene / acrylonitrile copolymer).
• PBT / ASA / PSAN polymer blends made of polybutylene terephthalate. Acrylonitrile / styrene / acrylic acid ester copolymer and polystyrene / acrylonitrile copolymer.
• Such materials are generally disclosed in DE-A 39 11 828.
• the exemplary embodiments relate to molding compositions with a high acrylonitrile content of the PSAN copolymers.
• molded parts made from these molding compounds like the majority of the materials mentioned above, have poor emission and odor behavior.
• Injection of the molding compound melt and the demolding of the injection molded part defined.
• the length of the cycle time has a direct effect on the number of pieces per injection molding system and thus on the cost of the injection molded part. It is true that the tendency of the molding compound to stick can be counteracted by cooling the injection molds. On the one hand, however, this involves a high level of technical complexity. Furthermore, cooling is repeated for each cycle a large number of cycles to a faster material fatigue of the injection mold due to the associated temperature fluctuations, which then has to be replaced more frequently.
• the object of the invention is to provide suitable molding compositions for the production of molded parts which are used in the interior of motor vehicles and for exterior parts of the body, which have a favorable property profile with regard to their mechanical, optical and surface properties, and in particular good heat resistance, heat aging resistance and a have good emission behavior and / or smell behavior.
• the molding compositions should have the lowest possible density. The low density is particularly advantageous in terms of fuel savings in motor vehicles.
• the molded parts should be easy to recycle.
• Another object is that the adhesiveness of the molding compositions is reduced by the injection molding process, without other properties being adversely affected by this reduction.
• the object is achieved by a molding composition comprising, based on the sum of components A to G, which gives a total of 100% by weight,
• component C2 10 to 50% by weight of acrylonitrile and / or methacrylonitrile as component C2, in each case based on component C,
• Component D The percentage by weight of acrylonitrile and / or methacrylonitrile in component C and component D is different.
• nucleating agent 0.01 to 10% by weight of at least one nucleating agent and at least one transesterification stabilizer.
• mass ratio of nucleating agent to transesterification stabilizer is 1: 100 to 100: 1, preferably 1:10 to 10: 1 and particularly preferably 1: 3 to 3: 1, as component F,
• component G 0.1 to 10% by weight of conventional additives such as carbon black.
• additives such as carbon black.
• UV stabilizers, oxidation retardants, lubricants and mold release agents as component G. The components that are different from one another are explained in detail below.
• the molding composition according to the invention contains up to 99.59% by weight of the molding composition, preferably 20 to 75% by weight, particularly preferably 30 to 60% by weight, of a preferably meltable polycondensate, preferably a polyester and particularly, as the remaining constituent preferably an aromatic polyester.
• a preferably meltable polycondensate preferably a polyester and particularly, as the remaining constituent preferably an aromatic polyester.
• the polycondensates contained in the molding compositions according to the invention are known per se. It is preferred that the polycondensates have a viscosity number (VZ) in the range from 40 to 170, preferably 80 to 140 and particularly preferably 100 to 135.
• the polyesters can preferably be prepared by reacting terephthalic acid, its esters or other ester-forming derivatives with 1,4-butanediol, 1,3-propanediol or 1,2-ethanediol in a manner known per se.
• terephthalic acid can be replaced by other dicarboxylic acids.
• examples include naphthalenedicarboxylic acids. Isophthalic acid, adipic acid, azelaic acid, sebacic acid. Dodecanedioic acid and cyclohexanedicarboxylic acids, mixtures of these carboxylic acids and ester-forming derivatives thereof.
• dihydroxy compounds 1, 4-butanediol, 1,3 propanediol or 1, 2-ethanediol can also be replaced by other dihydroxy compounds, e.g. 1,6-hexanediol, 1,4-hexanediol, 1,4-cyclohexanediol, 1,4-di (hydroxymethyl) cyclohexane.
• Bisphenol A Neopentylglycol, mixtures of these diols and ester-forming derivatives thereof are replaced.
• polytrimethylene terephthalate PTT
• PBT polybutylene terephthalate
• Terephthalic acid and the corresponding diols 1,2-ethanediol, 1,3-propanediol and 1, 4-butanediol are formed.
