EP4028465A1 - Hochvoltkomponenten - Google Patents
HochvoltkomponentenInfo
- Publication number
- EP4028465A1 EP4028465A1 EP20761853.9A EP20761853A EP4028465A1 EP 4028465 A1 EP4028465 A1 EP 4028465A1 EP 20761853 A EP20761853 A EP 20761853A EP 4028465 A1 EP4028465 A1 EP 4028465A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- polymer compositions
- mass
- parts
- voltage components
- glass
- 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.)
- Pending
Links
Classifications
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K13/00—Use of mixtures of ingredients not covered by one single of the preceding main groups, each of these compounds being essential
- C08K13/02—Organic and inorganic ingredients
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B7/00—Mixing; Kneading
- B29B7/80—Component parts, details or accessories; Auxiliary operations
- B29B7/88—Adding charges, i.e. additives
- B29B7/90—Fillers or reinforcements, e.g. fibres
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29B—PREPARATION OR PRETREATMENT OF THE MATERIAL TO BE SHAPED; MAKING GRANULES OR PREFORMS; RECOVERY OF PLASTICS OR OTHER CONSTITUENTS OF WASTE MATERIAL CONTAINING PLASTICS
- B29B9/00—Making granules
- B29B9/02—Making granules by dividing preformed material
- B29B9/06—Making granules by dividing preformed material in the form of filamentary material, e.g. combined with extrusion
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- 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
- B29C45/0001—Injection moulding, i.e. forcing the required volume of moulding material through a nozzle into a closed mould; Apparatus therefor characterised by the choice of material
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- 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
- B29C48/00—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor
- B29C48/022—Extrusion moulding, i.e. expressing the moulding material through a die or nozzle which imparts the desired form; Apparatus therefor characterised by the choice of material
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- 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
- B29C49/00—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor
- B29C49/0005—Blow-moulding, i.e. blowing a preform or parison to a desired shape within a mould; Apparatus therefor characterised by the material
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- 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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/28—Treatment by wave energy or particle radiation
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/016—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/005—Stabilisers against oxidation, heat, light, ozone
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
- C08K5/0066—Flame-proofing or flame-retarding additives
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K7/00—Use of ingredients characterised by shape
- C08K7/02—Fibres or whiskers
- C08K7/04—Fibres or whiskers inorganic
- C08K7/14—Glass
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- 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
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
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- 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
- B29K2067/006—PBT, i.e. polybutylene terephthalate
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- 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
- B29K2069/00—Use of PC, i.e. polycarbonates or derivatives thereof, as moulding material
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- 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
- B29K2995/00—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds
- B29K2995/0012—Properties of moulding materials, reinforcements, fillers, preformed parts or moulds having particular thermal properties
- B29K2995/0016—Non-flammable or resistant to heat
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B29—WORKING OF PLASTICS; WORKING OF SUBSTANCES IN A PLASTIC STATE IN GENERAL
- B29L—INDEXING SCHEME ASSOCIATED WITH SUBCLASS B29C, RELATING TO PARTICULAR ARTICLES
- B29L2031/00—Other particular articles
- B29L2031/34—Electrical apparatus, e.g. sparking plugs or parts thereof
- B29L2031/3406—Components, e.g. resistors
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- 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
- C08J2367/00—Characterised by the use of polyesters obtained by reactions forming a carboxylic ester link in the main chain; Derivatives of such polymers
- C08J2367/02—Polyesters derived from dicarboxylic acids and dihydroxy compounds
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/30—Sulfur-, selenium- or tellurium-containing compounds
- C08K2003/3009—Sulfides
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
- C08K5/16—Nitrogen-containing compounds
- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3442—Heterocyclic compounds having nitrogen in the ring having two nitrogen atoms in the ring
- C08K5/3462—Six-membered rings
- C08K5/3465—Six-membered rings condensed with carbocyclic rings
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L2203/00—Applications
- C08L2203/20—Applications use in electrical or conductive gadgets
Definitions
- the present invention relates to high-voltage components, in particular for electromobility, containing polymer compositions based on at least one polyester and at least one sulfide containing cerium, and their use for producing polyester-based high-voltage components or for marking polyester-based products as high-voltage components by means of lasers.
- thermoplastics such as polyester are an important material due to their good mechanical stability, chemical resistance, very good electrical properties and good processability, especially in the area of components for motor vehicles.
- WO 01/42371 A1 discloses polymer compositions based on Uralac® SN800, a polyester. According to claim 16, C 2 S 3 can be used as the rare earth metal sulfide.
- EP 0 041 274 B1 describes fluorescent compositions with the ability to change the wavelengths of light, moldings based on such compositions as elements converting light waves and devices for converting optical energy into electrical energy using such an element.
- EP 0 041 274 B1 among other things, 12H-phthaloperin-12-one in polyethylene terephthalate (PET) is used.
- Solvent Orange 60 12H-phthaloperin-12-one [CAS No. 6925-69-5], known as Solvent Orange 60, is available, for example, as Macrolex® Orange 3G from Lanxess Deutschland GmbH, Cologne.
- the Solvent Orange 60 migrates to the surface of the plastic (blooming). From there it can be rubbed off, washed off or dissolved, evaporate (fogging) or migrate into other materials (e.g. neighboring plastic or rubber parts) (bleeding). The concentration of Solvent Orange 60 in the original plastic is reduced, which leads to a decrease in color intensity.
- the migrated Solvent Orange 60 also has the disadvantage that it can be transported to neighboring components by mechanical or physical processes and there leads to negative functional impairments. For example, there is an increased electrical resistance in a switch contact, which can result from the deposition of solvent orange 60 on the surface of electrical contacts. In the area of electrical components, the migration of ingredients out of plastics is therefore generally undesirable, since it can influence the properties of the plastics and spatially adjacent parts, which may no longer guarantee the function of the electrical component.
- the object of the present invention was therefore to develop orange polymer compositions based on polyester for high-voltage components, in particular for high-voltage components in electric vehicles, which are less prone to migration, in particular bleeding, compared to the solution in EP 0 041 274 B1 based on 12H-phthaloperin-12-one.
- a suitable means of marking plastic-based components is laser labeling (see https://de.wikipedia.org/wiki/Laserbeschriftung), with diode lasers or ND: YAG lasers with a wavelength of 1064 nm being preferred.
- antimony trioxide in the case of inscriptions with a laser with a wavelength of 1064 nm, additives based on antimony trioxide are mostly used to improve the inscription contrast (see EP 3 281 974 A1).
- the use of antimony trioxide should preferably be avoided, as it has a negative connotation on the market due to an H351 hazard warning (“Can probably cause cancer”).
- Antimony trioxide can also have a negative effect on the tracking resistance according to IEC 60112, which would be particularly disadvantageous for applications in high-voltage components for electromobility, because if the tracking resistance is lower, the distance between current-carrying assemblies would have to be increased in order to exclude safety risks from undesired current flow.
- An additional object of the present invention is that it can be laser-inscribed at a laser wavelength of 1064 nm even without the addition of antimony trioxide or derivatives containing antimony trioxide and that, if possible, no disadvantages corresponding to the antimony trioxide due to a decrease in the tracking resistance have to be accepted .
- orange polyester-based molding compositions according to the invention should not only be laser-inscribable compared to the prior art cited above, but also have improved lightfastness and improved thermal stability, in that the original color obtained immediately after injection molding is under UV light or under thermal stress is maintained over a longer period of time than in comparison to 12H-phthaloperin-12-one.
- a longer period of time in relation to the thermal stress means storage in a hot air drying cabinet at 80 ° C. for 12 hours.
- a longer period of time with regard to light fastness means an irradiation time with a xenon lamp, 1500 watt, 45-130 klx, and wavelength 300-800 nm of 96 hours.
- high-voltage components in particular high-voltage components for electromobility, containing thermoplastic polymer compositions based on polyester and at least one sulfide containing cerium as an orange colorant, meet the requirements for bleeding as well as lightfastness and the required laser inscribability.
- the invention relates to polymer compositions containing at least one polyester and at least one sulfide containing cerium.
- polymer compositions in which, per 100 parts by mass of polyester, 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, of at least one sulphide containing cerium are used.
- the invention also relates, however, to high-voltage components, in particular
- Polymer compositions containing at least one polyester and at least one sulfide containing cerium are polymer compositions containing at least one polyester and at least one sulfide containing cerium.
- the invention also relates, however, to high-voltage components, in particular
- Polymer compositions containing, per 100 parts by mass of at least one polyester, 0.01 to 5 parts by mass, particularly preferably 0.01 to 3 parts by mass, of at least one sulfide containing cerium.
- the present invention also relates to the use of at least one sulphide containing cerium for the production of polyester-based polymer compositions, preferably polyester-based high-voltage components, in particular polyester-based high-voltage components for electromobility.
- the invention also relates to the use of at least one sulphide containing cerium for marking polyester-based products as high-voltage components using a laser, preferably using a diode laser or ND: YAG laser at a wavelength of 1064 nm.
- the present invention preferably relates to polymer compositions, molding compounds to be produced therefrom and, in turn, high-voltage components or high-voltage components for electromobility to be produced therefrom, with the proviso that these correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011 in the RAL color system.
- the present invention finally relates to one Method for marking polyester-based products as high-voltage components by irradiating the products using a laser, preferably using a diode laser or ND: YAG laser at a wavelength of 1064 nm, at least one sulphide containing cerium being used in the polyester.
- Preferred polyesters are C 2 -C 10 polyalkylene terephthalates or polycarbonate, in particular polybutylene terephthalate (PBT).
- PBT polybutylene terephthalate
- polyester-based polymer compositions according to the invention for use as high-voltage components is carried out by mixing the components A) polyester and B) at least one sulphide containing cerium in at least one mixing tool, with the proviso that the polymer compositions or the high-voltage components or high-voltage components to be produced therefrom for the electric mobility based on A) and B) in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011.
- molding compositions based on the polymer compositions according to the invention as intermediate products.
- These molding compounds can either consist exclusively of components A) and B), or else contain at least one further component in addition to components A) and B), with the proviso that the molding compounds or the high-voltage components or high-voltage components for electromobility to be produced from them based on A) and B) as well as any other components in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011.
- antimony-based components in particular the use of antimony trioxide-containing derivatives, is preferably dispensed with in the production of the polymer compositions or molding compounds.
