EP3810687A1 - Polyuréthane thermoplastique ignifugé - Google Patents

Polyuréthane thermoplastique ignifugé

Info

Publication number
EP3810687A1
EP3810687A1 EP19731756.3A EP19731756A EP3810687A1 EP 3810687 A1 EP3810687 A1 EP 3810687A1 EP 19731756 A EP19731756 A EP 19731756A EP 3810687 A1 EP3810687 A1 EP 3810687A1
Authority
EP
European Patent Office
Prior art keywords
composition
range
thermoplastic polyurethane
phosphorus
flame retardant
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
Application number
EP19731756.3A
Other languages
German (de)
English (en)
Inventor
Oliver Steffen Henze
Oliver Muehren
Birte NITZ
Tanja LANGE
Sabine Moeller
Alfons Bertels
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF SE
Original Assignee
BASF SE
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by BASF SE filed Critical BASF SE
Publication of EP3810687A1 publication Critical patent/EP3810687A1/fr
Pending legal-status Critical Current

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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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/53—Phosphorus bound to oxygen bound to oxygen and to carbon only
    • C08K5/5313—Phosphinic compounds, e.g. R2=P(:O)OR'
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/30—Low-molecular-weight compounds
    • C08G18/32—Polyhydroxy compounds; Polyamines; Hydroxyamines
    • C08G18/3203—Polyhydroxy compounds
    • C08G18/3206—Polyhydroxy compounds aliphatic
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/42—Polycondensates having carboxylic or carbonic ester groups in the main chain
    • C08G18/44—Polycarbonates
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/40—High-molecular-weight compounds
    • C08G18/48—Polyethers
    • C08G18/4854—Polyethers containing oxyalkylene groups having four carbon atoms in the alkylene group
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6633—Compounds of group C08G18/42
    • C08G18/6637—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/664—Compounds of group C08G18/42 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/28—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the compounds used containing active hydrogen
    • C08G18/65—Low-molecular-weight compounds having active hydrogen with high-molecular-weight compounds having active hydrogen
    • C08G18/66—Compounds of groups C08G18/42, C08G18/48, or C08G18/52
    • C08G18/6666—Compounds of group C08G18/48 or C08G18/52
    • C08G18/667—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38
    • C08G18/6674—Compounds of group C08G18/48 or C08G18/52 with compounds of group C08G18/32 or polyamines of C08G18/38 with compounds of group C08G18/3203
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/75—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic
    • C08G18/758—Polyisocyanates or polyisothiocyanates cyclic cycloaliphatic containing two or more cycloaliphatic rings
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G18/00—Polymeric products of isocyanates or isothiocyanates
    • C08G18/06—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen
    • C08G18/70—Polymeric products of isocyanates or isothiocyanates with compounds having active hydrogen characterised by the isocyanates or isothiocyanates used
    • C08G18/72—Polyisocyanates or polyisothiocyanates
    • C08G18/74—Polyisocyanates or polyisothiocyanates cyclic
    • C08G18/76—Polyisocyanates or polyisothiocyanates cyclic aromatic
    • C08G18/7657—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings
    • C08G18/7664—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups
    • C08G18/7671—Polyisocyanates or polyisothiocyanates cyclic aromatic containing two or more aromatic rings containing alkylene polyphenyl groups containing only one alkylene bisphenyl group
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • 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
    • C08K3/32—Phosphorus-containing compounds
    • 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
    • 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
    • C08K5/49—Phosphorus-containing compounds
    • C08K5/51—Phosphorus bound to oxygen
    • C08K5/52—Phosphorus bound to oxygen only
    • C08K5/5205—Salts of P-acids with N-bases
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/06—Polyurethanes from polyesters
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L75/00—Compositions of polyureas or polyurethanes; Compositions of derivatives of such polymers
    • C08L75/04—Polyurethanes
    • C08L75/08—Polyurethanes from polyethers
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B3/00—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties
    • H01B3/18—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances
    • H01B3/30—Insulators or insulating bodies characterised by the insulating materials; Selection of materials for their insulating or dielectric properties mainly consisting of organic substances plastics; resins; waxes
    • H01B3/302—Polyurethanes or polythiourethanes; Polyurea or polythiourea
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01B—CABLES; CONDUCTORS; INSULATORS; SELECTION OF MATERIALS FOR THEIR CONDUCTIVE, INSULATING OR DIELECTRIC PROPERTIES
    • H01B7/00—Insulated conductors or cables characterised by their form
    • H01B7/17—Protection against damage caused by external factors, e.g. sheaths or armouring
    • H01B7/29—Protection against damage caused by extremes of temperature or by flame
    • H01B7/295—Protection against damage caused by extremes of temperature or by flame using material resistant to flame
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • 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
    • C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
    • C08K3/20—Oxides; Hydroxides
    • C08K3/22—Oxides; Hydroxides of metals
    • C08K2003/2237—Oxides; Hydroxides of metals of titanium
    • C08K2003/2241—Titanium dioxide
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/002—Physical properties
    • C08K2201/005—Additives being defined by their particle size in general
    • 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
    • C08K2201/00—Specific properties of additives
    • C08K2201/019—Specific properties of additives the composition being defined by the absence of a certain additive

Definitions

  • the present invention relates to compositions comprising at least one thermoplastic polyurethane, a first phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphates and a further phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid, where the Composition is free from melamine cyanurate, and the use of such a composition for the production of cable jackets.
  • F1 phosphorus-containing flame retardant
  • F2 phosphorus-containing flame retardant selected from the group consisting of melamine polyphosphates
  • F2 phosphorus-containing flame retardant
  • thermoplastic polyurethanes are developed that have lower smoke gas toxicities and have good mechanical properties, abrasion resistance and flexibility. Because of the insufficient flame behavior, compositions based on thermoplastic polyurethanes are developed which contain various flame retardants.
  • thermoplastic polyurethanes are primarily used in cable manufacture as a cable sheath. Often, thin cables with thin cable sheaths are required, which both pass the relevant flame tests (e.g. VW1) and also have sufficient mechanical properties.
  • thermoplastic polyurethanes Both halogen-containing and halogen-free flame retardants can be added to the thermoplastic polyurethanes (TPU).
  • the halogen-free, flame-retardant thermoplastic polyurethanes generally have the advantage that they develop less toxic and less corrosive flue gases when they burn.
  • Halogen-free, flame-retardant TPUs are described, for example, in EP 0 617 079 A2, WO 2006/121549 A1 or
  • US 2013/0059955 A1 also discloses halogen-free TPU compositions with flame retardants based on phosphate.