• the aromatic polyesters can also be used in whole or in part in the form of polyester recyclates, such as PET regrind from bottle material or from waste from bottle production.
• component A consists of
• a2) 0 to 50% by weight. 0 to 20% by weight. particularly preferably 0 to 10% by weight of a further polycondensate.
• the molding composition contains no PET.
• molding compositions are preferred in which component A
• the molding composition according to the invention contains 1 to 20% by weight, preferably 2 to 8% by weight, particularly preferably 2.5 to 7% by weight, in particular 3 to 6% by weight, of at least one particulate graft copolymer with a
• Glass transition temperature of the soft phase below 0 ° C and an average particle size of 50 to 1000 nm.
• Component B is preferably a graft copolymer
• the particulate graft base B1 cannot contain from 70 to 100% by weight of a Ci to Cio-conjugated diene or both, preferably a Ci to Go alkyl ester of acrylic acid, 0 to 30% by weight of a difunctional monomer with two olefinic mixtures conjugated double bonds exist.
• grafting bases are used, for example, in ABS polymers or MBS polymers
• Component B used.
• the graft base B1 consists of the monomers
• the graft base B1 is an elastomer which has a glass transition temperature of preferably below -20 ° C. particularly preferably below -30 ° C.
• the main monomers B1 are esters of
• Particularly preferred monomers B 11 are iso- and n-butyl acrylate and 2-ethylhexyl acrylate, of which butyl acrylate is particularly preferred.
• 0.1 to 10 preferably 0.1 to 5, particularly preferably 1 to 4% by weight of a polyfunctional monomer having at least two olefinic, non-conjugated double bonds are used as the crosslinking monomer B12.
• a polyfunctional monomer having at least two olefinic, non-conjugated double bonds are used as the crosslinking monomer B12.
• examples are divinylbenzene, diallyl fumarate, diallyl phthalate, triallyl cyanurate, triallyl isocyanurate, tricylodecenyl acrylate and dihydricicyclopentadienyl acrylate, of which the latter two are particularly preferred.
• the graft base B1 does not contain 1,3-butadiene, in particular the graft base B1 consists exclusively of the components B1 and B12.
• graft base B1 On the graft base B1 is a graft B2 from the monomers
• b21 50 to 90% by weight, preferably 60 to 90% by weight, particularly preferably 65 to 80% by weight of a vinylaromatic monomer as component B21 and b22) 10 to 50% by weight, preferably 10 to 40% by weight .-%, particularly preferably 20 to 35 wt .-% acrylonitrile or methacrylonitrile or mixtures thereof
• vinyl aromatic monomers are unsubstituted styrene and substituted styrenes such as ⁇ -methylstyrene, p-chlorostyrene and p-chloro- ⁇ -methylstyrene. Unsubstituted styrene and ⁇ -methylstyrene are preferred; unsubstituted styrene is particularly preferred.
• the average particle size of component B is 50 to 200 nm, preferably 55 to 150 nm.
• the average particle size of component B is 200 to 1000 nm, preferably 400 to 550 nm.
• the particle size distribution of component B is bimodal, component B being 10 to 90% by weight, preferably 30 to 90% by weight, particularly preferably 50 to 75% by weight, from one small-sized graft copolymer with a medium
• Particle size of 50 to 200 nm Preferably 55 to 150 nm and 10 to 90% by weight, preferably 10 to 70% by weight, particularly preferably 25 to 50% by weight, of a large-particle graft copolymer with an average particle size of 250 to 1000 nm, preferably about 400 to 550 nm.
• the sizes determined from the integral mass distribution are given as the average particle size or particle size distribution.
• the mean particle sizes according to the invention are in all cases the weight average of the particle sizes, as determined by means of an analytical ultra-centrifuge according to the method of W. Scholtan and H. Lange, Kolloid-Z. and Z.-Polymer 250 (1972), pages 782 to 796.
• the ultracentrifuge measurement provides the integral mass distribution of the particle diameter of a sample. From this it can be seen what percentage by weight of the particles have a diameter equal to or smaller than a certain size.
• the mean particle diameter which is also referred to as the dso value of the integral mass distribution, is defined as the particle diameter at which 50% by weight of the particles have a smaller diameter than the diameter of which corresponds to the d 5 o value. Likewise, 50% by weight of the particles then have a larger diameter than the dso value.