- plastic plates are made from a polyester composition to be examined and containing colorants with dimensions of 60 * 40 * 2 mm 3.
- colorants with dimensions of 60 * 40 * 2 mm 3.
- at least one sulfide containing cerium is used as the colorant.
- a soft PVC film with the dimensions 30 * 20 * 2 mm 3 is clamped between two of the initially manufactured plastic sheets and the entirety of all sheets is stored in an air drying cabinet at 80 ° C. for 12 hours.
- the subsequent assessment of the colorant migrated from the two plastic sheets into the soft PVC is then carried out visually according to the gray scale according to ISO 105-A02, where '5' means that the PVC film shows no color change (no visually recognizable colorant transfer from the polyester plastic sheets on the PVC film) and '1' means that the PVC film shows a strong change in color (strong, visually recognizable colorant transfer from the polyester plastic plates to the PVC film).
- the discoloration is assessed visually based on the Blue Wool Scale in accordance with DIN EN ISO 105-B02, where '8' stands for excellent light fastness (slight color change) and 'T' stands for very low light fastness (strong color change).
- the term "high voltage” is used in section 2.17 Voltage ”) is described as a voltage for which an electrical component or circuit is designed, the rms value of the operating voltage is> 60 V and ⁇ 1 500 V (direct current) or> 30 V and ⁇ 1 000 V (alternating current).
- high-voltage component is understood to mean components or products that are exposed to an operating voltage in accordance with Section 2.17 of Regulation No. 100 of the United Nations Economic Commission for Europe (UNECE) described above.
- high-voltage components for electromobility are preferably components in electric vehicles that have an operating voltage greater than or equal to 30V (direct current) or greater than or equal to 20 V (alternating current), particularly preferably - based on voltage class B of ISO6469-3: 2018 - a Operating voltages greater than 60V (direct current) or greater than 30V (alternating current) are exposed.
- the high-voltage components for electromobility include both those components that are in direct contact with the live parts and those that have the function of contact protection, warning signs or shielding in the immediate vicinity or spatial proximity, whereby components, which are in direct contact with the live parts are preferred according to the invention.
- Polymer compositions according to the invention are colored orange due to the at least one sulphide containing cerium, with colors in the RAL color system of the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 and RAL2011, are particularly preferred and the color tones that correspond to the color number RAL2003, RAL2004, RAL2008 and RAL2009 in the RAL color system are particularly preferred and RAL 2003 is particularly preferred.
- orange In the context of the present invention, orange is a color that in the RAL color system according to https: //de.wikipedia.0rg/wiki/RAL-Farbe#Orange has a color number in the RAL color table that begins with a "2". On the filing date of the present invention, a distinction is made between orange tones according to Table 1:
- the color model is standardized in EN ISO 11664-4 "Colorimetry - Part 4: CIE 1976 L * a * b * Color space”.
- L * a * b * color space also: CIELAB
- Each color in the color space is defined by a color location with the Cartesian coordinates ⁇ L * , a * , b * ⁇ .
- the a * axis describes the green or red component of a color, with negative values for green and positive values represent red.
- the b * axis describes the blue or yellow component of a color, with negative values for blue and positive values for yellow.
- the a * values range from approx. -170 to +100, the b * values from -100 to +150, with the maximum values only being achieved with medium brightness of certain color tones.
- the CIELAB color body has its greatest expansion in the middle lightness range, which, however, varies in height and size depending on the color range.
- polymer compositions and high-voltage components to be produced therefrom are preferred whose color value comes as close as possible to RAL 2003, pastel orange with L * a * b * 66.02 / 41.22 / 52.36, if not exactly the same.
- the person skilled in the art will select the amounts of the components to be used in the polymer compositions according to the invention in such a way that the result achieved is as much as possible RAL 2003.
- the invention relates to polymer compositions, high-voltage components, in particular
- High-voltage components for electromobility containing in addition to components A) and B) also C) at least one filler and / or reinforcing material, preferably 1 to 150 parts by mass, particularly preferably 5 to 80 parts by mass, very particularly preferably 10 to 50 parts by mass, each based on 100 parts by mass of component A) with the proviso that the polymer compositions or the high-voltage components or high-voltage components to be produced from them for electromobility in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferred the color numbers RAL2003, RAL2004, RAL2008 or RAL2009, most preferably the color number RAL 2003.
- the invention relates to:
- High-voltage components for electromobility containing in addition to components A), B) and C) or instead of C) also D) at least one flame retardant, preferably 3 to 100 parts by mass, particularly preferably 5 to 80 parts by mass, very particularly preferably 10 up to 50 parts by mass, in each case based on 100 parts by mass of component A) with the proviso that the polymer compositions or the high-voltage components or high-voltage components to be produced therefrom for electromobility based on A), B), C) and D) or based on A), B) and D) in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferably the color numbers RAL2003, RAL2004, RAL2008 or RAL2009, very particularly preferably the color number RAL 2003.
- the invention relates to polymer compositions, high-voltage components, in particular
- High-voltage components for electromobility including in addition to the components
- E) is preferably used with the proviso that the polymer compositions or the high-voltage components or high-voltage components to be produced therefrom for electromobility on the basis of A), B), C), D) and E) or on the basis of A), B), E) or on the basis of A), B), C) and E) or on the basis of A),
- B), D) and E) in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferably the color numbers RAL2003, RAL2004, RAL2008 or RAL2009, very particularly preferably the color number RAL 2003.
- polyesters to be used preferably as component A) are C 2 -C 10 polyalkylene terephthalates or reaction products of an alcohol part with 2 to 10 carbon atoms in the alcohol part and terephthalic acid.
- C 2 -C 10 polyalkylene terephthalates are known to the person skilled in the art and are adequately described in the literature. They contain an aromatic ring in the main chain, which is derived from terephthalic acid, and an aliphatic part, which is derived from a dihydroxy compound. The aromatic ring of terephthalic acid can also be substituted.
- Preferred substituents are halogens or C 1 -C 4 -alkyl groups. Preferred halogens are chlorine or bromine.
- Preferred CC 4 alkyl groups are methyl, ethyl, n-propyl or n-, i- or t-butyl groups.
- C 2 -C 0 -Polyalkylenterephthalate may be prepared by reacting aromatic dicarboxylic acids, their esters or other derivatives estersometimesenden with aliphatic dihydroxy compounds in a known manner to the skilled person can be produced.
- C 2 -C 0 -Polyalkylenterephthalate a part of the mole for the production thereof to be used terephthalic acid, up to 30%, by 2,6-naphthalenedicarboxylic acid, or isophthalic acid or mixtures thereof are replaced.
- Up to 70 mol%, preferably not more than 10 mol% of the terephthalic acid can be replaced by aliphatic or cycloaliphatic dicarboxylic acids such as adipic acid, azelaic acid, sebacic acid, dodecanedioic acids and cyclohexanedicarboxylic acids.
- diols with 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 are preferred.
- Particularly preferred polyalkylene terephthalates are derived from alkanediols having 2 to 4 carbon atoms.
- polyethylene terephthalate, polypropylene terephthalate and polybutylene terephthalate or mixtures thereof are particularly preferred.
- PET and / or PBT which contain up to 1% by weight, preferably up to 0.75% by weight, 1,6-hexanediol and / or 2-methyl-1,5-pentanediol as further monomer units.
- C 2 -C 10 polyalkylene terephthalates to be used as component A) preferably have a viscosity number m, to be determined according to ISO 1628, in the range from 50 to 220, preferably in the range from 80 to 160, with in a 0.5% strength by weight solution in a phenol / o-dichlorobenzene mixture, weight ratio 1: 1 at 25 ° C.
- preferred C 2 -C 10 polyalkylene terephthalates to be used as component A) preferably have a carboxyl end group content of up to 100 meq / kg polyester, particularly preferably up to 50 meq / kg polyester and particularly preferably up to 40 meq / kg polyester.
- Such C 2 -C 0 - polyalkylene terephthalates for example, by the process of DE-A 44 01 055. are prepared.
- the carboxyl end group content is usually determined by titration methods, in particular potentiometry.
- C 2 -C 0 - polyalkylene terephthalates are produced with Ti catalysts. After the polymerization, these preferably have a residual Ti content of ⁇ 250 ppm, particularly preferably ⁇ 200 ppm, very particularly preferably ⁇ 150 ppm.
- the polybutylene terephthalate (PBT) [CAS No. 24968-12-5] to be preferably used as component A) according to the invention is produced from terephthalic acid or its reactive derivatives and butanediol by known methods (Kunststoff-Handbuch, Vol. VIII, pp. 695-743, Karl Hanser Verlag, Kunststoff 1973).
- the PBT to be used as component A) preferably contains at least 80 mol%, preferably at least 90 mol%, based on the dicarboxylic acid, of terephthalic acid residues.
- the PBT to be used as component A) according to the invention in one embodiment, in addition to terephthalic acid residues, can contain up to 20 mol% residues of other aromatic dicarboxylic acids with 8 to 14 carbon atoms or residues of aliphatic dicarboxylic acids with 4 to 12 carbon atoms, in particular residues of phthalic acid, Isophthalic acid, naphthalene-2,6-dicarboxylic acid, 4,4'-diphenyldicarboxylic acid,
- Succinic acid adipic acid, sebacic acid, azelaic acid, cyclohexanediacetic acid, cyclohexanedicarboxylic acid, 2,5-furanedicarboxylic acid.
- the PBT to be used as component A) according to the invention can in one embodiment contain up to 20 mol% of other aliphatic diols with 3 to 12 carbon atoms or up to 20 mol% of cycloaliphatic diols with 6 to 21 carbon atoms in addition to butanediol, preferably Residues of propanediol-1,3, 2-ethylpropanediol-1,3, neopentylglycol, pentanediol-1,5, hexanediol-1,6, 1,4-cyclohexanedimethanol, 3-methylpentanediol-2,4, 2-methylpentanediol-2, 4, 2,2,4-trimethylpentanediol-1, 3, 2,2,4-trimethylpentanediol-1, 5, 2- ethylhexanediol-1, 3, 2,2-diethylpropanediol-1, 3, hex
- PBT to be used preferably as component A) has an intrinsic viscosity according to EN-ISO 1628/5 in the range from 40 to 170 cm 3 / g, particularly preferably in the range from 50 to 150 cm 3 / g, very particularly preferably in the range from 65 to 135 cm 3 / g, each measured in an Ubbelohde viscometer in phenol / o-dichlorobenzene (1: 1 parts by weight) at 25 ° C.