  • US 2013/0081853 A1 relates to halogen-free flame retardant compositions comprising a TPU polymer and a polyolefin as well as phosphorus-based flame retardants and other additives. According to US 2013/0081853 A1, the compositions have good mechanical properties.
  • WO 97/00916 A describes melamine cyanurate in combination with tungsten acid / tungstic acid salts as a flame retardant for aliphatic polyamides.
  • EP 0 019 768 A1 discloses the flame-retardant treatment of polyamides with a mixture of melamine cyanurate and red phosphorus.
  • materials that contain only melamine cyanurate as flame retardants have neither a good oxygen index (Limiting Oxygen Index, LOI) nor a good flame resistance, for example determined by the performance in a UL 94 test, with thin wall thicknesses.
  • WO 2006/121549 A1 also describes materials which contain a combination of melamine polyphosphate, phosphinate and borate as flame retardants. These materials achieve high LOI values with thin wall thicknesses, but not good results in the UL 94 test.
  • TPU materials tend to flow because the urethane bonds split when the temperature rises. In vertical flame tests, flowing the TPU causes the layers of material facing the flame to flow away and new material to be exposed to the flame. The formation of a stable protective layer can therefore usually only be achieved with high levels of flame retardants. However, these high levels of filling result in a drop in properties, for example a significantly reduced tensile strength.
  • compositions known from the prior art accordingly either do not have sufficient mechanical properties or have inadequate flame properties, such as flame retardancy and performance, in the UL 94V test.
  • PCT / EP2015 / 053192 discloses compositions which contain a thermoplastic polyurethane, melamine cyanurate and a combination of phosphorus-containing flame retardants. According to PCT / EP2015 / 053192, these compositions have the advantage of good flame resistance combined with good mechanical properties and good chemical resistance.
  • thermoplastic polyurethanes that have high tensile strengths, high elongation at break and low abrasion values are also frequently required. Such materials are required for a wide variety of applications, e.g. Hoses, foils and cables but also for injection molded parts.
  • VDE standard EN 50363-10-2 requires materials for cable sheaths that have a tensile strength of at least 25 MPa determined according to DIN EN ISO 527.
  • thermoplastic polyurethanes with a low smoke density are required, especially if the products are to be used in closed rooms.
  • Materials with low corrosiveness of the combustion gases are also advantageous, since the damage in the event of a fire is less.
  • Materials with good UV resistance are also often required. This is especially the case when the articles are exposed to direct sunlight. For example, for colored cables in daily use such as power cables, cables for headphones or data transfer cables, high lightfastness is required.
  • TPU materials there are also very high requirements with regard to the processing of TPU materials.
  • the materials should be able to be processed homogeneously and evenly in the extrusion.
  • Low nozzle abrasion is particularly important here.
  • the TPU materials should also have good aging resistance and be less susceptible to hydrolysis.
  • the materials should have good media resistance.
  • good resistance to various oils is required.
  • good resistance to, for example, ketchup and sun creams is required.
  • the present invention was accordingly based on the object of providing flame-retardant thermoplastic polyurethanes which have good mechanical properties, show good flame retardant properties, at the same time have good mechanical and chemical resistance and, in addition, undergo little or no discoloration when exposed to UV radiation.
  • composition comprising at least components (i) to (iii):
  • thermoplastic polyurethane (i) a thermoplastic polyurethane
  • a first phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphates and
  • a further phosphorus-containing flame retardant selected from the group consisting of derivatives of phosphinic acid, the composition being free from melamine cyanurate.
  • compositions according to the invention contain at least one thermoplastic polyurethane and a combination of two phosphorus-containing flame retardants (F1) and (F2) and are free from melamine cyanurate. It has surprisingly been found that the compositions according to the invention have an optimized property profile due to the combination of the components according to the invention, in particular for use as cable sheathing. It was surprisingly found that the compositions according to the invention have improved properties compared to the compositions known from the prior art, for example increased flame retardancy and, in particular, do not or only slightly discolor when exposed to UV radiation.
  • the compositions according to the invention contain a thermoplastic polyurethane as component (i), a first phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphates as component (ii) and a further phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid as component (iii).
  • the composition is free from melamine cyanurate.
  • free from melamine cyanurate means that the composition contains less than 50 ppm melamine cyanurate, preferably less than 20 ppm melamine cyanurate.
  • the composition has 0 ppm melamine cyanurate.
  • composition according to the invention preferably contains only small amounts of polyhydric alcohols, for example 3-, 4-, 5- and 6-valent alcohols.
  • the composition according to the invention is further preferably free from polyhydric alcohols, in particular is free from 3-, 4-, 5- and 6-valent alcohols.
  • the present invention accordingly relates to a composition as described above, the composition being free from 3-, 4-, 5- and 6-valent alcohols, for example from sugars.
  • “free of 3-, 4-, 5- and 6-valent alcohols” or “free of polyhydric alcohols” means that the composition contains less than 50 ppm of polyhydric alcohols, preferably less than 20 ppm polyhydric alcohols.
  • the composition has 0 ppm of polyhydric alcohols.
  • the flame retardant (F1) is selected from the group consisting of melamine polyphosphates.
  • melamine polyphosphate in the context of the present invention one understands u. a. all commercial and commercially available product qualities.
  • known melamine polyphosphates can be used, for example those with a phosphorus content in the range from 7 to 20% by weight, preferably in the range from 10 to 17% by weight, more preferably in the range from 12 to 14% by weight.
  • the present invention accordingly relates to a composition as described above, the melamine polyphosphate having a phosphorus content in the range from 7 to 20% by weight.
  • the melamine polyphosphate suitable according to the invention preferably consists of particles which usually have an average particle diameter D50 in the range from 0.1 pm to 100 pm, preferably from 0.5 pm to 60 pm, particularly preferably 1 pm to 10 pm.
  • the particles preferably have an average particle diameter D99 of less than 100 pm, more preferably less than 90 pm.
  • the particles preferably have an average particle diameter D50 in the range from 0.1 pm to 100 pm and an average particle diameter D99 of less than 100 pm.
  • the particle size distribution in the context of the present invention can be monomodal or multimodal, for example bimodal.
  • the present invention therefore relates to a composition as described above, the melamine polyphosphate having a particle size in the range from 0.1 to 100 ⁇ m.
  • a melamine polyphosphate is preferably used which has a pH in the range from 3 to 7, more preferably in the range from 3.5 to 6.5, particularly preferably in the range from 4 to 6 in aqueous solution , each determined according to ISO 976.