• the d 10 and d 90 values resulting from the integral mass distribution are used. The DIO or d 9 o of the cumulative mass distribution thereby corresponding to the d 5 o-defined value, with the difference that they are based on 10 and 90 wt .-% of the particles. The quotient
• Emulsion polymers A which can be used according to the invention as component A preferably have Q values less than 0.5, in particular less than 0.35.
• the graft copolymer B is generally one or more stages, i. H. a polymer composed of a core and one or more shells.
• the polymer consists of a basic stage (graft core) B 1 and one or - preferably - several stages B2 (graft support) grafted thereon, the so-called graft stages or graft shells.
• One or more graft shells can be applied to the rubber particles by simple grafting or multiple grafting, each graft sheath having a different composition.
• grafting monomers polyfunctional crosslinking or reactive groups can be included
• Monomers are also grafted on (see e.g. EP-A 0 230 282, DE-A 36 01 419, EP-A O 269 861).
• crosslinked acrylic acid ester polymers with a glass transition temperature below serve as the graft base B1
• the crosslinked acrylic ester polymers should preferably be one Glass transition temperature below -20 ° C, especially below -30 ° C, have.
• a multi-layer structure of the graft copolymer is also possible, with at least one inner shell having a glass transition temperature of below 0 ° C. and the outermost shell having a glass transition temperature of more than 23 ° C.
• the graft B2 consists of at least one graft shell and the outermost graft shell thereof has a glass transition temperature of more than 30 ° C, one of which consists of the monomers
• Graft pad B2 formed polymer would have a glass transition temperature of more than 80 ° C.
• Suitable preparation processes for graft copolymers B are emulsion, solution, bulk or suspension polymerization. The are preferred
• Graft copolymers B prepared by radical emulsion polymerization, at temperatures from 20 ° C to 90 ° C using water-soluble and / or oil-soluble initiators such as peroxodisulfate or benzyl peroxide. or with the help of redox initiators. Redox initiators are also suitable for polymerization below 20 ° C.
• Suitable emulsion polymerization processes are described in DE-A-28 26 925, DE-A 31 49 358 and in DE-C-12 60 135.
• the graft casings are preferably constructed in the emulsion polymerization process, as described in DE-A-32 27 555, 31 49 357, 31 49 358, 34 14 118.
• the particle sizes according to the invention are preferably set from 50 to 1000 nm according to the processes described in DE-C-12 60 135 and DE-A-28 26 925, or Applied Polymer Science, Volume 9 (1965), page 2929.
• the molding compositions according to the invention contain, as component C, 0.1 to 20% by weight, preferably 5 to 15% by weight, particularly preferably 8 to 12% by weight, of a copolymer of the monomers
• cl 50 to 90% by weight, preferably 75 to 90% by weight, particularly preferably 85 to 80
• Suitable vinyl aromatic monomers are the above-mentioned monomers C1 and the above-mentioned vinyl aromatic monomers as component B21.
• Component C is preferably an amorphous polymer, as described above as graft B2.
• a copolymer of styrene and / or ⁇ -methylstyrene with acrylonitrile is used as component C.
• the acrylonitrile content in these copolymers of component C is not above 25% by weight and is generally 10 to 25% by weight, preferably 10 to 22% by weight. particularly preferably 10 to 19% by weight, in particular 15 to 19% by weight.
• a copolymer of component C is preferably a styrene / acrylonitrile copolymer.
• a styrene / acrylonitrile copolymer an ⁇ -methylstyrene / acrylonitrile copolymer or an ⁇ -methylstyrene / styrene / acrylonitrile polymer.
• the acrylonitrile content in these copolymers does not exceed 25% by weight, in particular 19% by weight, and is at least 1% by weight.
• the copolymers can be used individually or as a mixture for component C, so that the additional, separately produced component C of the molding compositions according to the invention is, for example
• styrene / acrylonitrile copolymer PSAN
• ⁇ - MethylstyroI / acrylonitrile copolymer can act.
• the acrylonitrile content of the various copolymers of component C can also be different.
• component C preferably consists only of one or more styrene / acrylonitrile copolymers, it being possible for the copolymers to have a different acrylonitrile content.