- the intrinsic viscosity IV also referred to as the Staudinger index or limiting viscosity, is proportional to the average molecular weight according to the Mark-Houwink equation and is the extrapolation of the viscosity number VN for the case of vanishing polymer concentrations.
- the VN [ml / g] is obtained from the measurement of the solution viscosity in a capillary viscometer, for example an Ubbelohde viscometer.
- the solution viscosity is a measure of the average molecular weight of a plastic.
- the determination is carried out on dissolved polymer, different solvents (m-cresol, tetrachloroethane, phenol, 1,2-dichlorobenzene, etc.) and concentrations being used.
- the viscosity number VN enables the processing and usage properties of plastics to be checked.
- the PBT which is preferably to be used as component A), can also be used in a mixture with other polymers.
- the PBT blends to be used according to the invention are produced by compounding. During such compounding, customary additives, in particular mold release agents or elastomers, can also be mixed in in the melt, as a result of which the properties of the blends are improved.
- PBT to be used with preference according to the invention can be obtained as Pocan® B 1300 from Lanxess GmbH, Cologne.
- thermoplastic from the group of polycarbonates can also be used as the polyester of component A).
- Polycarbonates to be used with preference according to the invention are those homopolycarbonates or copolycarbonates based on bisphenols of the general formula (I),
- At least one polycarbonate based on bisphenols of the formula (Ia) is preferably used as component A) (la), in which
- a for a single bond or for a radical from the series CrC 5 alkylene, C 2 -C 5 alkylidene, C 5 -C 6 cycloalkylidene, -O-, -SO-, -CO-, -S-, -S0 2 -, C 6 -C 12 arylene is what further aromatic rings, optionally containing heteroatoms, can be condensed, or A represents a radical of the formula (II) or (III) wherein
- R 7 and R 8 are individually selectable for each Y and independently represent hydrogen or C 1 -C 6 -alkyl, preferably represent hydrogen, methyl or ethyl
- B each represents Ci-Ci -alkyl, preferably methyl, halogen, preferably chlorine and / or bromine
- x each independently represents 0, 1 or 2
- p represents 1 or 0,
- Y is carbon and m is an integer from 4 to 7, preferably 4 or 5, with
- R 7 and R 8 simultaneously represent alkyl.
- Y is -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -; when m is 5, Y is - CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -; when m is 6, Y is -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -; and when m is 7, Y is -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -CR 7 R 8 -.
- Preferred bisphenols containing the general formula (II) are bisphenols from the group dihydroxydiphenyls, bis (hydroxyphenyl) alkanes, bis (hydroxyphenyl) cycloalkanes, indan bisphenols, bis (hydroxyphenyl) sulfides, bis (hydroxyphenyl) - ethers, bis (hydroxyphenyl) ketones, bis (hydroxyphenyl) sulfones, bis (hydroxyphenyl) sulfoxides and ⁇ , ⁇ '-bis (hydroxyphenyl) diisopropylbenzenes.
- Derivatives of the bisphenols mentioned which are preferably obtainable by alkylation or halogenation on the aromatic rings of the bisphenols mentioned, are preferably bisphenols containing the general formula (II) to be used.
- Particularly preferred bisphenols containing the general formula (II) are hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis (4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) sulfone, bis (3,5-dimethyl-4 -hydroxyphenyl) methane, bis (3,5-dimethyl-4-hydroxyphenyl) -sulfone, 1, 1 -Bis- (3,5-dimethyl-4-hydroxyphenyl) -p / m-diisopropylbenzene, 1, 1- Bis- (4-hydroxyphenyl) -1-phenyl-ethane, 1,1-bis- (3,5-dimethyl-4-hydroxyphenyl) -cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3- methylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3-dimethylcyclohexane, 1,1-bis
- the bisphenols of the general formula (II) described can be prepared by processes known to the person skilled in the art, preferably from the corresponding phenols and ketones.
- the polycarbonates to be used as component A) can also be produced by known processes.
- Preferred processes for the production of polycarbonates are, for example, the production from bisphenols with phosgene by the phase interface process, or from bisphenols with phosgene by the process in the homogeneous phase, the so-called pyridine process, or from bisphenols with carbonic acid esters by the melt transesterification process.
- the mentioned Bisphenols and processes for their preparation are described, for example, in the monograph H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, pp.
- Indane bisphenols and their preparation are described, for example, in US Pat. No. 3,288,864, in JP-A 60 035 150 and in US Pat. No. 4,334,106.
- Indane bisphenols can be obtained, for example, from isopropenylphenol or its derivatives or from dimers of isopropenylphenol or its derivatives in Presence of a Friedel-Craft catalyst in organic solvents.
- melt transesterification process is described in H. Schnell, "Chemistry and Physics of Polycarbonates", Polymer Reviews, Volume 9, pp. 44 to 51, Interscience Publishers, New York, London, Sydney, 1964 and in DE-A 1 031 512.
- the bisphenols and the carbonic acid derivatives used should be as free as possible from alkali ions and alkaline earth ions.
- Such pure raw materials can be obtained, for example, by recrystallizing, washing or distilling the carbonic acid derivatives, in particular carbonic acid esters, and the bisphenols.
- the polycarbonates to be used with preference according to the invention preferably have a weight average molar mass M w in the range from 10,000 to 200,000 g / mol, which is obtained by ultracentrifugation (see K. Schilling, Analytical Ultrazentrifugation, Nanolytics GmbH, Dallgow, pages 1-15) or have scattered light measurement determined in accordance with DIN EN ISO 16014-5: 2012-10.
- the polycarbonates to be used particularly preferably have a weight average molar mass in the range from 12,000 to 80,000 g / mol, particularly preferably a weight average molar mass in the range from 20,000 to 35,000 g / mol.
- the mean molar mass of the polycarbonates to be used preferably as component A) according to the invention can preferably be adjusted in a known manner by means of a corresponding amount of chain terminators.
- the chain terminators can be used individually or as a mixture of different chain terminators.
- Preferred chain terminators are both monophenols and monocarboxylic acids.
- Preferred monophenols are phenol, p-chlorophenol, p-tert-butylphenol, cumylphenol or 2,4,6-tribromophenol, as well as long-chain alkylphenols, in particular 4- (1,1,3,3-tetra-methylbutyl) -phenol or monoalkylphenols or dialkylphenols with a total of 8 to 20 carbon atoms in the alkyl substituents, in particular 3,5-di-tert-butylphenol, p-tert-octylphenol, p-dodecylphenol, 2- (3,5-dimethyl-heptyl) - phenol or 4- (3,5-dimethylheptyl) phenol.
- Preferred monocarboxylic acids are benzoic acid, alkylbenzoic acids or halobenzoic acids.
- Particularly preferred chain terminators are phenol, p-tert-butylphenol, 4- (1,1,3,3-tetra-methylbutyl) -phenol or cumylphenol.
- the amount of chain terminators to be used is preferably in the range from 0.25 to 10 mol%, based on the sum of the bisphenols used in each case.
- the polycarbonates to be used with preference as component A) according to the invention can be branched in a known manner, preferably through the incorporation of trifunctional or more than trifunctional branching agents.
- Preferred branching agents are those with three or more than three phenolic groups or those with three or more than three carboxylic acid groups.
- branching agents are phloroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) -hepten-2, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) ) -heptane, 1, 3,5-tri- (4-hydroxyphenyl) -benzene, 1, 1, 1-tris- (4-hydroxyphenyl) -ethane, tri- (4-hydroxyphenyl) -phenylmethane, 2,2- Bis- [4,4-bis- (4-hydroxyphenyl) -cyclohexyl] -propane, 2,4-bis- (4-hydroxyphenyl-isopropyl) -phenol, 2,6-bis- (2-hydroxy-5'- methylbenzyl) -4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) propane, hexa- (4- (4-hydroxyphenylisopropyl) phenylj-tere
- Very particularly preferred branching agents are 1,1,1-tris- (4-hydroxyphenyl) -ethane or 3,3-bis- (3-methyl-4-hydroxyphenyl) -2-oxo-2,3-dihydroindole.
- the amount of branching agents to be used is preferably in the range from 0.05 mol% to 2 mol%, based on the moles of bisphenols used.
- the branching agents are preferably initially introduced in the aqueous alkaline phase, or dissolved in an organic solvent and added together with the carbonic acid derivatives.
- the branching agents are preferably initially introduced in the aqueous alkaline phase, or dissolved in an organic solvent and added together with the carbonic acid derivatives.
- the branching agents are preferably metered in together with the dihydroxyaromatics or bisphenols.
- Catalysts to be used with preference in the production of polycarbonate to be used preferably as component A) according to the invention by the melt transesterification process are ammonium salts and phosphonium salts, as described, for example, in US-A 3442864, JP-A-14742/72, US-A 5399659 or DE-A
- copolycarbonates can also be used as component A).
- Copolycarbonates in the context of the invention are in particular polydiorganosiloxane-polycarbonate block copolymers whose weight average molar mass M w is preferably in the range from 10,000 to 200,000 g / mol, particularly preferably in the range from 20,000 to 80,000 g / mol, determined by Gel chromatography according to DIN EN ISO 16014-5: 2012-10 after prior calibration by light scattering measurement or ultracentrifugation.
- the content of aromatic carbonate structural units in the polydiorganosiloxane-polycarbonate block copolymers is preferably in the range from 75 to 97.5% by weight, particularly preferably in the range from 85 to 97% by weight.
- the content of polydiorganosiloxane structural units in the polydiorganosiloxane-polycarbonate block copolymers is preferably in the range from 25 to 2.5% by weight, particularly preferably in the range from 15 to 3% by weight.
- the polydiorganosiloxane-polycarbonate block copolymers can preferably be prepared starting from a, w-bishydroxyaryloxy end-group-containing polydiorganosiloxanes with an average degree of polymerization P n in the range from 5 to 100, particularly preferably with an average degree of polymerization P n in the range from 20 to 80 .
- those to be used preferably as component A) Polycarbonates are available, for example, under the Makroion® brand from Covestro AG, Leverkusen.
- the polycarbonates to be used as component A) can be admixed with conventional additives, in particular mold release agents, in the melt or applied to the surface.