  • Melamine polyphosphate is present in the composition according to the invention in suitable amounts.
  • the proportion of melamine polyphosphate in the composition is in the range from 2 to 35% by weight, based on the overall composition, in particular in the range from 3 to 30% by weight, preferably composition in the range from 4 to 25% by weight.
  • % based on the total composition, in particular composition in the range from 5 to 20% by weight, based on the total composition.
  • the present invention therefore relates to a composition as described above, the proportion of melamine polyphosphate in the composition being in the range from 2 to 35% by weight, based on the overall composition.
  • the sum of the components of the composition is 100% by weight.
  • the flame retardant (F2) is preferably selected from derivatives of phosphinic acid, salts with organic or inorganic cations or organic esters.
  • Organic esters are derivatives of phosphinic acid, in which at least one oxygen atom bonded directly to the phosphorus is esterified with an organic radical.
  • the organic ester is an alkyl ester, in another preferred embodiment an aryl ester. All hydroxyl groups of phosphinic acid are particularly preferably esterified.
  • the radicals R 1 , R 2 and R 3 are either aliphatic or aromatic and have 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 3.
  • Preferably at least one of the radicals is aliphatic, preferably all radicals are aliphatic, whole R 1 and R 2 are particularly preferred ethyl radicals.
  • R 3 is furthermore preferably an ethyl radical or a methyl radical. In a preferred embodiment, R 1 , R 2 and R 3 are simultaneously ethyl or methyl.
  • Phosphinates ie the salts of phosphinic acid
  • the radicals R 1 and R 2 are either aliphatic or aromatic and have 1 to 20 carbon atoms, preferably 1 to 10, more preferably 1 to 3.
  • Preferred salts of the phosphinic acids are aluminum, calcium or zinc salts, more preferably aluminum or zinc salts.
  • a preferred embodiment is diethyl aluminum phosphinate.
  • the present invention therefore relates to a composition as described above, the phosphorus-containing flame retardant (F2) being a phosphinate.
  • the present invention therefore relates to a composition as described above, the phosphinate being selected from the group consisting of aluminum phosphinates or zinc phosphinates.
  • the proportion of the flame retardant (F2) in the composition according to the invention is, for example, in the range from 5 to 45% by weight, based on the overall composition, in particular 7 to 40% by weight, based on the total composition, preferably in the range from 8 to 38% by weight, based on the overall composition, in particular in the range from 10 to 35% by weight based on the total composition , more preferably in the range from 12 to 32% by weight, based on the overall composition, particularly preferably in the range from 15 to 30% by weight based on the overall composition.
  • the present invention therefore relates to a composition as described above, the proportion of the flame retardant (F2) in the composition being in the range from 5 to 45% by weight, based on the overall composition ,
  • the proportion of the sum of the phosphorus-containing flame retardant (F1) and the phosphorus-containing flame retardant (F2) in the composition is preferably in the range from 7 to 40% by weight, based on the overall composition, more preferably in the range from 10 to 35%. %, particularly preferably in the range from 15 to 30% by weight, in each case based on the overall composition.
  • the present invention accordingly relates to a composition as described above, the proportion of the sum of the phosphorus-containing flame retardant (F1) and the phosphorus-containing flame retardant (F2) in the composition being in the range from 7 to 40% by weight , based on the total composition.
  • Flame retardants (F1) and / or (F2) are preferably used in the context of the present invention, the particles having an average particle diameter D50 in the range from 0.1 pm to 100 pm, preferably from 0.5 pm to 60 pm, particularly preferably 20 pm to 40 pm.
  • the particles preferably have an average particle diameter D99 of less than 100 pm, more preferably less than 90 pm.
  • the particles preferably have an average particle diameter D50 in the range from 0.1 pm to 100 pm and an average particle diameter D99 of less than 100 pm.
  • the particle size distribution in the context of the present invention can be monomodal or also multimodal, for example bimodal
  • the composition can also contain further flame retardants, for example further phosphorus-containing flame retardants such as phosphoric acid esters.
  • further flame retardants for example further phosphorus-containing flame retardants such as phosphoric acid esters.
  • the composition preferably contains further phosphorus-containing flame retardants in an amount in the range from 2 to 10% by weight.
  • Derivatives of phosphoric acid, derivatives of phosphonic acid or derivatives of phosphinic acid or mixtures of two or more of these derivatives are suitable, for example.
  • Suitable other flame retardants can, for example, be liquid at 21 ° C.
  • the derivatives of phosphoric acid, phosphonic acid or phosphinic acid are preferably salts with organic or inorganic cations or organic esters.
  • Organic esters are derivatives of phosphorus-containing acids, in which at least one oxygen atom bonded directly to the phosphorus is esterified with an organic radical.
  • the organic ester is an alkyl ester, in another preferred embodiment an aryl ester. All hydroxyl groups of the corresponding phosphorus-containing acid are particularly preferably esterified.
  • a preferred resorcinol is resorcinol bis-diphenyl phosphate (RDP), which is usually present in oligomers.
  • BDP bisphenol-A bis (diphenyl phosphate)
  • DPK diphenyl cresyl phosphate
  • the composition according to the invention further contains at least one thermoplastic polyurethane.
  • Thermoplastic polyurethanes are generally known.
  • the preparation is usually carried out by reacting components (a) isocyanates and (b) compounds which are reactive toward isocyanates and optionally (c) chain extenders, if appropriate in the presence of at least one (d) catalyst and / or (e) customary auxiliaries and / or additives.
  • Components (a) isocyanate, (b) compounds reactive toward isocyanates, (c) chain extenders are addressed individually or together as structural components.
  • the organic isocyanates (a) used are preferably aliphatic, cycloaliphatic, araliphatic and / or aromatic isocyanates, more preferably tri, tetra, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl-pentamethylene diisocyanate -1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-isocyanato-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane (Isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3- bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, 1-methyl-2, 4- and / or -2, 6-cyclohexane diiso
  • MDI 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate
  • NDI 1,5-naphthylene diisocyanate
  • TDI 2,4- and / or 2,6-tolylene diisocyanate
  • 4'-MDI is particularly preferably used.
  • the present invention therefore relates to a composition as described above, the thermoplastic polyurethane being based on diphenylmetal diisocyanate (MDI).
  • MDI diphenylmetal diisocyanate
  • all suitable compounds known to the person skilled in the art can be used as compounds (b) which are reactive toward isocyanates.
  • at least one diol is used as the compound (b) which is reactive toward isocyanates.
  • diols can be used in the context of the present invention, for example polyether diols or polyester diols or mixtures of two or more thereof.