• styrene / acrylonitrile copolymer PSAN
• ⁇ - MethylstyroI / acrylonitrile copolymer ⁇ - MethylstyroI / acrylonitrile copolymer
• component C consists of only one styrene / acrylonitrile copolymer.
• the molding compositions according to the invention contain, as component D, 0 to 20% by weight, preferably 0.1 to 12.5% by weight, particularly preferably 5 to 7.5% by weight of one
• Copolymers as in component C the percentage by weight of acrylonitrile and / or methacrylonitrile, preferably acrylonitrile, being different in components C and D.
• the acrylonitrile and / or methacrylonitrile content of the copolymer of component D is preferably above that in component C.
• a copolymer of styrene and / or ⁇ -methylstyrene with acrylonitrile is used as component D.
• the acrylonitrile content in these copolymers of component C is above 25% by weight and is generally> 25 to 40% by weight and in particular> 25 to 35% by weight.
• a copolymer of component D is preferably a styrene / acrylonitrile copolymer, an ⁇ -methylstyrene / acrylonitrile copolymer or an ⁇ -methylstyrene / styrene / acrylonitrile terpolymer. It is also preferred here that the content of acrylonitrile in these copolymers in
• the copolymers can be used individually or as a mixture for component D, so that the additional, separately produced component D of the molding compositions according to the invention is, for example, a mixture of a styrene / acrylonitrile copolymer (PSAN) and an ⁇ -SAN
• PSAN styrene / acrylonitrile copolymer
• Methyl styrene / acrylonitrile copolymer can act. Also the acrylonitrile content the different copolymers of component D can be different. However, component D preferably consists only of one or more styrene / acrylonitrile copolymers, it being possible for the copolymers to have a different acrylonitrile content. In a particularly preferred embodiment, component C consists of only one styrene acrylonitrile
• the molding composition according to the invention contains 0.1 to 20, preferably 0.1 to 15 and particularly preferably 0.1 to 10% by weight, based on the total molding composition, of a polyester different from component A as component E.
• Polyester of component E has at least 50, preferably at least 70 and particularly preferably 100% by weight of polyethylene terephthalate (PET), based on component E.
• PET polyethylene terephthalate
• the aromatic polyesters already defined above are preferred as further polyesters of component E.
• the PET can be used either directly from the synthesis or as a recyclate, preferably from regrind from PET bottles.
• the use of recycled PET is advisable on the one hand for reasons of cost and on the other hand because of the effect of the recycled material on improving the toughness of the molding compound.
• the PET used in component E according to the invention thus preferably consists of at least 50, preferably at least 80 and particularly preferably 100% of recycled PET.
• the molding composition according to the invention contains 0.01 to 10, preferably 0.02 to 5 and particularly preferably 0.05 to 2% by weight of at least one nucleating agent and at least one transesterification stabilizer, the ratio of nucleating agent to transesterification stabilizer 0: 1 to 1: 10, preferably 5: 1 to 1
• the nucleating agent in component F is a particulate solid with a grain size in the range from 0.1 to 15 ⁇ m, or the transesterification stabilizer contains at least one phosphorus-containing one
• Compound, or the nucleating agent is a predominantly inorganic.
• Such compounds forming the transesterification stabilizer can be both organic and inorganic phosphorus compounds.
• organic compounds forming the transesterification stabilizer can be both organic and inorganic phosphorus compounds.
• Phosphorus compounds are particularly preferred organic phosphites.
• Such a phosphite is tetrakis (2,4-di-tert-butylphenyl) bisphenyl diphosphite (Igaphos PEPQ from Ciba Geigy AG).
• Inorganic phosphorus compounds for example monozinc phosphates, in particular as mono- or dihydrate or mixtures thereof, are particularly suitable as inorganic phosphorus compounds, with monozinc phosphate dihydrate being particularly preferred.
• the transesterification catalyst is preferably used in the range from 0.01 to 5, preferably 0.05 to 2 and particularly preferably 0.1 to 0.3% by weight, based on the molding composition.
• transesterification inhibitors work by deactivating residues of the catalyst required in the synthesis of polyesters.