- the polycarbonates to be used as component A) preferably already contain mold release agents prior to subsequent compounding with the other components, whereby the person skilled in the art understands compounding to be a term from plastics technology which is to be equated with plastics processing and describes the refinement process of plastics by adding aggregates (fillers, additives, etc.) for the targeted optimization of the property profiles.
- Compounding is preferably carried out in extruders, particularly preferably in co-rotating twin-screw extruders, counter-rotating twin-screw extruders, planetary roller extruders or co-kneaders and comprises the process operations conveying, melting, dispersing, mixing, degassing and pressure build-up.
- blends of polycarbonate and polyalkylene terephthalates can also be used as component A), which are also offered by Covestro AG under the trademark Makroblend®.
- component A which are also offered by Covestro AG under the trademark Makroblend®.
- PC-PET blends are preferably PC-PET blends, PC-PBT blends or PC-PCT-G blends, where PC stands for polycarbonate, PET for polyethylene terephthalate, PBT for polybutylene terephthalate and PCT for polycyclohexylene dimethylene terephthalate.
- At least one sulfide containing cerium is used as component B).
- Preferred sulfides containing cerium are cerium (III) sulfide (Ce 2 S 3 ) [CAS no. 12014- 93-6], also known as Cl Pigment Orange 75, or cerium (III) sulfide / lanthanum (III) sulfide (Ce 2 S 3 / La 2 S 3 ) [CAS no. 12014-93-6; CAS no. 12031-49-1] also known as CI Pigment Orange 78.
- the mixed sulphide cerium (III) sulphide / lanthanum (III) sulphide (CI Pigment Orange 78) is particularly preferably used as the sulphide containing cerium.
- Cl classification see https://de.wikipedia.org/wiki/Colour_lndex.
- Pigment Orange 75 and Pigment Orange 78 can be obtained from Chemikos, Dr. Oliver Schmitt, Düsseldorf, Germany
- Neolor® Orange S or Neolor® Light Orange S from Baotou Hongbo Te Technology co. Ltd., 'Inner Mongolia', China.
- the at least one sulphide containing cerium can be used individually or in a mixture with at least one further sulphide containing cerium, mixed oxides or mixed sulphides of cerium with other lanthanides, preferably with lanthanum, being included according to the invention, with the proviso that the polymer compositions or the
- the high-voltage components or high-voltage components to be produced from them for electromobility in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferably the color numbers RAL2003, RAL2004, RAL2008 or RAL2009, very particularly preferably the color number RAL 2003.
- the at least one sulphide containing cerium to be used according to the invention as component B) can be used directly as a powder, or else in the form of a paste or a masterbatch, compact or concentrate in component A), masterbatches being preferred and masterbatches in one of the respective component A) corresponding polymer matrix are particularly preferred.
- At least one filler or reinforcing material is used as component C). Mixtures of two or more different fillers or reinforcing materials can also be used here.
- At least one filler or reinforcing material from the group of carbon fibers [CAS No. 7440-44-0], glass spheres or solid or hollow glass spheres, glass fibers, ground glass, amorphous quartz glass, aluminum borosilicate glass with an alkali content of 1% (E-glass ) [CAS No. 65997-17-3], amorphous silica [CAS No. 7631-86- 9], quartz flour [CAS No. 14808-60-7], calcium silicate [CAS No. 1344-95-2], calcium metasilicate [CAS No. 10101-39-0], magnesium carbonate [CAS No. 546-93-0], kaolin [CAS No. 1332-58-7], calcined kaolin [CAS No.
- glass fibers and wollastonite are particularly preferred, with glass fibers being very particularly preferred.
- Carbon fibers can also be used as filler or reinforcing material.
- cut fibers also referred to as short fibers, with a length in the range from 0.1 to 1 mm, and long fibers with a Length in the range from 1 to 50 mm and continuous fibers with a length L> 50 mm.
- Short fibers are preferably used in injection molding technology and can be processed directly with an extruder.
- Long fibers can also be processed in extruders. They are widely used in fiber spraying. Long fibers are often mixed with thermosetting plastics as fillers. Continuous fibers are used as rovings or fabrics in fiber-reinforced plastics. Products with continuous fibers achieve the highest levels of rigidity and strength. Furthermore, ground glass fibers are offered, the length of which after grinding is typically in the range from 70 to 200 ⁇ m.
- preferred glass fibers to be used as component C) are cut long glass fibers with an average initial length to be determined by laser diffractometry according to ISO 13320 in the range from 1 to 50 mm, particularly preferably in the range from 1 to 10 mm, very particularly preferably in the range from 2 to 7 mm .
- laser diffractometry according to ISO 13320 standard see: https://de.wikipedia.org/wiki/Laserbeugungs-P
- Preferred glass fibers to be used as component C) have an average fiber diameter to be determined by means of laser diffractometry in accordance with ISO 13320 in the range from 7 to 18 ⁇ m, particularly preferably in the range from 9 to 15 ⁇ m.
- the fillers to be used as component C), preferably glass fibers, are provided in a preferred embodiment with a suitable size system or an adhesion promoter or adhesion promoter system.
- a sizing system or a silane-based adhesion promoter is preferably used.
- Particularly preferred adhesion promoters based on silane for the treatment of component C), in particular for the treatment of glass fibers, are silane compounds of the general formula (I)
- X stands, q in formula (I) stands for an integer from 2 to 10, preferably 3 to 4, r in formula (I) stands for an integer from 1 to 5, preferably 1 to 2, and k in formula (I) stands for an integer from 1 to 3, preferably 1.
- Particularly preferred flaft mediators are silane compounds from the group aminopropyltrimethoxysilane, aminobutyltrimethoxysilane, aminopropyltriethoxysilane, aminobutyltriethoxysilane and the corresponding silanes which contain a glycidyl or a carboxyl group as substituent X, with carboxyl groups being particularly preferred.
- the flaft promoter preferably the silane compounds according to formula (I)
- the flaft promoter is preferably used in amounts in the range from 0.05 to 2% by weight, particularly preferably in amounts in the range of 0.25 to 1.5% by weight and very particularly preferably in amounts in the range from 0.5 to 1% by weight, based in each case on 100% by weight of component C).
- the glass fibers to be preferably used as component C) can be shorter in the composition or in the product than the glass fibers originally used due to the processing into the composition or the product.
- the arithmetic mean value of the glass fiber length to be determined by means of high-resolution X-ray computer tomography is often only in the range of 150 gm to 300 gm after processing.
- glass fibers are produced using the melt spinning process (nozzle drawing, rod drawing and nozzle blowing processes).
- the hot glass mass flows through hundreds of nozzle bores in a platinum spinning plate using gravity.
- the filaments can be pulled in unlimited lengths at a speed of 3 - 4 km / minute.
- E-glass fibers have become the most important for plastic reinforcement.
- E stands for electrical glass, as it was originally mainly used in the electrical industry.
- glass melts are made from pure quartz with additives from limestone, kaolin and boric acid. In addition to silicon dioxide, they contain various amounts of various metal oxides.
- the composition determines the properties of the products.
- at least one type of glass fibers from the group E-glass, H-glass, R, S-glass, D-glass, C-glass and quartz glass is used, particularly preferably glass fibers made of E-glass.
- Glass fibers made from E-glass are the most widely used reinforcement material.
- the strength properties correspond to those of metals (e.g. aluminum alloys), with the specific gravity of laminates containing E-glass fibers being lower than that of metals.
- E-glass fibers are incombustible, heat-resistant up to approx. 400 ° C and resistant to most chemicals and weather influences.
- acicular mineral fillers are also preferably used as component C).
- acicular mineral fillers are understood to mean a mineral filler with a strongly pronounced acicular character.
- the acicular mineral filler to be used preferably as component C) is wollastonite.
- the needle-shaped, mineral filler preferably has a length: diameter ratio to be determined by means of high-resolution X-ray computed tomography in the range from 2: 1 to 35: 1, particularly preferably in the range from 3: 1 to 19: 1, particularly preferably in the range from 4: 1 up to 12: 1.
- the mean particle size of the needle-shaped mineral fillers to be determined by means of high-resolution X-ray computed tomography is preferably less than 20 ⁇ m, particularly preferably less than 15 ⁇ m, particularly preferably less than 10 ⁇ m.
- d90 values their determination and their meaning, see Chemie Ingenieurtechnik (72) pp. 273-276, 3/2000, Wiley-VCH Verlags GmbH, Weinheim, 2000, according to which the d90 value is the particle size below which 90% of the amount of particles are.
- the non-fibrous and non-foamed ground glass is of particulate, non-cylindrical shape and has a length to thickness ratio of less than 5, preferably less than 3, particularly preferably less than 2, to be determined by means of laser diffractometry in accordance with ISO 13320 of course excluded.
- the non-foamed and non-fibrous ground glass which is particularly preferred to be used as component C) in one embodiment, is also characterized in that it does not have the typical glass geometry for fibrous glass with a cylindrical or oval cross-section with a length to be determined by means of laser diffractometry in accordance with ISO 13320 Diameter ratio (L / D ratio) greater than 5.
- the non-foamed and non-fibrous ground glass to be used particularly preferably according to the invention as component C) in one embodiment is preferably obtained by grinding glass with a mill, preferably a ball mill and particularly preferably with subsequent sifting or sieving.
- Preferred starting materials for the grinding of the non-fibrous and non-foamed, ground glass to be used as component C) in one embodiment are also glass waste, such as those found in the manufacture of glass products as an undesired by-product and / or as a main product that does not meet specifications (so-called off-spec goods ) attack.
- the glass can be colored, with non-colored glass being preferred as the starting material for use as component C).
- At least one flame retardant is used as component D).
- Preferred flame retardants are mineral flame retardants other than component C), nitrogen-containing flame retardants or phosphorus-containing flame retardants.
- Magnesium hydroxide is particularly preferred among the mineral flame retardants.
- Magnesium hydroxide [CAS No. 1309-42-8] can be contaminated due to its origin and manufacturing method. Typical impurities are, for example, silicon, iron, calcium and / or aluminum-containing species, which can be embedded in the magnesium hydroxide crystals, for example in the form of oxides.
- the magnesium hydroxide to be used as a mineral flame retardant can be uncoated or provided with a size.