  • polyester diol in principle, according to the invention, all suitable polyester diols can be used, where in the context of the present invention the term polyester diol also includes polycarbonate diols.
  • a polycarbonate diol or a polytetrahydrofuran polyol is used.
  • Suitable polytetrahydrofuran polyols have, for example, a molecular weight in the range from 500 to 5000 g / mol, preferably 500 to 2000 g / mol, particularly preferably 800 to 1200 g / mol.
  • Suitable polycarbonate diols are, for example, polycarbonate diols based on alkane diols. Suitable polycarbonate diols are strictly difunctional OH-functional polycarbonate diols, preferably strictly difunctional OH-functional aliphatic polycarbonate diols.
  • Suitable polycarbonate diols are based, for example, on 1,4-butanediol, 1,5-pentanediol or 1,6-hexanediol, in particular 1,4-butanediol, 1,5-pentanediol, 1,6-hexanediol, 3-methylpentane (1 , 5) -diol or mixtures thereof, particularly preferably 1, 4-butanediol, 1, 5-pentanediol, 1, 6-hexanediol or mixtures thereof.
  • polycarbonate diols based on 1,4-butanediol and 1,6-hexanediol preference is given to polycarbonate diols based on 1,4-butanediol and 1,6-hexanediol, polycarbonate diols based on 1,5-pentanediol and 1,6-hexanediol, polycarbonate diols based on 1,6-hexanediol, and mixtures of two or more of these polycarbonate diols are used.
  • compositions according to the invention preferably contain at least one thermoplastic polyurethane selected from the group consisting of thermoplastic polyurethanes based on at least one diisocyanate and at least one polycarbonate diol and thermoplastic polyurethanes based on at least one diisocyanate and polytetrahydrofuran polyol. Accordingly, at least one polycarbonate diol or one polytetrahydrofuran polyol is used as component (b) to produce the polyurethanes contained in the compositions according to the invention.
  • the present invention therefore relates to a composition as described above, the thermoplastic polyurethane being selected from the group consisting of at least one diisocyanate and at least one polycarbonate diol-based thermoplastic polyurethane and at least one diisocyanate and polytetrahydrofuran polyol based thermoplastic polyurethanes.
  • the present invention also relates to a composition as described above, the thermoplastic polyurethane being selected from the group consisting of at least one aromatic diisocyanate and at least one polymer. carbonate diol-based thermoplastic polyurethanes and at least one aromatic diisocyanate and polytetrahydrofuran polyol-based thermoplastic polyurethanes.
  • the present invention also relates to a composition as described above, the thermoplastic polyurethane being a thermoplastic polyurethane based on at least one diisocyanate and at least one polycarbonate diol.
  • the polycarbonate diols used preferably have a number average molecular weight Mn in the range from 500 to 4000 g / mol, determined by GPC, preferably in the range from 650 to 3500 g / mol, determined by GPC, particularly preferably in the range from 800 to 2500 g / mol, determined via GPC, on.
  • the present invention also relates to a composition as described above, the thermoplastic polyurethane being a thermoplastic polyurethane based on at least one diisocyanate and at least one polycarbonate diol and the at least one polycarbonate diol being selected from the group consisting of polycarbonate diols based on 1,4-butanediol and 1,6-hexanediol, polycarbonate diols based on 1,5-pentanediol and 1,6-hexanediol, polycarbonate diols based on 1,6-hexanediol, and mixtures of two or more of these polycarbonate diols , Copolycarbonate diols based on the diols 1, 5-pentanediol and 1, 6-hexanediol are further preferred, preferably with a molecular weight Mn of approximately 2000 g / mol.
  • the present invention therefore relates to a composition as described above, the polycarbonate diol having a number-average molecular weight Mn in the range from 500 to 5000 g / mol, determined via GPC, preferably in the range from 650 to 3500 g / mol, determined via GPC, more preferably in the range from 800 to 2500 g / mol, determined via GPC.
  • Chain extenders (c) which can preferably be used are aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds having a molecular weight of 0.05 kg / mol to 0.499 kg / mol, preferably 2-functional compounds, for example diamines and / or alkanediols with 2 to 10 carbon atoms in the alkylene radical, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols with 3 to 8 carbon atoms, in particular 1, 2-ethylene glycol, 1 , 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, preferably corresponding oligo- and / or polypropylene glycols, it also being possible to use mixtures of the chain extenders.
  • the compounds (c) preferably have only primary hydroxyl groups; 1,4-
  • a polyhydric alcohol for example propanediol and / or a further diol, which was obtained at least in part from renewable raw materials. It is possible that the polyhydric alcohol was partly or wholly obtained from renewable raw materials. According to the invention, at least one of the polyhydric alcohols used is at least partially obtained from renewable raw materials.
  • So-called bio-1, 3-propanediol can be obtained, for example, from corn and / or sugar. Another option is the conversion of glycerin waste from biodiesel production.
  • the polyhydric alcohol is 1,3-propanediol, which has been obtained at least in part from renewable raw materials.
  • the present invention accordingly relates to a composition as described above, the thermoplastic polyurethane being based on at least 30% on renewable raw materials.
  • a suitable method of determination is, for example, the C14 method.
  • catalysts (d) which in particular accelerate the reaction between the NCO groups of the diisocyanates (a) and the hydroxyl groups of the isocyanate-reactive compound (b) and the chain extender (c), are tertiary amines, in particular triethylamine , Dimethylcyclohexylamine, N-methylmorpholine, N, N'-dimethylpiperazine, 2- (dimethylaminoethoxy) ethanol, diazabicyclo (2,2,2) octane, in another preferred embodiment these are organic metal compounds, such as titanium acid esters, iron compounds , preferably iron (III) acetylacetonate, tin compounds, preferably tin diacetate, tin dioctoate, tin dilaurate or the tin dialkyl salts of aliphatic carboxylic acids, preferably dibutyltin diacetate, dibutyltin dilaurate or bismuth salts
  • the carboxylic acids used are preferably carboxylic acids having 6 to 14 carbon atoms, particularly preferably having 8 to 12 carbon atoms.
  • suitable bismuth salts are bismuth (III) neodecanoate, bismuth 2-ethylhexanoate and bismuth octanoate.
  • the catalysts (d) are preferably used in amounts of 0.0001 to 0.1 part by weight per 100 parts by weight of the compound (b) reactive with isocyanates.
  • Tin catalysts are preferably used, in particular tin dioctoate.
  • auxiliaries can also be added to the structural components (a) to (c).