• These catalysts are organotitanium compounds such as alkyl titanates. These are able to activate ester groups or initiate transesterification reactions via free coordination points. This leads to the formation of copolyesters. which are characterized by a lower crystallinity, which increases the undesirable tendency to stick when demolding injection molded parts.
• Transesterification inhibitors are coordinated to the titanate; the resulting Zn / Ti complex is inactive towards the ester groups.
• the molding composition according to the invention preferably contains in the range from 0.01 to 5, preferably 0.02 to 1 and particularly preferably 0.05 to 0.2% by weight of nucleating agent.
• Component F can also be used to reduce the adhesiveness of the molding compositions according to the invention.
• the adhesiveness of the molding compositions to the surface of injection molds is reduced.
• a reduction in the adhesiveness in the range of the processing temperature of the molding composition according to the invention and particularly in a temperature range from 200 to 300, preferably 250 to 300 ° C. is particularly preferred. which prevails in the injection molding process.
• Adhesion-reducing agents of this type are those known to the person skilled in the art for such molding compositions. This means that both the injection molding process and the molding compound are preferably free of adhesion-reducing agents.
• the molding compositions according to the invention contain 0.1 to 10% by weight as component G.
• additives % usual additives.
• additives are: UV stabilizers, oxidation retarders, lubricants and mold release agents, dyes,
• Pigments, colorants, antistatic agents Pigments, colorants, antistatic agents.
• These additional additives can be metered in at any stage of the production process, but preferably at an early stage in order to take advantage of the stabilizing effects (or other special effects) of the additive at an early stage.
• Heat stabilizers or oxidation retardants are usually metal halides (chlorides, bromides, iodides) which are derived from metals of group I of the periodic table of the elements (such as Li, Na, K, Cu).
• Suitable stabilizers are the usual hindered phenols, but also vitamin E or compounds with an analog structure. Also HALS stabilizers (hindered amine light stabilizers). Benzophenone, Resorcine, Salicvlate. Benzotriazoles and other compounds are suitable (e.g. Irganox®, Tinuvin®, such as
• Tinuvin® 770 HALS absorber. Bis (2,2.6.6-tetramethyl-4-piperidyl) sebacate) or Tinuvin®P (UV absorber - (2H-benzotriazol-2-yl) -4-methylphenol). Topanol®). These are usually used in amounts of up to 2% by weight (based on the mixture as a whole).
• Suitable lubricants and mold release agents are stearic acid, stearyl alcohol, stearic acid esters or generally higher fatty acids, their derivatives and corresponding fatty acid mixtures with 12 to 30 carbon atoms.
• the amounts of these additives are in the range from 0.05 to 1% by weight.
• Silicone oils, oligomeric isobutylene or similar substances can also be used as additives; the usual amounts are 0.05 to 5% by weight.
• Cadmium sulfides, derivatives of perylene tetracarboxylic acid can also be used.
• Processing aids and stabilizers such as UV stabilizers, lubricants and antistatic agents are usually used in amounts of 0.01 to 5% by weight, based on the total molding composition.
• Plasticizers such as dioctyl phthalate, dibenzyl phthalate, butyl phthalate, hydrocarbon oils, N- (n-butyl) benzene sulfonamide. o- and p-
• Toluene ethyl sulfonamide are advantageous in amounts of up to about 5% by weight. based on the molding compound added.
• Colorants such as dyes and pigments, can be added in amounts of up to about 5% by weight, based on the molding composition.
• the molding composition according to the invention has a component G with a copolymer which contains no butadiene or isoprene derivative or neither.
• the molding compositions of the invention additionally comprise, as component H, 0 to 30, preferably 0 to 20 and particularly preferably 0.1 to 12% by weight of their mass of a polycarbonate.
• All polycarbonates known to the person skilled in the art are suitable as polycarbonates, the meltable ones being particularly suitable.
• "An Introduction Polymer Chemistry,” 2 n 2 n Edition Edition George Odian Whiley Interscience is on, Malcolm P. Stevens Oxford University Press. 1990. Pages 400-403 and "Principles of Polymerization ''...
• Particularly suitable polycarbonates have a high flowability, preferably an MVR at 300 ° C and 1.2 kg of> 9, preferably> 13 and more preferably> 20 cm3 / 10 min, wherein components a H preferred MVR according to ISO 1133 of up to Show 100, preferably 90 and particularly preferably 50 cm / 10 min.