- a size affects the quality and promotes the mechanical bond between the plastic (matrix) and the component to be provided with the size.
- the magnesium hydroxide to be preferably used as a mineral flame retardant is preferably provided with sizes based on stearates or aminosiloxanes, particularly preferably with aminosiloxanes.
- Magnesium hydroxide to be used preferably as a mineral flame retardant has an average particle size d50 to be determined by means of laser diffractometry according to ISO 13320 in the range from 0.5 ⁇ m to 6 ⁇ m, with ad50 in the range from 0.7 ⁇ m to 3.8 ⁇ m being preferred and ad50 in the range from 1.0 pm to 2.6 pm is particularly preferred.
- Magnesium hydroxide types suitable according to the invention as mineral flame retardants are, for example, Magnifin® H5IV from Martinswerk GmbH, Bergheim, Germany or Hidromag® Q2015 TC from Penoles, Mexico City, Mexico.
- Preferred nitrogen-containing flame retardants are the reaction products of trichlorotriazine, piperazine and morpholine in accordance with CAS No. 1078142-02-5, in particular MCA PPM Triazin HF from MCA Technologies GmbH, Biel-Benken, Switzerland, and also melamine cyanurate and condensation products of melamine, in particular Miere, Melam, melon or more highly condensed compounds of this type.
- Preferred inorganic nitrogen-containing compounds are ammonium salts.
- salts of aliphatic and aromatic sulfonic acids and mineral flame retardant additives in particular aluminum hydroxide or Ca-Mg-carbonate hydrates (DE-A 4236 122).
- Zinc-free compounds are preferred, in particular molybdenum oxide, magnesium oxide, magnesium carbonate, calcium carbonate, calcium oxide, titanium nitride, magnesium nitride, calcium phosphate, calcium borate, magnesium borate or mixtures thereof.
- zinc-containing compounds can also be used as component D), if required.
- component D which includes preferably zinc oxide, zinc borate, zinc stannate, zinc hydroxystannate, zinc sulfide and zinc nitride, or mixtures thereof.
- Preferred phosphorus-containing flame retardants are organic metal phosphinates, aluminum salts of phosphonic acid, red phosphorus, inorganic metal hypophosphites, metal phosphonates, derivatives of 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides (DOPO derivatives), resorcinol bis (diphenyl phosphate ) (RDP) including oligomers, bisphenol-A-bis-diphenyl phosphate (BDP) including oligomers,
- DOPO derivatives 9,10-dihydro-9-oxa-10-phosphaphenanthrene-10-oxides
- RDP resorcinol bis
- BDP bisphenol-A-bis-diphenyl phosphate
- a preferred metal organic phosphinate is aluminum tris (diethyl phosphinate).
- a preferred inorganic metal hypophosphite is aluminum hypophosphite.
- flame retardants to be used as component D) are carbon formers, particularly preferably phenol-formaldehyde resins, polycarbonates, polyimides, polysulfones, polyether sulfones or polyether ketones, and anti-drip agents, in particular tetrafluoroethylene polymers.
- the flame retardants to be used as component D) can be added to component A) in their pure form or via masterbatches or compacts.
- halogen-containing flame retardants can also be used as flame retardants - if required, taking into account the disadvantages due to the fact that the flame retardants are not halogen-free.
- Preferred halogen-containing flame retardants are commercially available organic halogen compounds, particularly preferably ethylene-1,2-bistetrabromophthalimide, decabromodiphenylethane, tetrabromobisphenol-A-epoxy-oligomer, tetrabromobisphenol-A-oligocarbonate, tetrachlorobisphenol-a-phenol or brominated polyphenyl-bisphenol-a-bromobenzene, the polyphenyl-styrene-a-oligobenzarbonate alone, or the polypropylene-bromobystyrene-bromylate-oligobenzarbonate can be used in combination with synergists, with brominated polystyrene being particularly preferred among the halogen-containing flame
- Brominated polystyrene is preferably used at 10-30% by weight, particularly preferably at 15-25% by weight, based in each case on the overall composition, with at least one of the other components being reduced to such an extent that the sum of all weight percentages always equals 100.
- flame retardant synergists can also be used - if required and taking into account the disadvantages described at the beginning with regard to the hazard classification H351 and the under Detrimental effects on the tracking resistance - also antimony trioxide and antimony pentoxide are used.
- Brominated polystyrene is commercially available in various product grades. Examples include FireMaster ® PBS64 the company. Lanxess, Cologne, Germany and Saytex ® HP-3010 of the company. Albemarle, Baton Rouge, United States.
- flame retardants to be used as component D are aluminum tris (diethylphosphinate)] [CAS No. 225789-38-8] and the combination of aluminum tris (diethylphosphinate) and melamine polyphosphate or the combination of aluminum tris (diethylphosphinate) and at least an aluminum salt of phosphonic acid is very particularly preferred, the latter combination being particularly preferred.
- the proportion of aluminum tris (diethylphosphinate) is preferably in the range from 40 to 90 parts by weight, particularly preferably in Range from 50 to 80 parts by weight, very particularly preferably in the range from 60 to 70 parts by weight, in each case based on 100 parts by weight of the combination of aluminum tris (diethylphosphinate) and melamine polyphosphate or the combination of aluminum tris (diethylphosphinate) and at least one aluminum salt Phosphonic acid.
- Exolit ® As component D) to be assigned aluminum tris (diethylphosphinate) in the art as Exolit ® OP1230 or OP1240, Exolit ® is the Fa. Clariant International Ltd. Muttenz, Switzerland, known. Melamine polyphosphate is commercially available in various product grades. Examples of this are, for example, Melapur® 200/70 from BASF, Ludwigshafen, Germany and Budit® 3141 from Budenheim, Budenheim, Germany.
- Preferred aluminum salts of phosphonic acid are selected from the group of primary aluminum phosphonate [AI (H 2 P0 3 ) 3 ], basic aluminum phosphonate [AI (OH) H 2 P0 3 ) 2 -2H 2 0],
- AI 2 (HP0 3 ) u (H 2 P0 3 ) t ⁇ (H 2 0) S of the formula (IV), wherein u in the range from 2 to 2.99, t in the range from 2 to 0.01 and s im Range from 0 to 4, where in formula (III) z, y and v and in formula (IV) u and t can only assume such numbers that the corresponding aluminum salt of the phosphonic acid is uncharged as a whole.
- Preferred alkali metals M in formula (III) are sodium and potassium.
- the aluminum salts of phosphonic acid described can be used individually or as a mixture.
- Particularly preferred aluminum salts of phosphonic acid are selected from the group consisting of primary aluminum phosphonate [AI (H 2 P0 3 ) 3 ], secondary aluminum phosphonate [AI 2 (HP0 3 ) 3 ], basic aluminum phosphonate [AI (OH) H 2 P0 3 ) 2 -2H 2 0],
- the position of aluminum salts of phosphonic acid to be used according to the invention as component D) is described, for example, in WO 2013/083247 A1. It is usually carried out by reacting an aluminum source, preferably aluminum isopropoxide, aluminum nitrate, aluminum chloride or aluminum hydroxide, with a phosphorus source, preferably phosphonic acid, ammonium phosphonate, alkali metal phosphonate, and optionally with a template in a solvent at 20 to 200 ° C for a period of up to 4 days .
- the aluminum source and phosphorus source are mixed for this purpose, heated under hydrothermal conditions or under reflux, filtered off and washed dried.
- Preferred templates are 1,6 hexanediamine, guanidine carbonate or ammonia.
- the preferred solvent is water.
- At least one further additive different from components B) to D) is used as component E).
- Preferred additives to be used as component E) are antioxidants, heat stabilizers, UV stabilizers, gamma ray stabilizers, components for reducing water absorption or hydrolysis stabilizers, antistatic agents, emulsifiers, nucleating agents, plasticizers, processing aids, impact modifiers, lubricants and / or mold release agents, components for reducing the amount of mold release agents Water absorption, flow aids or elastomer modifiers. Chain-lengthening additives, colorants other than component B) and, if required, further laser absorbers.
- the additives can be used alone or in a mixture or in the form of masterbatches.
- Preferred thermal stabilizers for component E) are sterically hindered phenols, in particular those containing at least one 2,6-di-tert-butylphenyl group and / or 2-tert-butyl-6-methylphenyl group, and also phosphites, hypophosphites, in particular Sodium hypophosphite NaH 2 P0 2, hydroquinones, aromatic secondary amines, substituted resorcinols, salicylates, benzotriazoles and benzophenones, 3,3'-thiodipropionic esters and variously substituted representatives of these groups or mixtures thereof.
- copper salts preferably in combination with sodium hypophosphite NaH 2 P0 2
- the preferred copper salt used is copper (l) iodide [CAS No. 7681-65-4] and / or copper (triphenylphosphino) iodide [CAS No. 47107-74-4].
- the copper salts are preferably used in combination with sodium hypophosphite NaH 2 P0 2 or with at least one alkali iodide.
- the preferred alkali iodide is potassium iodide [CAS No. 7681-11-0].
- Thermal stabilizers to be used as component E) are preferably used in amounts of 0.01 to 2 parts by mass, particularly preferably 0.05 to 1 part by mass, in each case based on 100 parts by mass of component A).
- UV stabilizers to be used as component E) are preferably substituted resorcinols, salicylates, benzotriazoles and benzophenones, HALS derivatives (“hindered amine light stabilizers”) containing at least one 2,2,6,6-tetramethyl-4-piperidyl unit or benzophenones used.
- UV stabilizers to be used as component E) are preferably used in amounts of 0.01 to 2 parts by mass, particularly preferably 0.1 to 1 part by mass, in each case based on 100 parts by mass of component A).
- inorganic pigments are preferably used as component E) and different from component B), particularly preferably ultramarine blue, bismuth vanadate [CAS No. 14059-33-7], iron oxide [CAS No. 1309-37-1], titanium dioxide [CAS No. 13463-67-7 (rutile) or CAS No. 1317-70-0 (anatase)], barium sulfate [CAS No. 7727-43-7], zinc sulfide [CAS No. 1314-98-3] or Tin-titanium-zinc oxides [CAS No. 923954-49-8], particularly preferably barium sulfate.