  • examples include surface-active substances, fillers, other flame retardants, nucleating agents, oxidation stabilizers, lubricants and mold release agents, dyes and pigments, optionally stabilizers, e.g. against hydrolysis, light, heat or discoloration, inorganic and / or organic fillers, reinforcing agents and plasticizers.
  • Suitable auxiliaries and additives can be found, for example, in the plastics handbook, volume VII, published by Vieweg and Höchtlen, Carl Hanser Verlag, Kunststoff 1966 (pp. 103-1 13).
  • thermoplastic polyurethanes are disclosed, for example, in EP 0 922 552 A1, DE 101 03 424 A1 or WO 2006/072461 A1.
  • the production is usually carried out on a belt system or a reaction extruder, but can also be carried out on a laboratory scale, for example in the hand casting process.
  • they are all mixed directly with one another or individual components are premixed and / or pre-reacted, for example to form prepolymers, and only then brought to polyaddition.
  • a thermoplastic polyurethane is first produced from the structural components, optionally with a catalyst, into which auxiliary substances may also be incorporated.
  • At least one flame retardant is then introduced into this material and distributed homogeneously.
  • the homogeneous distribution is preferably carried out in an extruder, preferably in a twin-screw extruder.
  • the amounts of the structural components (b) and (c) used can be varied in relatively wide molar ratios, the hardness usually increasing with increasing content of chain extender (c).
  • thermoplastic polyurethanes e.g.
  • the essentially difunctional polyhydroxyl compounds (b) and chain extenders (c) can advantageously be used in molar ratios of 1: 1 to 1: 5, preferably 1: 1, 5 to 1: 4.5, so that the resulting mixtures of the build-up components (b) and (c) have a hydroxyl equivalent weight of greater than 200, and in particular from 230 to 450, own while producing harder TPU, e.g.
  • the thermoplastic polyurethane used according to the invention preferably has a hardness in the range from 68A to 100A, determined in accordance with DIN ISO 7619-1 (Shore hardness test A (3s)), preferably in the range from 70A to 98A, determined in accordance with DIN ISO 7619-1 preferably in the range from 75A to 95A, determined according to DIN ISO 7619-1, particularly preferably in the range from 75A to 90A, determined according to DIN ISO 7619-1, in particular in the range from 78A to 85A, determined according to DIN ISO 7619-1.
  • the thermoplastic polyurethane used preferably has a hardness in the range from 70 A to 80 A, determined in accordance with DIN ISO 7619-1 (Shore hardness test A (3s)).
  • the present invention therefore relates to a composition as described above, the thermoplastic polyurethane having a Shore hardness in the range from 68A to 100A, determined in accordance with DIN 53505.
  • the structural components (a), (b) and (c) are preferably reacted in the presence of catalysts (d) and, if appropriate, auxiliaries and / or additives (e) in amounts such that the Equivalence ratio of NCO groups of the diisocyanates (a) to the sum of the hydro- xyl groups of the structural components (b) and (c) is 0.9 to 1.1: 1, preferably 0.95 to 1.05: 1 and in particular approximately 1.0 to 1.04: 1.
  • the composition according to the invention contains the at least one thermoplastic polyurethane in an amount in the range from 60% by weight to 93% by weight, based on the overall composition, in particular in the range from 65% by weight to 92% by weight. , based on the entire composition, preferably in the range from 68% by weight to 90% by weight, more preferably in the range from 70% by weight to 88% by weight and particularly preferably in the range from 70% by weight. -% 85 wt .-%, each based on the entire composition.
  • the present invention therefore relates to a composition as described above, the proportion of the thermoplastic polyurethane in the composition being in the range from 60% by weight to 93% by weight, based on the overall composition.
  • thermoplastic polyurethanes in which the thermoplastic polyurethane has an average molecular weight (Mw) in the range from 50,000 to 500,000 Da are preferably used according to the invention.
  • the upper limit for the average molecular weight (Mw) of the thermoplastic polyurethanes is generally determined by the processability and also the desired property spectrum. More preferably, the thermoplastic polyurethane has an average molecular weight (Mw) in the range from 100,000 to 300,000 Da, more preferably in the range from 120,000 to 250,000, particularly preferably in the range from 150,000 to 250,000 Da.
  • the present invention therefore relates to a composition as described above, the thermoplastic polyurethane having an average molecular weight (Mw) in the range from 100,000 to 300,000 Da.
  • thermoplastic polyurethanes with a molecular weight (Mw) in the range from 100,000 to 300,000 Da leads to compositions which have particularly advantageous combinations of properties.
  • the composition can contain two or more thermoplastic polyurethanes which differ, for example, in their average molecular weight or in their chemical composition.
  • the composition according to the invention can contain a first thermoplastic polyurethane TPU-1 and a second thermoplastic polyurethane TPU-2, for example a thermoplastic polyurethane TPU-1 based on an aliphatic diisocyanate, and a further TPU-2, the based on an aromatic diisocyanate.
  • An aliphatic isocyanate is used to produce TPU-1
  • an aromatic isocyanate is used to produce TPU-2.
  • organic isocyanates (a) for the production of TPU-1 aliphatic or cycloaliphatic isocyanates are preferably used, more preferably tri, tetra, penta-, hexa-, hepta- and / or octamethylene diisocyanate, 2-methyl-pentamethylene diisocyanate-1, 5, 2-ethyl-butylene-diisocyanate-1, 4, pentamethylene-diisocyanate-1, 5, butylene-diisocyanate-1, 4, 1-isocyanato-3,3,5-trimethyl-5- isocyanatomethyl-cyclohexane (isophorone diisocyanate, IPDI), 1, 4- and / or 1, 3-bis (isocyanatomethyl) cyclohexane (HXDI), 1, 4-cyclohexane diisocyanate, 1-methyl-2,4- and / or -2, 6-cyclohexane diisocyanate and /
  • the present invention therefore relates to a composition as described above, the thermoplastic polyurethane TPU-1 being based on at least one aliphatic diisocyanate selected from the group consisting of hexamethylene diisocyanate and di (isocyanatocyclohexyl) methane.
  • Araliphatic and / or aromatic isocyanates are preferably used as organic isocyanates (a) for the production of TPU-2, more preferably 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate (MDI), 1 , 5-naphthylene diisocyanate (NDI), 2,4- and / or 2,6-tolylene diisocyanate (TDI), 3,3'-dimethyl-diphenyl-diisocyanate, 1, 2-diphenylethane diisocyanate and / or phenylene diisocyanate.