• MVR MVR at 300 ° C and 1.2 kg of> 9, preferably> 13 and more preferably> 20 cm3 / 10 min
• components a H preferred MVR according to ISO 1133 of up to Show 100 preferably 90 and particularly preferably 50 cm / 10 min.
• Component H is preferred Lexan 121R from General Electric Plastics. Furthermore, the use of PC recyclate as both “post industrial” and “post consumer recyclate” * has proven to be particularly suitable, since it can be processed particularly well.
• the molding composition is free of polycarbonate.
• the molding composition according to the invention can contain, in addition to 0 to 30% by weight of its mass, a polycarbonate as component H and from 0.1 to 100, preferably 1 to 50 and particularly preferably 10 to 30% by weight of its mass a fiber as component I. or contain both in one embodiment.
• Such fibers generally have an average length of 0.1 to 0.5, preferably 0.1 to 0.4 mm, and a diameter in the range of 6 to 20 ⁇ m.
• the fibers can be coated with organosilanes, epoxysilanes or other polymer coatings.
• the components can be mixed in any desired manner by all known methods.
• the components can be used as such or in the form of mixtures of one component with one or more of the other components.
• the component can be used as such or in the form of mixtures of one component with one or more of the other components.
• the component can be used as such or in the form of mixtures of one component with one or more of the other components.
• the component can be used as such or in the form of mixtures of one component with one or more of the other components.
• the component can be used as such or in the form of mixtures of one component with one or more of the other components.
• the component can be used as such or in the form of mixtures of one component with one or more of the other components.
• components B, C and D have been prepared, for example, by emulsion polymerization, it is possible to mix the polymer dispersions obtained with one another, to precipitate the polymers together, and to work up the polymer mixture.
• components B, C and D are preferably mixed by extruding, kneading or rolling the components together, components B, C and D having, if necessary, been isolated beforehand from the solution or aqueous dispersion obtained in the polymerization.
• thermoplastic molding compositions according to the invention can be produced, for example, by melting component A with components B, C or D with a mixture of these, and optionally with the other components, in an extruder and feeding the fibers through an inlet on the extruder ,
• the molding compositions according to the invention can by the known methods of Thermoplastic processing to be molded.
• they can be produced by thermoforming, extrusion, injection molding, calendering, blow molding, pressing, press sintering, deep drawing or sintering, preferably by injection molding.
• the moldings produced from the molding compositions according to the invention are also the subject of the present invention.
• the molded parts produced from the molding compositions according to the invention have only low emissions of volatile constituents with a noticeable odor.
• the olfactory behavior of polymer materials is assessed according to DEN 50011 / PV 3900 and applies to components of the vehicle interior. The result of
• odor testing according to this standard is generally better than grade 5, preferably better than grade 4.5 and particularly preferably better than grade 4.
• the carbon emission of the shaped parts according to PV 3341 is generally ⁇ 50 ⁇ g / g, preferably ⁇ 40 ⁇ g / g, particularly preferably ⁇ 35 ⁇ g / g.
• the lower limit is preferably 20 ⁇ g / g.
• the moldings according to the invention also have good heat resistance.
• the Vicat B softening temperature is generally> 120 ° C, preferably> 125 ° C and particularly preferably 130 ° C.
• the upper limit of the Vicat B softening temperature is preferably 160 ° C.
• the moldings according to the invention also have good impact strength, even in the cold. This manifests itself in the fact that the molded parts formed from the molding compositions according to the invention show no breakage even at low temperatures.
• the modulus of elasticity is preferably> 2000, preferably> 3500 MPa, maximally 15000 MPa, and their tensile stress in general> 40, preferably> 70 MPa. however preferably at a maximum of 150 MPa, their impact strength according to ISO 179 / leU is unbreakable, preferably it lies in the
• Range from 30 to 80 kJ / m " and their flowability as MVR (Melt-Volume-Ratio 275 ° C / 2.16 kp bearing force according to ISO 1133) is> 10, preferably> 15 cm 3/10 min, with a maximum at 30 cm / 10 min.
• the molded parts according to the invention show no splintering behavior in the puncture test (2 and 3 mm plate diameter, in accordance with ISO 6603/2).