- Colorants to be used as component E) and different from component B) are preferably used in one embodiment, organic colorants, particularly preferably phthalocyanines, quinacridones, benzimidazoles, in particular Ni-2-hydroxynaphylbenzimidazole [CAS No. 42844-93-9] and / or pyrimidine-azo-benzimidazole [CAS No. 72102-84-2] and / or Pigment Yellow 192 [CAS No. 56279-27-7], also perylenes, anthraquinones, in particular Cl Solvent Yellow 163 [CAS No. 13676-91-0].
- organic colorants particularly preferably phthalocyanines, quinacridones, benzimidazoles, in particular Ni-2-hydroxynaphylbenzimidazole [CAS No. 42844-93-9] and / or pyrimidine-azo-benzimidazole [CAS No. 72102-84-2] and / or Pigment Yellow 192 [CAS No. 56279-27-7], also pery
- component E The list of inorganic or organic colorants to be used as component E) is not exhaustive.
- carbon black or nigrosine can be used as the colorant.
- titanium dioxide is used as the colorant for component E) titanium white, also referred to as pigment white 6 or CI 77891.
- Nucleating agents to be used as component E) are preferably sodium or calcium phenyl phosphinate, aluminum oxide or silicon dioxide, and very particularly preferably talc, although this list is not exhaustive.
- Flow aids to be used as component E) are preferably copolymers of at least one ⁇ -olefin with at least one methacrylic acid ester or acrylic acid ester of an aliphatic alcohol.
- Copolymers in which the ⁇ -olefin is composed of ethene and / or propene and the methacrylic acid ester or acrylic acid ester as the alcohol component are linear or are particularly preferred contains branched alkyl groups with 6 to 20C atoms.
- Acrylic acid (2-ethyl) hexyl ester is very particularly preferred.
- Copolymers suitable as flow aids are distinguished not only by their composition but also by their low molecular weight.
- copolymers are particularly suitable which have an MFI value measured at 190 ° C. and a load of 2.16 kg of at least 100 g / 10 min, preferably at least 150 g / 10 min , particularly preferably of at least 300 g / 10 min.
- the MFI Melt-Flow-Index
- a copolymer of ethene and acrylic acid (2-ethyl) -hexyl ester with MFI is particularly preferred as a flow aid 550, known as Lotryl® 37EH550.
- Chain-extending additives to be used as component E) are preferably di- or polyfunctional branching or chain-extending additives containing at least two branching or chain-extending functional groups per molecule.
- branching or chain-extending additives low molecular weight or oligomeric compounds are preferred which have at least two chain-extending functional groups per molecule which can react with primary and / or secondary amino groups and / or amide groups and / or carboxylic acid groups.
- Functional groups with a chain-lengthening effect are preferably isocyanates, alcohols, blocked isocyanates, epoxides, maleic anhydride, oxazolines, oxazines, oxazolones, epoxides being preferred.
- Particularly preferred di- or polyfunctional branching or chain-extending additives are diepoxides based on diglycidyl ether (bisphenol and epichlorohydrin), based on amine epoxy resin (aniline and epichlorohydrin), based on diglycidyl esters (cycloaliphatic dicarboxylic acids and epichlorohydrin) individually or in mixtures -Bis [p-hydroxyphenyl] propane diglycidyl ether, bis [p- (N-methyl-N-2,3-epoxy-propylamino) -phenyl] -methane and epoxidized fatty acid esters of glycerol, containing at least two epoxy groups per Molecule.
- diglycidyl ether bisphenol and epichlorohydrin
- amine epoxy resin aniline and epichlorohydrin
- diglycidyl esters cycloaliphatic dicarboxylic acids and epichlorohydrin
- Particularly preferred di- or polyfunctional branching or chain-extending additives are glycidyl ethers, very particularly preferably bisphenol A diglycidyl ether [CAS No. 98460-24-3] or epoxidized fatty acid esters of glycerol, and also very particularly preferably epoxidized soybean oil [CAS No. 8013- 07-8] and / or epoxidized linseed oil.
- Plasticizers to be used with preference as component E) are dioctyl phthalate, dibenzyl phthalate, butylbenzyl phthalate, hydrocarbon oils or N- (n-butyl) benzenesulfonamide.
- Elastomer modifiers to be used preferably as component E) include, inter alia, one or more graft polymers of
- the graft base E.2 generally has an average particle size d50 to be determined by laser diffractometry in accordance with ISO 13320 in the range from 0.05 to 10 ⁇ m, preferably in the range from 0.1 to 5 ⁇ m, particularly preferably in the range from 0.2 until 1 pm.
- Monomers for E.1 are preferably mixtures of
- E.1.2 1 to 50% by weight of vinyl cyanides, in particular unsaturated nitriles such as acrylonitrile and methacrylonitrile, and / or (meth) acrylic acid (CC 8 ) alkyl esters, in particular methyl methacrylate, glycidyl methacrylate, n-butyl acrylate, t-butyl acrylate, and / or derivatives, in particular anhydrides and imides of unsaturated carboxylic acids, in particular maleic anhydride or N-phenyl maleimide, the percentages by weight being based on 100% by weight of the elastomer modifier.
- unsaturated nitriles such as acrylonitrile and methacrylonitrile
- CC 8 acrylic acid alkyl esters
- Preferred monomers E.1.1 are to be selected from at least one of the monomers styrene, ⁇ -methylstyrene and methyl methacrylate
- preferred monomers E.1.2 are selected from at least one of the monomers acrylonitrile, maleic anhydride, glycidyl methacrylate and methyl methacrylate.
- Particularly preferred monomers are E.1.1 styrene and E.1.2 acrylonitrile.
- Graft bases E.2 suitable for the graft polymers to be used in the elastomer modifiers are, for example, diene rubbers, EPDM rubbers, i.e. those based on ethylene / propylene and optionally diene, and also acrylate, polyurethane, silicone, chloroprene and ethylene / vinyl acetate rubbers.
- EPDM stands for ethylene propylene diene rubber.
- Preferred graft bases E.2 are diene rubbers, in particular based on butadiene, isoprene, etc. or mixtures of diene rubbers or copolymers of diene rubbers or mixtures thereof with other copolymerizable monomers, in particular according to E.1.1 and E.1.2, with the proviso that the glass transition temperature of the Component E.2 is ⁇ 10 ° C, preferably ⁇ 0 ° C, particularly preferably ⁇ -10 ° C.
- Particularly preferred graft bases E.2 are ABS polymers (emulsion, bulk and suspension ABS) where ABS stands for acrylonitrile-butadiene-styrene, such as those used, for example, in US Pat. B. in DE-A 2 035 390 or in DE-A 2 248 242 or in Ullmann, Enzyklopadie der Technischen Chemie, Vol. 19 (1980), pp. 277-295.
- the gel fraction of the graft base E.2 is preferably at least 30% by weight, particularly preferably at least 40% by weight (measured in toluene).
- the elastomer modifiers or graft polymers to be used as component E) are produced by free-radical polymerization, preferably by emulsion, suspension, solution or bulk polymerization, in particular by emulsion or bulk polymerization.
- Particularly suitable graft rubbers are also ABS polymers which are produced by redox initiation with an initiator system of organic hydroperoxide and ascorbic acid according to US Pat. No. 4,937,285.
- graft polymers are also understood to mean those products which are obtained by (co) polymerization of the graft monomers in the presence of the graft base and which are also obtained during processing.
- Acrylate rubbers which are also suitable are based on graft bases E.2, the preferred polymers of acrylic acid alkyl esters, optionally with up to 40% by weight, based on E.2 other polymerizable, ethylenically unsaturated monomers.
- the preferred polymerizable acrylic acid esters include CrCg-alkyl esters, preferably methyl, ethyl, butyl, n-octyl and 2-ethylhexyl esters; Haloalkyl esters, preferably Halogen-CrCg-alkyl esters, such as chloroethyl acrylate, glycidyl esters and mixtures of these monomers.
- Graft polymers with butyl acrylate as the core and methyl methacrylates as the shell in particular Paraloid® EXL2300, from Dow Corning Corporation, Midland, Michigan, USA, are particularly preferred.
- crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate; polyunsaturated heterocyclic compounds, preferably trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
- crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups.
- Very particularly preferred crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine, triallylbenzenes.
- the amount of crosslinked monomers is preferably 0.02 to 5% by weight, in particular 0.05 to 2% by weight, based on the graft base E.2.
- Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to produce the graft base E.2, are acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl-C 1 -C 6 -alkyl ethers, methyl methacrylate, glycidyl methacrylate, butadiene .
- Preferred acrylate rubbers as the graft base E.2 are emulsion polymers which have a gel content of at least 60% by weight.
- Suitable graft bases according to E.2 are silicone rubbers with graft-active sites, as are described in DE-A 3 704 657, DE-A 3 704 655, DE-A 3 631 540 and DE-A 3631 539.
- Preferred graft polymers with a silicone component are those which have methyl methacrylate or styrene-acrylonitrile as the shell and a silicone / acrylate graft as the core.
- the preferred styrene-acrylonitrile shell to be used is Metabien ® SRK200.
- Metabien ® S2001 or S2030 Metabien ® or Metabien ® SX-005th Metabien is particularly preferred ® S2001.
- the products with the trade name Metabien ® are available from Mitsubishi Rayon Co., Ltd., Tokyo, Japan.
- crosslinking monomers with more than one polymerizable double bond can be copolymerized.
- Preferred examples of crosslinking monomers are esters of unsaturated monocarboxylic acids with 3 to 8 carbon atoms and unsaturated monohydric alcohols with 3 to 12 carbon atoms, or saturated polyols with 2 to 4 OH groups and 2 to 20 carbon atoms, preferably ethylene glycol dimethacrylate, allyl methacrylate ; polyunsaturated heterocyclic compounds, preferably trivinyl and triallyl cyanurate; polyfunctional vinyl compounds, preferably di- and trivinylbenzenes; but also triallyl phosphate and diallyl phthalate.
- Preferred crosslinking monomers are allyl methacrylate, ethylene glycol dimethacrylate, diallyl phthalate and heterocyclic compounds which have at least 3 ethylenically unsaturated groups.
- crosslinking monomers are the cyclic monomers triallyl cyanurate, triallyl isocyanurate, triacryloylhexahydro-s-triazine and triallylbenzenes.
- the amount of crosslinked monomers is preferably 0.02 to 5% by weight, in particular 0.05 to 2% by weight, based on the graft base E.2.