  • MDI 2,2'-, 2,4'- and / or 4,4'-diphenylmethane diisocyanate
  • NDI 5-naphthylene diisocyanate
  • TDI 2,4- and / or 2,6-tolylene diisocyanate
  • 4,4 ' -MDI is particularly preferably used.
  • the present invention therefore relates to a composition as described above, the thermoplastic polyurethane TPU-2 being based on diphenylmethane diisocyanate (MDI).
  • MDI diphenylmethane diisocyanate
  • a polycarbonate diol or a polytetrahydrofuran polyol is preferably used as the compounds (b) which are reactive toward isocyanates for TPU-1 and TPU-2.
  • Suitable polytetrahydrofuran polyols have, for example, a molecular weight in the range from 500 to 5000, preferably 500 to 2000, particularly preferably 800 to 1200.
  • At least one polycarbonate diol is preferably used for producing the TPU-1 and the TPU-2, preferably an aliphatic polycarbonate diol.
  • Suitable polycarbonate diols are, for example, polycarbonate diols based on alkane diols.
  • Suitable polycarbonate diols are strictly difunctional OH-functional polycarbonate diols, preferably strictly difunctional OH-functional aliphatic polycarbonate diols.
  • Suitable polycarbonate diols are based, for example, on butanediol, pentanediol or hexanediol, in particular 1,4-butanediol,
  • Polycarbonate diols based on butanediol and hexanediol, polycarbonate diols based on pentanediol and hexanediol, polycarbonate diols based on hexanediol, and mixtures of two or more of these polycarbonate diols are preferably used in the context of the present invention.
  • the polycarbonate diols used to prepare the TPU-1 and TPU-2 preferably have a number average molecular weight Mn in the range from 500 to 4000, determined via GPC, preferably in the range from 650 to 3500, determined via GPC, particularly preferably in the range from 800 to 3000, determined via GPC.
  • chain extenders (c) for the production of TPU-1 and TPU-2 preferably aliphatic, araliphatic, aromatic and / or cycloaliphatic compounds with a molecular weight of 0.05 kg / mol to 0.499 kg / mol, preferably 2-functional compounds, are used, for example diamines and / or alkanediols with 2 to 10 carbon atoms in the alkylene radical, di-, tri-, tetra-, penta-, hexa-, hepta-, octa-, nona- and / or decaalkylene glycols with 3 up to 8 carbon atoms, in particular 1, 2-ethylene glycol, 1, 3-propanediol, 1, 4-butanediol, 1, 6-hexanediol, preferably corresponding oligo- and / or polypropylene glycols, it also being possible to use mixtures of the chain extenders.
  • the compounds (c) preferably have only primary hydroxyl groups, very particularly preferably mixtures of 1,4-butanediol with a further chain extender selected from the compounds mentioned above are used, for example mixtures containing 1,4-butanediol and a second chain extender in one molar ratio in the range from 100: 1 to 1: 1, preferably in a range from 95: 1 to 5: 1, particularly preferably in a range from 90: 1 to 10: 1.
  • the present invention therefore relates to a composition as described above, a mixture of 1,4-butanediol and a further chain extender being used as chain extender to produce the thermoplastic polyurethane.
  • the amounts of structural components (b) and (c) used can be varied in relatively wide molar ratios, the hardness usually increasing with increasing content of chain extender (c) ,
  • the TPU-1 preferably has a hardness in the range from 85A to 70D, determined in accordance with DIN ISO 7619-1, preferably in the range from 95A to 70D, determined in accordance with DIN ISO 7619-1, more preferably in the range from 55D to 65D, determined according to DIN ISO 7619-1.
  • the TPU-2 preferably has a hardness in the range from 70A to 70D, determined in accordance with DIN ISO 7619-1, more preferably in the range from 80A to 60D, determined in accordance with DIN ISO 7619-1, particularly preferably in the range from 80A up to 90A, determined according to DIN ISO 7619-1.
  • the present invention therefore relates to a composition as described above, the thermoplastic polyurethane TPU-1 having a Shore hardness in the range from 85A to 65D, determined in accordance with DIN ISO 7619-1.
  • the present invention therefore relates to a composition such as previously described, the thermoplastic polyurethane TPU-2 having a Shore hardness in the range from 70A to 65D, determined in accordance with DIN ISO 7619-1.
  • the TPU-1 preferably has a molecular weight of greater than 100,000 Da
  • the TPU-2 preferably has a molecular weight in the range from 150,000 to 300,000 Da.
  • the upper limit for the number average molecular weight of the thermoplastic polyurethanes is generally determined by the processability and also the desired property spectrum.
  • the present invention therefore relates to a composition as described above, the thermoplastic polyurethane TPU-1 having a molecular weight in the range from 100,000 Da to 400,000 Da. According to a further embodiment, the present invention therefore relates to a composition as described above, the thermoplastic polyurethane TPU-2 having a molecular weight in the range from 150,000 to 300,000 Da.
  • the composition according to the invention contains the at least one thermoplastic polyurethane TPU-1 and the at least one thermoplastic polyurethane TPU-2 in total in an amount in the range from 60% by weight to 93% by weight, based on the overall composition , in particular in the range from 68% by weight to 92% by weight, based on the overall composition, preferably in the range from 70% by weight to 88% by weight, more preferably in the range from 70% by weight to 85% by weight, based on the total composition.
  • the ratio of the thermoplastic polyurethanes used can vary within wide ranges.
  • the thermoplastic polyurethane TPU-1 and the thermoplastic polyurethane TPU-2 are used in a ratio in the range from 2: 1 to 1: 5.
  • the thermoplastic polyurethane TPU-1 and the thermoplastic polyurethane TPU-2 are preferably in a ratio in the range from 1: 1 to 1: 5, more preferably in the range from 1: 2 to 1: 4, particularly preferably in the range from 1: 2 , 5 to 1: 3 used.
  • the present invention accordingly relates to a composition as described above, the composition comprising a mixture comprising thermoplastic polyurethane TPU-1, which is based on an aliphatic diisocyanate, and a thermoplastic polyurethane TPU-2, which is based on an aromatic Based on diisocyanate.
  • thermoplastic polyurethane and flame retardants (F1) and (F2) are processed in one work step in order to produce the compositions according to the invention.
  • a thermoplastic polyurethane is first produced using a reaction extruder, a belt system or other suitable devices, preferably in the form of granules, in which the flame retardants are then added in at least one further working step or even several working steps (F1) and (F2) are introduced.
  • the thermoplastic polyurethane is mixed with the other components in a mixing device, which is preferably an internal kneader or an extruder, preferably a twin-screw extruder.