• the density of the molding composition is in the range from 1.1 to 1.5, preferably from 1.2 to 1.4 and particularly preferably from 1.2 to 1.3 g / cm.
• the invention further relates to a laminate which contains a molded part according to the invention and a polycondensate foam.
• molded part and polycondensate foam are advantageously, molded part and
• Polycondensate foam is firmly bonded to one another via their surfaces.
• the laminates are notable for excellent foam adhesion to the surface of the molded part, without the need to pretreat the surface of the molded part, for example with a primer.
• a primer When the foam is pulled off or peeled off from the molded part surface, cohesive breakage is observed; foam residues remain on the surface.
• All foamable polycondensates known to the person skilled in the art can be used for the polycondensate foam.
• it is preferred that the foam is applied to the molding surfaces without the use of a primer.
• polyamides and polyurethanes are preferred and polyurethanes are particularly preferred.
• polyurethane foams semi-rigid and flexible foams are again particularly preferred; if necessary, these may include adhesion promoters.
• the product Elastoflex from Elastogran GmbH, Lemförde is used as the polyurethane foam.
• Further suitable polyurethanes can be found in the plastics handbook volume 7 "Polyurethane '", 3.
• the molding compositions according to the invention and subsequent moldings or structures are suitable for recycling.
• the recyclates obtained from the molding compositions and moldings according to the invention can be processed again to give moldings which have at least one of the material properties described above.
• Recycled molded parts of this type have at least 10, preferably at least 20 and particularly preferably at least 70% by weight, based on the molded part, of recyclate.
• the recycling takes place according to methods generally known to the person skilled in the art.
• the molding compositions according to the invention in particular facilitate the comminution and the thermal recycling of the molded parts. In this Connection-free molding compounds are particularly preferred.
• recycling technology takes the usual steps such as dismantling easily separable materials and fasteners, peeling off polyurethane foam when it has been applied to the composites according to the invention, crushing, separating and classifying, further preparation steps such as mixing and homogenizing in suitable devices, cleaning and dedusting under process conditions generally known to the person skilled in the art. This is followed by reprocessing the polymer in the manner described above.
• the molding compositions or moldings or laminates or recyclates or at least two of them according to the invention are suitable for use in structures, in particular for applications in the interior of motor vehicles or for exterior parts of motor vehicles.
• the invention relates to structures, preferably for the interior of Motor vehicles or for exterior parts of motor vehicles, including molding compositions or molded parts according to the invention or laminates or recyclates or at least two of them.
• the molded parts or structures according to the invention can be laser patterned.
• Moldings or structures according to the invention for the motor vehicle interior are therefore preferably covers, storage compartments, instrument panel supports, door sills, parts for the center console and brackets for radio and
• Air conditioning Panels for the center console, panels for the radio, air conditioning and ashtray, extensions of the center console, storage pockets. Storage for the driver and front passenger door, storage for the center console. Components for the driver and front passenger seat, such as seat panels.
• Light switch housing Lamp housing, housing for vehicle electronics, such as anti-lock braking system, anti-slip control, electronic stability control. Gearbox, seat, mirror motor, window lift motor, convertible top control, airbag release, seat occupancy detection, interior security, acceleration sensor and ignition electronics, power strips, connectors, locking system housing, wiper housing covers, lock housing and luggage rack roof rails, defroster channel.
• Sunroof elements such as sunroof frames. Instrument scoops and covers, instrument mounts, upper and lower shells for the steering column, air ducts, air vents and intermediate pieces for inflows and defroster ducts, door side panels, panels in the knee area, air outlet nozzles, defroster openings, switches and levers.
• Fenders tailgates. Side panels. Bumpers, planking, identification Drawing board supports, panels, sunroof panels or frames as well as bumpers or their components are preferred.
• boat hulls, lawn mower housings, garden furniture, motorcycle parts, camera housings, cell phone housings, sockets for binoculars, vapor channels for extractor hoods, parts for pressure cookers, housings for hot air grills and pump housings are only examples of other moldings or structures that are not limited to the motor vehicle sector.
• the use of the molding compounds has proven particularly useful in connectors.