- Preferred "other" polymerizable, ethylenically unsaturated monomers which, in addition to the acrylic acid esters, can optionally be used to produce the graft base E.2, are acrylonitrile, styrene, ⁇ -methylstyrene, acrylamides, vinyl-C 1 -C 6 -alkyl ethers, methyl methacrylate, glycidyl methacrylate, butadiene.
- Preferred acrylate rubbers as the graft base E.2 are emulsion polymers which have a gel content of at least 60% by weight.
- elastomer modifiers that are not based on graft polymers and have glass transition temperatures ⁇ 10 ° C., preferably ⁇ 0 ° C., particularly preferably ⁇ -20 ° C. exhibit.
- Lubricants and / or mold release agents to be used as component E) are preferably long-chain fatty acids, especially stearic acid or behenic acid, their salts, especially Ca or Zn stearate, and their ester derivatives, especially those based on pentaerythritol, especially fatty acid esters of pentaerythritol or amide derivatives , in particular ethylene-bis-stearylamide, montan waxes and low molecular weight polyethylene or polypropylene waxes.
- montan waxes are mixtures of straight-chain, saturated carboxylic acids with chain lengths in the range from 28 to 32 carbon atoms.
- lubricants and / or mold release agents from the group of esters of saturated or unsaturated aliphatic carboxylic acids with 8 to 40 carbon atoms with aliphatic saturated alcohols or amides of amines with 2 to 40 carbon atoms with unsaturated aliphatic carboxylic acids with 8 to 40 are particularly preferred C atoms or, instead of the carboxylic acids, metal salts of saturated or unsaturated aliphatic carboxylic acids with 8 to 40 C atoms are used.
- Lubricants and / or mold release agents to be used very particularly preferably as component E) are to be selected from the group pentaerythritol tetrastearate [CAS No. 115-83-3], ethylene-bis-stearylamide, calcium stearate and ethylene glycol dimontanate. Calcium stearate [CAS No. 1592-23-0] or ethylene-bis-stearylamide [CAS No. 110-30-5] is particularly preferred.
- Ethylene-bis-stearylamide (Loxiol® EBS from Emery Oleochemicals) is particularly preferably used.
- Hydrolysis stabilizers or components for reducing water absorption which are preferably used as component E) are preferably polyesters, polybutylene terephthalate and / or polyethylene terephthalate being preferred and polyethylene terephthalate being very particularly preferred.
- the polyesters are preferably used in concentrations of 5 to 20% by weight and particularly preferably in concentrations of 7 to 15% by weight, each based on the total polymer composition and with the proviso that the sum of all percent by weight of the polymer composition is always 100% by weight .-% results.
- Laser absorbers to be used with preference as component E) are selected from the group consisting of tin oxide, tin orthophosphate, barium titanate, aluminum oxide, Copper hydroxyphosphate, copper orthophosphate, potassium copper diphosphate, copper hydroxide, bismuth trioxide and antraquinone. Tin oxide is particularly preferred.
- antimony tin oxide, antimony trioxide or antimony pentoxide can also be used as the laser absorber - if required, taking into account the disadvantages described at the beginning with regard to the hazard classification H351 and the adverse effects on the tracking resistance.
- the laser absorber can be used directly as a powder or in the form of masterbatches.
- Preferred masterbatches are those based on polyester and / or polyolefins, preferably polyethylene.
- the laser absorber can be used individually or as a mixture of several laser absorbers.
- Laser absorbers can absorb laser light of a certain wavelength. In practice, this wavelength is in the range from 157 nm to 10.6 pm. Examples of lasers of these wavelengths are described in WO2009 / 003976 A1.
- Nd YAG lasers, with which wavelengths of 1064, 532, 355 and 266 nm can be achieved, and CO2 lasers are preferred.
- high-voltage components in particular high-voltage components for electromobility, based on polymer compositions, are preferred.
- the high-voltage components or high-voltage components for electromobility in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferably the Color numbers RAL2003
- floch-voltage components in particular floch-voltage components for electromobility, based on polymer compositions, are preferred.
- the floch voltage components or floch voltage components for electromobility in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferably the color numbers RAL2003, RAL2004, RAL2008 or RAL2009, most preferably the color number RAL 2003.
- floch-voltage components in particular floch-voltage components for electromobility, based on polymer compositions, are preferred.
- floch-volt components in particular floch-volt components for electromobility, based on polymer compositions, are particularly preferred
- the high-voltage components or high-voltage components for electromobility in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferably the color numbers RAL2003
- high-voltage components in particular high-voltage components for electromobility, based on polymer compositions, are preferred.
- C) 1 to 150 parts by mass of at least one filler or reinforcing material preferably to be selected from the group of glass spheres or solid or hollow glass spheres, or glass fibers, or ground glass, amorphous quartz glass, aluminum borosilicate glass with an alkali content of 1% (E glass), amorphous silica , Quartz flour, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or ground quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite,
- Flame retardants or phosphorus-containing flame retardants with the proviso that the high-voltage components or high-voltage components for electromobility in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferably the color numbers RAL2003, RAL2004, RAL2008 or RAL2009, very particularly preferably the color number RAL 2003.
- high-voltage components in particular high-voltage components for electromobility, based on polymer compositions, are particularly preferred
- C) 1 to 150 parts by mass of at least one filler or reinforcing material preferably to be selected from the group of glass spheres or solid or hollow glass spheres, or glass fibers, or ground glass, amorphous quartz glass, aluminum borosilicate glass with an alkali content of 1% (E glass), amorphous silica , Quartz flour, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or ground quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite, pseudoboehmite of the formula AIO (OH), magnesium carbonate and talc, in particular and
- flame retardant additive preferably selected from mineral flame retardants, nitrogen-containing flame retardants or phosphorus-containing flame retardants
- high-voltage components in particular high-voltage components for electromobility, based on polymer compositions, are preferred A) to 100 parts by mass of at least one polyester, preferably C 2 -C 10 polyalkylene terephthalate or polycarbonate, in particular PBT,
- C) 1 to 150 parts by mass of at least one filler and reinforcing material preferably to be selected from the group of glass spheres or solid or hollow glass spheres, or glass fibers, or ground glass, amorphous quartz glass, aluminum borosilicate glass with an alkali content of 1% (E glass), amorphous Silica, quartz flour, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or ground quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite,
- At least one heat stabilizer preferably to be selected from the group of sterically hindered phenols, in particular those containing at least one 2,6 di-tert-butylphenyl group and / or 2-tert-butyl-6- methylphenyl group, also the phosphites, the hypophosphites, especially sodium hypophosphite NaH 2 P0 2 , the hydroquinones, the aromatic secondary amines and the 3,3'-thiodipropionic acid ester, with the proviso that the high-voltage components or high-voltage components for electromobility in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferably the color numbers RAL2003, RAL2004, RAL2008 or RAL2009, very particularly preferably the color number RAL 2003. Titanium dioxide is preferably used as component E).
- high-voltage components in particular high-voltage components for electromobility, based on polymer compositions, are preferred.
- C) 1 to 150 parts by mass of at least one filler and reinforcing material preferably to be selected from the group of glass spheres or solid or hollow glass spheres, or glass fibers, or ground glass, amorphous quartz glass, Aluminum borosilicate glass with an alkali content of 1% (E glass), amorphous silica, quartz powder, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or ground quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite , Pseudoboehmite of the formula AIO (OH), magnesium carbonate and talc, especially glass fibers, and
- At least one thermal stabilizer preferably to be selected from the group of sterically hindered phenols, in particular those containing at least one 2,6 di-tert-butylphenyl group and / or 2-tert-butyl-6- methylphenyl group, also the phosphites, the hypophosphites, especially sodium hypophosphite NaH 2 P0 2 , the hydroquinones, the aromatic secondary amines and the 3,3'-thiodipropionic acid ester with the proviso that the high-voltage components or high-voltage components for electromobility in the RAL color system Color numbers RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011 correspond, particularly preferably the color numbers RAL2003, RAL2004, RAL2008 or RAL2009, very particularly preferably the color number RAL 2003. Titanium dioxide is preferably used as component E).
- high-voltage components in particular high-voltage components for electromobility, based on polymer compositions, are preferred.
- C) 1 to 150 parts by mass of at least one filler and reinforcing material preferably to be selected from the group of glass spheres or solid or hollow glass spheres, or glass fibers, or ground glass, amorphous quartz glass, aluminum borosilicate glass with an alkali content of 1% (E glass), amorphous Silicic acid, quartz flour, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or ground quartz, mica, phlogopite, barium sulphate, feldspar, wollastonite, montmorillonite, pseudoboehmite of the formula AIO (OH), especially magnesium carbonate and talc , D) 3 to 100 parts by mass of at least one flame retardant additive, preferably to be selected from mineral flame retardants, containing nitrogen
- RAL2008, RAL2009, RAL2010 or RAL2011 particularly preferably the
- Color numbers RAL2003, RAL2004, RAL2008 or RAL2009 very particularly preferably the color number RAL 2003.
- Titanium dioxide is preferably used as component E).
- high-voltage components in particular high-voltage components for electromobility, based on polymer compositions, are particularly preferred
- C) 1 to 150 parts by mass of at least one filler and reinforcing material preferably to be selected from the group of glass spheres or solid or hollow glass spheres, or glass fibers, or ground glass, amorphous quartz glass, aluminum borosilicate glass with an alkali content of 1% (E glass), amorphous Silica, quartz flour, calcium silicate, calcium metasilicate, magnesium carbonate, kaolin, calcined kaolin, chalk, kyanite, powdered or ground quartz, mica, phlogopite, barium sulfate, feldspar, wollastonite, montmorillonite,
- Flame retardants or phosphorus-containing flame retardants and E) 0.01 to 2 parts by mass of at least one thermal stabilizer, preferably to be selected from the group of sterically hindered phenols, in particular those containing at least one 2,6 di-tert-butylphenyl group and / or 2-tert-butyl-6- methylphenyl group, also the phosphites, the hypophosphites, especially sodium hypophosphite NaH 2 P0 2 , the hydroquinones, the aromatic secondary amines and the 3,3'-thiodipropionic acid ester, with the proviso that the high-voltage components or high-voltage components for electromobility in the RAL color system correspond to the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferably the color numbers RAL2003, RAL2004, RAL2008 or RAL2009, very particularly preferably the color number RAL 2003. Titanium dioxide is preferably used as component E
- the present invention also relates to a process for the preparation of the high-voltage components, in particular in high-voltage components of the electric mobility, employed polymer compositions by reacting A) at least one polyester, preferably polyester, C 2 is preferably -C 0 -Polyalkylenterephthalat or polycarbonate, particularly PBT, and B ) at least one sulphide containing cerium, and optionally at least one of the further components C), D) or E) in at least one mixing tool, with the proviso that the high-voltage components or high-voltage components for electromobility in the RAL color system of the color number RAL2003, RAL2004, RAL2007, RAL2008, RAL2009, RAL2010 or RAL2011, particularly preferably the color numbers RAL2003, RAL2004, RAL2008 or RAL2009, very particularly preferably the color number RAL 2003.