  • At least one flame retardant introduced into the mixing device in the at least one further working step is liquid, ie liquid at a temperature of 21 ° C.
  • the flame retardant introduced is at least partially liquid at a temperature which prevails in the extruder behind the filling point in the flow direction of the filling material.
  • the composition can contain further flame retardants, for example phosphorus-containing flame retardants.
  • the composition can contain a further phosphorus-containing flame retardant (F3), for example phosphoric acid esters.
  • composition according to the invention contains no further flame retardants in addition to the phosphorus-containing flame retardants (F1) and (F2).
  • the hardness of the compositions according to the invention can vary within wide ranges.
  • the hardness of the composition can be in the range from 68A to 100A, determined in accordance with DIN ISO 7619-1 (Shore hardness test A (3s)), preferably in the range from 70A to 98A, determined in accordance with DIN ISO 7619-1.
  • the composition can also contain further constituents, for example customary auxiliaries and additives for thermoplastic polyurethanes.
  • the composition preferably contains no further flame retardants.
  • the composition according to the invention further preferably contains exactly one phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphates, and exactly one phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid.
  • the composition according to the invention can contain fillers or dyes, preferably in an amount in the range from 0.1 to 5% by weight, based on the overall composition.
  • the present invention accordingly relates to a composition as described above, the composition comprising titanium dioxide in an amount in the range from 0.1 to 5% by weight, based on the overall composition.
  • the present invention also relates to the use of the composition according to the invention containing at least one flame-retardant thermoplastic polyurethane as described above for the production of coatings, damping elements, bellows, foils or fibers, moldings, floors for buildings and transport, “non-woven” fabrics, preferably seals, rollers, shoe soles, hoses, cables, cable plugs, cable sheathing, pillows, laminates, profiles, belts, saddles, foams, plug connections,
  • Trailing cables, solar modules, cladding in automobiles are preferred. They are preferably produced from granules, by injection molding, calendering, powder sintering, or extrusion and / or by additional foaming of the composition according to the invention.
  • the present invention also relates to the use of a composition
  • a composition comprising at least one thermoplastic polyurethane, a first phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphates and a further phosphorus-containing flame retardant (F2) selected from the group consisting of derivatives of phosphinic acid, the composition being free from melamine cyanurate as described above for the manufacture of cable jackets.
  • compositions according to the invention allow the production of particularly thin cables, for example such cables with an outside diameter of less than 2 mm and a jacket thickness of less than 0.5 mm. Accordingly, according to a further embodiment, the present invention also relates to the use of a composition as described above for the production of cable jackets with a jacket thickness in the range from 0.1 to 0.5 mm.
  • Composition comprising at least components (i) to (iii):
  • thermoplastic polyurethane (i) a thermoplastic polyurethane
  • composition according to embodiment 1, wherein the composition is free from 3-, 4-, 5- and 6-valent alcohols.
  • Composition comprising at least components (i) to (iii):
  • thermoplastic polyurethane (i) a thermoplastic polyurethane
  • a first phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphates and
  • a further phosphorus-containing flame retardant selected from the group consisting of derivatives of phosphinic acid, the composition being free from melamine cyanurate, and the composition being free from 3-, 4-, 5- and 6-valent alcohols.
  • composition according to embodiment 4 wherein the phosphinate is selected from the group consisting of aluminum phosphinates or zinc phosphinates.
  • composition comprising at least components (i) to (iii):
  • thermoplastic polyurethane (i) a thermoplastic polyurethane
  • a first phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphates and
  • F2 phosphorus-containing flame retardant
  • composition according to one of the embodiments 1 to 6 the proportion of the sum of the phosphorus-containing flame retardant (F1) and the phosphorus-containing flame retardant (F2) in the composition being in the range from 7 to 40% by weight, based on the overall composition , lies.
  • Composition comprising at least components (i) to (iii):
  • thermoplastic polyurethane (i) a thermoplastic polyurethane
  • a first phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphates and
  • composition according to one of the embodiments 1 to 8 the melamine polyphosphate having a phosphorus content in the range from 7 to 20% by weight.
  • Composition comprising at least components (i) to (iii):
  • thermoplastic polyurethane (i) a thermoplastic polyurethane
  • a first phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphates and
  • thermoplastic polyurethane is selected from the group consisting of thermoplastic polyurethanes based on at least one aromatic diisocyanate and at least one polycarbonate diol and based on at least one aromatic diisocyanate and poly-tetrahydrofuran polyol thermoplastic polyurethanes.
  • the composition comprising a mixture comprising thermoplastic polyurethane TPU-1, which is based on an aliphatic diisocyanate, and a thermoplastic polyurethane TPU-2, which is based on an aromatic diisocyanate.
  • Composition comprising at least components (i) to (iii):
  • thermoplastic polyurethane (i) a thermoplastic polyurethane
  • a first phosphorus-containing flame retardant (F1) selected from the group consisting of melamine polyphosphates and
  • the composition being free from 3-, 4-, 5- and 6-valent alcohols, the proportion of the sum of the phosphorus-containing flame retardant (F1) and the phosphorus-containing flame retardant (F2) in the composition being in the range from 7 to 40% by weight %, based on the total composition, the melamine polyphosphate having a phosphorus content in the range from 7 to 20% by weight, and the composition comprising a mixture comprising thermoplastic polyurethane TPU-1, which is based on an aliphatic diisocyanate, and contains a thermoplastic polyurethane TPU-2 based on an aromatic diisocyanate.
  • thermoplastic polyurethane is based at least 30% on renewable raw materials.
  • composition according to one of the embodiments 1 to 16 the proportion of the thermoplastic polyurethane in the composition being in the range from 60 to 93% by weight, based on the overall composition.
  • composition according to one of the embodiments 1 to 17 the composition comprising titanium dioxide in an amount in the range from 0.1 to 5% by weight, based on the entire composition. 19. Composition according to one of the embodiments 1 to 18, the composition having a Shore hardness in the range from 68A to 100A, determined in accordance with DIN ISO 7619-1 (Shore hardness test A (3s)).
  • composition according to one of the embodiments 1 to 19 the proportion of the sum of the phosphorus-containing flame retardant (F1) and the phosphorus-containing flame retardant (F2) in the composition being in the range from 10 to 20% by weight, based on the overall composition , lies.
  • composition according to one of the embodiments 1 to 20 the proportion of the phosphorus-containing flame retardant (F1) in the composition being in the range from 2 to 15% by weight, based on the overall composition.