• Housing parts in particular for automotive electronics, such as in particular ABS / ASR, ESP gearbox, seat, mirror motor, window lift motor, convertible top control, airbag release, interior security, acceleration sensor and ignition electronics as well as electronics for detection the seat occupancy.
• automotive electronics such as in particular ABS / ASR, ESP gearbox, seat, mirror motor, window lift motor, convertible top control, airbag release, interior security, acceleration sensor and ignition electronics as well as electronics for detection the seat occupancy.
• the molding compositions according to the invention for locking system housings, car relays, covers for wiper housings and for lock housings.
• Another preferred group of molded parts or structures that can be produced from the molding compositions according to the invention are gas meter housings. wind deflectors,
• the servomotors are preferably used in motor vehicle construction, drilling machine parts, furnace parts, in particular for thermal insulation, such as holding buttons and furnace handles, windshield wiper parts, in particular
• Wiper blade holders for spoilers, mirror support plates for automotive mirrors, and housings for washing machine controls.
• the molding compositions according to the invention are suitable for other moldings used in the household area, preferably in the kitchen area. These include bread makers, toasters, table grills, kitchen machines, electric can openers and juicers.
• the molding compositions according to the invention are preferably used for switches, housings, handles and Lid made.
• the molding compositions according to the invention can furthermore be used for molded parts of stoves. For cookers, stove handles, stove knobs and switches are particularly preferred.
• molding compositions according to the invention are in moldings which meet the requirements of the Federal Drug Administration or comparable national authorities in other countries.
• pharmaceutical packaging and containers for pharmaceutical kits are particularly preferred.
• molding compositions according to the invention can be used in the field of food packaging.
• molded parts from the molding compositions according to the invention such as boxes, pots, trays and containers of other types, are preferred.
• Such molded parts are, in particular, headlight parts which are used in the area of the headlight in which temperatures above 100 ° C., preferably 110 ° C. and particularly preferred during operation of the headlight
• Such parts can be both glass fiber reinforced and glass fiber unreinforced.
• the advantage of using the molding compositions according to the invention is, in particular, that it is used in such headlight parts with reflective metallized
• molding compositions according to the invention so that even during prolonged operation of the headlamp there are no deposits on the transparent areas of the headlamp through which the light passes, and the reflective properties of metallized surfaces of these moldings are retained.
• the molding compositions according to the invention can also be used to produce further
• headlight components include, in particular, headlight housings, frames, holders and guides, headlight frames being preferred.
• Molding compounds such as low cycle times, no formation of mold during injection molding, excellent quality of the metallized surfaces.
• the use of the molding compositions according to the invention has proven itself in the production of large-area moldings which are comparatively thin in relation to their area and which require excellent demolding behavior.
• large-area molded parts are, in particular, sunroof cross members, body parts, air inlet grilles, parts of instrument panels, such as instrument panel supports, covers, air ducts, add-on parts, in particular for the center console, part of a glove compartment and speedometer covers.
• PBT is a polybutylene terephthalate with a viscosity number of 130 (determined in a polymer solution (0.05 g / ml) from phenol and 1, 2-dichloromethane (1: 1)).
• Pl is a small-part ASA graft rubber with 25% by weight acrylonitrile in the SAN
• PSAN 33 is a styrene-acrylonitrile copolymer with 33% by weight acrylonitrile.
• PSAN 19 is a styrene / acrylonitrile copolymer with 19% by weight acrylonitrile.
• the mold release agent is Loxiol VPG 861 / 3.5 from Henkel.
• the nucleating agent is Talc IT Extra.
• Transesterification stabilizer is monozinc phosphate dihydrate.
• Soot is Black Pearls 880.
• Table 2 contains the results of the tests carried out.
• the cycle time was determined on a demolding bar (bar with 40 short ribs).
• the molded part had the following dimensions:
• Kegelanguß Spraying / tool temperature 270 ° C / 80 ° C
• the cooling time and thus the cycle time are reduced until the molded part with its ribs gets caught in the tool. Getting stuck is a clear assessment criterion.
• the minimum cycle time is the time that is just one

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• 1999
  • 1999-06-25 DE DE19929302A patent/DE19929302A1/de not_active Withdrawn
• 2000
  • 2000-06-23 EP EP00943880A patent/EP1194484B1/de not_active Expired - Lifetime
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