- sulfide containing cerium are cerium (III) sulfide (Ce 2 S 3 ) or cerium (III) sulfide / lanthanum (III) sulfide.
- the present invention also relates to a method for producing high-voltage components, in particular high-voltage components for electromobility, by using the polymer compositions in injection molding, including the special processes GIT (gas injection technology), WIT (water injection technology) and PIT (projectile injection technology), in extrusion processes, including in the profile -Extrusion, or further processed by blow molding.
- GIT gas injection technology
- WIT water injection technology
- PIT projectile injection technology
- the polymer compositions are discharged into strands before further processing, cooled to granulability, if appropriate dried and granulated.
- the polymer composition is temporarily stored as granules.
- the invention preferably relates to a method for producing
- High-voltage components in particular high-voltage components for electromobility, by adding A) at least one polyester, preferably C 2 -C 10 polyalkylene terephthalate or polycarbonate, in particular PBT, and B) at least one sulfide containing cerium, preferably to 100 parts by mass of at least one polyester 0.01 up to 5 parts by mass of at least one sulphide containing cerium with one another
- sulfides containing cerium are cerium (III) sulfide (Ce 2 S 3 ) or cerium (III) sulfide / lanthanum (III) sulfide.
- Preferred high-voltage components in particular high-voltage components for electromobility, are used in the electric drive train and / or in the battery system.
- Particularly preferred high-voltage components are covers for electrics or electronics, control units, covers / housings for fuses, relays, battery cell modules, fuse holders, fuse plugs, connection terminals, cable holders or sheaths, in particular sheaths for high-voltage power rails and high-voltage power distribution rails ("bus bar").
- polyester-based polymer compositions were first prepared by compounding.
- the individual components were mixed in a twin-screw extruder (ZSK 25 Compounder from Coperion Werner & Pfleiderer (Stuttgart, Germany)) at temperatures between 270 and 300 ° C., discharged as a strand, cooled to granulability and granulated.
- ZSK 25 Compounder from Coperion Werner & Pfleiderer (Stuttgart, Germany)
- the granules were processed at temperatures in the range from 270 to 290 ° C. to form standard test specimens for the respective tests.
- the measure of bleeding was the discoloration of a soft PVC film (W-PVC, FB110 white, normal cold-resistant from Game Kunststofftechnik GmbH, Eitorf, Germany) with the dimensions 30 * 20 * 2 mm 3, which was stored in a hot air oven at 80 ° C for 12 hours * 40 * 2mm 3 clamped between two plastic boards with the dimensions 60 on the basis of the compositions described in Table 2 below.
- the assessment was then carried out visually according to the gray scale according to ISO 105-A02, where '5' means that the PVC film showed no change in color and 'T' means that the PVC film showed a marked change in color.
- the measure of lightfastness was the discoloration of the molding compositions described in Table 2 in the form of 60 * 40 * 2 mm 3 sheets after UV storage with a UV light (Suntest CPS +, 300-800 nm , 45-130 klx, with Window Glass Filter 250-765 W / m 2 from Atlas Material Testing Technology GmbH, Linsenrich, Germany) for 96 hours.
- the discoloration was assessed visually based on the Blue Wool Scale in accordance with DIN EN ISO 105-B02, where '8' stands for excellent light fastness (slight color change) and 'T' stands for very low light fastness (strong color change).
- the contrast of a surface treated with a laser beam compared to a surface not treated with the laser beam is a measure of the quality of laser inscribability at 1064 nm.
- the DPL-Genesis-Marker (8W) laser marking device from ACI Laser GmbH, Chemnitz, Germany, was used, which was equipped with the MagicMarkV3 marking software and the F-Theta 163 focusing lens.
- a Nd: YAG laser crystal acted as the laser and delivered laser light with a wavelength of 1064 nm.
- the contrast was classified as follows using the gray scale according to ISO 105-A03: Classification (-): The laser-irradiated area differed from the non-laser-irradiated area comparable to a gray scale according to ISO 105-A03 of class 3, 3/4, 4, 4/5 or 5. The laser-irradiated area could therefore not be distinguished, or only poorly, from the non-laser-irradiated area.
- Classification (+) The laser-irradiated area differed from the non-laser-irradiated area comparable to a gray scale according to ISO 105-A03 of classes 1 to 2/3. The laser-irradiated area could thus be easily distinguished from the non-laser-irradiated area
- Component A Linear polybutylene terephthalate (Pocan® B 1300, commercial product of Lanxess Germany GmbH, Cologne, Germany) with a
- Component B1 cerium (III) sulfide / lanthanum (III) sulfide [C.I. Pigment Orange 78 (Neolor Light Orange S from Baotou Hongbo Te Technology Co. Ltd., 'Inner Mongolia', China)
- Component X / 1) 12H-phthaloperin-12-one [CAS No. 6925-69-5] as Macrolex® Orange 3G from Lanxess Deutschland GmbH, Cologne
- Tab. II The results in Tab. II show that only example 1 according to the invention also showed a sufficiently good contrast after laser inscription with an Nd: YAG laser crystal at 1064 nm with simultaneously high lightfastness and very little tendency to bleeding, whereas the colorants according to the prior art did not have both good contrast and good lightfastness and a low tendency to bleeding at the same time.
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Medicinal Chemistry (AREA)
- Polymers & Plastics (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Compositions Of Macromolecular Compounds (AREA)
- Manufacture Of Macromolecular Shaped Articles (AREA)
- Processes Of Treating Macromolecular Substances (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| EP19196336.2A EP3792303A1 (de) | 2019-09-10 | 2019-09-10 | Hochvoltkomponenten |
| PCT/EP2020/074239 WO2021047937A1 (de) | 2019-09-10 | 2020-08-31 | Hochvoltkomponenten |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP4028465A1 true EP4028465A1 (de) | 2022-07-20 |
Family
ID=67909305
Family Applications (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19196336.2A Withdrawn EP3792303A1 (de) | 2019-09-10 | 2019-09-10 | Hochvoltkomponenten |
| EP20761853.9A Pending EP4028465A1 (de) | 2019-09-10 | 2020-08-31 | Hochvoltkomponenten |
Family Applications Before (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP19196336.2A Withdrawn EP3792303A1 (de) | 2019-09-10 | 2019-09-10 | Hochvoltkomponenten |
Country Status (6)
| Country | Link |
|---|---|
| US (1) | US20220348744A1 (de) |
| EP (2) | EP3792303A1 (de) |
| JP (1) | JP7472273B2 (de) |
| KR (1) | KR20220062507A (de) |
| CN (1) | CN114364728B (de) |
| WO (1) | WO2021047937A1 (de) |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115042497B (zh) * | 2022-08-16 | 2022-11-01 | 杭州和顺科技股份有限公司 | 一种双向拉伸阻燃聚酯薄膜及其制备方法 |
| CN121844000A (zh) | 2023-09-05 | 2026-04-10 | 朗盛德国有限责任公司 | 电动汽车部件 |
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| GB1122003A (en) | 1964-10-07 | 1968-07-31 | Gen Electric | Improvements in aromatic polycarbonates |
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| US3644574A (en) | 1969-07-17 | 1972-02-22 | Eastman Kodak Co | Shaped articles of blends of polyesters and polyvinyls |
| DE2036052A1 (en) | 1970-07-21 | 1972-01-27 | Milchwirtschafthche Forschungs und Untersuchungs Gesellschaft mbH, 2100 Hamburg | Working up of additives in fat and protein - contng foodstuffs |
| DE2063050C3 (de) | 1970-12-22 | 1983-12-15 | Bayer Ag, 5090 Leverkusen | Verseifungsbeständige Polycarbonate, Verfahren zu deren Herstellung und deren Verwendung |
| US4013613A (en) | 1971-10-01 | 1977-03-22 | General Electric Company | Reinforced intercrystalline thermoplastic polyester compositions |
| DE2211956A1 (de) | 1972-03-11 | 1973-10-25 | Bayer Ag | Verfahren zur herstellung verseifungsstabiler blockcopolycarbonate |
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| EP3281974A1 (de) | 2016-08-11 | 2018-02-14 | Innocabs B.V. | Lasermarkierungsadditiv |
| JP7054105B2 (ja) * | 2017-08-22 | 2022-04-13 | 三菱エンジニアリングプラスチックス株式会社 | レーザー溶着用樹脂組成物及びその溶着体 |
-
2019
- 2019-09-10 EP EP19196336.2A patent/EP3792303A1/de not_active Withdrawn
-
2020
- 2020-08-31 CN CN202080063100.2A patent/CN114364728B/zh active Active
- 2020-08-31 US US17/641,173 patent/US20220348744A1/en not_active Abandoned
- 2020-08-31 EP EP20761853.9A patent/EP4028465A1/de active Pending
- 2020-08-31 WO PCT/EP2020/074239 patent/WO2021047937A1/de not_active Ceased
- 2020-08-31 KR KR1020227007375A patent/KR20220062507A/ko not_active Ceased
- 2020-08-31 JP JP2022515737A patent/JP7472273B2/ja active Active
Also Published As
| Publication number | Publication date |
|---|---|
| US20220348744A1 (en) | 2022-11-03 |
| JP7472273B2 (ja) | 2024-04-22 |
| JP2022546868A (ja) | 2022-11-09 |
| EP3792303A1 (de) | 2021-03-17 |
| CN114364728B (zh) | 2023-11-28 |
| KR20220062507A (ko) | 2022-05-17 |
| WO2021047937A1 (de) | 2021-03-18 |
| CN114364728A (zh) | 2022-04-15 |
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