  • composition according to one of the embodiments 1 to 21 the proportion of the phosphorus-containing flame retardant (F2) in the composition being in the range from 5 to 45% by weight, based on the overall composition.
  • Elastollan A TPU with Shore hardness 85A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, based on polytetrahydrofuran polyol (PTHF) with a molecular weight of 1000 g / mol, 1,4-butanediol, diphenylmethane-4,4 ' diisocyanate.
  • PTHF polytetrahydrofuran polyol
  • Elastollan B TPU with Shore hardness 90A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, is based on polycarbonate polyol from Fi.
  • Ube Electroniccoll PH-200D, based on 1,5-pentanediol and 1,6-hexanediol
  • Ube Eternacoll PH-200D, based on 1,5-pentanediol and 1,6-hexanediol
  • Ube Eternacoll PH-200D, based on 1,5-pentanediol and 1,6-hexanediol
  • 1,4-butanediol diphenylmethane-4,4'-diisocyanate.
  • Elastollan C TPU with Shore Hardness 60D from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, is based on polytetrahydrofuran polyol (PTHF) with a molecular weight of 1000 g / mol, 1,4-butanediol, 4,4'-diisocyanatodicyclohexylmethane , TPU 1: TPU with Shore hardness 85A from BASF Polyurethanes GmbH, Elastogranstrasse 60, 49448 Lemförde, is based on polytetrahydrofuran polyol (PTHF) with a molecular weight of 1000 g / mol, 1,4-butanediol and propanediol in a molar ratio of 3: 1 , Diphenylmethane-4,4'-diisocyanate.
  • PTHF polytetrahydrofuran polyol
  • Disflamoll DPK Kresyldiphenylphosphate, CAS #: 026444-49-5, LANXESS GmbH, 51369 Leverkusen, Germany, acid number ⁇ 0.1 mg KOH / g, water content% (w / w) ⁇ 0.1.
  • Tinuvin 234 2- (2H-benzzotriazol-2-yl) 4,6-bis (1-ethyl-1-phenylethylphenol
  • Hombitan LW-S Anatase microcrystals without surface treatment, CAS #: 1317-70-0, Sachtleben Chemie GmbH, Duisburg, GERMANY, Ti02 share 99.2%; Average particle size 0.3 pm.
  • the following tables 1 a, 1 b and 1c list compositions in which the individual starting materials are given in parts by weight (GT).
  • the mi were each produced using a ZE 40 A twin-screw extruder from Berstorff with a partial process length of 35 D divided into 10 casings.
  • thermoplastic polyurethanes or mixtures of different polyurethanes used have an average molecular weight of greater than 150,000 Da.
  • the mixtures were extruded with an Arenz single-screw extruder with a three-zone screw with mixing part (screw ratio 1: 3) to give films with a thickness of 1.6 mm.
  • the density, shore hardness, tensile strength, tear propagation resistance, abrasion and elongation at break of the corresponding specimen were measured. All compositions have good mechanical properties. The results are in the following
  • cables were produced on a conventional extrusion line (smooth tube extruder, extruder diameter 45 mm) for cable insulation and cable sheathing.
  • a conventional three-zone screw with a compression ratio of 2.5: 1 was used.
  • the wires (4 twisted individual wires) were isolated with the respective mixtures using the tube method with 0.1 mm of the respective mixtures.
  • the diameter of the insulated wires was 0.7 mm.
  • Three of these cores were stranded and a sheath (sheath thickness 0.3 mm) was extruded using the tube method.
  • the outer diameter of the entire cable was 2 mm.
  • a VW 1 test (UL Standard 1581, ⁇ 1080 - VW-1 (vertical specimen) flame test) was then carried out on the cables. The test was carried out on 3 cables each. The results are summarized in Table 4.
  • a small value for delta E means less discoloration caused by the test. The less discoloration in the test, the less the discoloration to be expected in practical use, for example under the influence of sunlight.
  • Examples 18, 19 and 23 are advantageous because good UV resistance is achieved with very low stickiness.
  • Example 23 is particularly advantageous because good mechanical properties (tensile strength) are combined with good flame resistance, good UV resistance and low resilience.
  • Shore hardness A DIN ISO 7619-1
  • Shore hardness test A (3s) tensile strength: DIN EN ISO 527

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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)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Compositions Of Macromolecular Compounds (AREA)
  • Polyurethanes Or Polyureas (AREA)
  • Organic Insulating Materials (AREA)
  • Paints Or Removers (AREA)
  • Manufacturing Of Electric Cables (AREA)

Abstract

La présente invention concerne des compositions contenant au moins un polyuréthane thermoplastique, un premier agent ignifuge (F1) contenant du phosphore sélectionné parmi le groupe constitué de polyphosphates de mélamine et un autre agent ignifuge (F2) contenant du phosphore sélectionné parmi le groupe constitué de dérivés d'acide hypophosphoreux, la composition étant dépourvue de cyanurates de mélamine. L'invention concerne également l'utilisation d'une telle composition pour la fabrication de gainages de câbles.
EP19731756.3A 2018-06-25 2019-06-24 Polyuréthane thermoplastique ignifugé Pending EP3810687A1 (fr)

Applications Claiming Priority (2)

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EP18179577 2018-06-25
PCT/EP2019/066618 WO2020002200A1 (fr) 2018-06-25 2019-06-24 Polyuréthane thermoplastique ignifugé

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JP (1) JP7391894B2 (fr)
KR (1) KR20210022745A (fr)
CN (1) CN112313273B (fr)
MX (1) MX2021000091A (fr)
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KR20240035635A (ko) * 2021-08-03 2024-03-15 바스프 에스이 열가소성 폴리우레탄 조성물로 적어도 부분적으로 피복된 버스바
TW202402863A (zh) 2022-03-29 2024-01-16 德商巴斯夫歐洲公司 基於聚丙二醇之阻燃熱塑性聚氨酯 (tpu)
WO2024002869A1 (fr) 2022-06-27 2024-01-04 Basf Se Composition de polyuréthane thermoplastique (tpu) présentant des propriétés améliorées
CN115572476A (zh) * 2022-10-10 2023-01-06 孙明亮 一种抗菌阻燃耐水聚氨酯弹性体及制备方法

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TW202000789A (zh) 2020-01-01
MX2021000091A (es) 2021-03-25
CN112313273B (zh) 2023-08-22
JP7391894B2 (ja) 2023-12-05
US20210189100A1 (en) 2021-06-24
JP2021529854A (ja) 2021-11-04
KR20210022745A (ko) 2021-03-03
WO2020002200A1 (fr) 2020-01-02

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