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EP4341339A1 - Composition ignifuge contenant de 0,040 à 0,095 % en poids d'un retardateur de flamme - Google Patents

Composition ignifuge contenant de 0,040 à 0,095 % en poids d'un retardateur de flamme

Info

Publication number
EP4341339A1
EP4341339A1 EP22727195.4A EP22727195A EP4341339A1 EP 4341339 A1 EP4341339 A1 EP 4341339A1 EP 22727195 A EP22727195 A EP 22727195A EP 4341339 A1 EP4341339 A1 EP 4341339A1
Authority
EP
European Patent Office
Prior art keywords
weight
polycarbonate
group
formula
carbon atoms
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
EP22727195.4A
Other languages
German (de)
English (en)
Inventor
Helmut Werner Heuer
Michael Erkelenz
Christian Kaiser
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.)
Covestro Deutschland AG
Original Assignee
Covestro Deutschland AG
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 Covestro Deutschland AG filed Critical Covestro Deutschland AG
Publication of EP4341339A1 publication Critical patent/EP4341339A1/fr
Pending legal-status Critical Current

Links

Classifications

    • 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
    • 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
    • C08G63/00—Macromolecular compounds obtained by reactions forming a carboxylic ester link in the main chain of the macromolecule
    • C08G63/02—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds
    • C08G63/12—Polyesters derived from hydroxycarboxylic acids or from polycarboxylic acids and polyhydroxy compounds derived from polycarboxylic acids and polyhydroxy compounds
    • C08G63/16—Dicarboxylic acids and dihydroxy compounds
    • C08G63/18—Dicarboxylic acids and dihydroxy compounds the acids or hydroxy compounds containing carbocyclic rings
    • C08G63/19—Hydroxy compounds containing aromatic rings
    • C08G63/193—Hydroxy compounds containing aromatic rings containing two or more aromatic rings
    • C08G63/195—Bisphenol A
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/04—Reinforcing macromolecular compounds with loose or coherent fibrous material
    • C08J5/0405—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres
    • C08J5/043—Reinforcing macromolecular compounds with loose or coherent fibrous material with inorganic fibres with glass fibres
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/41—Compounds containing sulfur bound to oxygen
    • C08K5/42—Sulfonic acids; Derivatives thereof
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • 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
    • C08K5/36—Sulfur-, selenium-, or tellurium-containing compounds
    • C08K5/43—Compounds containing sulfur bound to nitrogen
    • C08K5/435—Sulfonamides
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/541—Silicon-containing compounds containing oxygen
    • C08K5/5415—Silicon-containing compounds containing oxygen containing at least one Si—O bond
    • C08K5/5419—Silicon-containing compounds containing oxygen containing at least one Si—O bond containing at least one Si—C bond
    • 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
    • C08K5/54—Silicon-containing compounds
    • C08K5/549—Silicon-containing compounds containing silicon in a ring
    • 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
    • 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
    • C08J2369/00—Characterised by the use of polycarbonates; Derivatives of polycarbonates
    • 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
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2201/00—Properties
    • C08L2201/02—Flame or fire retardant/resistant
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L2205/00—Polymer mixtures characterised by other features
    • C08L2205/02—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group
    • C08L2205/025—Polymer mixtures characterised by other features containing two or more polymers of the same C08L -group containing two or more polymers of the same hierarchy C08L, and differing only in parameters such as density, comonomer content, molecular weight, structure

Definitions

  • the present invention relates to compositions containing linear polycarbonate, branched polycarbonate and a small amount of salts of sulfonic acid, sulfonamide or sulfonimide derivatives.
  • the invention also relates to the use of branched polycarbonate in a polycarbonate composition to achieve a UL94 classification of V-0 with a layer thickness of 2.00 mm, preferably 1.5 mm.
  • Polycarbonate compositions enjoy a wide range of uses. However, they often have to be additionally admixed with flame retardants, especially for thin-walled applications, in order to be able to meet the high requirements for flame retardant properties.
  • flame retardants especially for thin-walled applications
  • the focus is always on reducing the quantity or even banning different flame retardants, since depending on the chemical nature of the flame retardants, they are already classified as "substances of very high concern, SVHC".
  • SVHC very high concern
  • halogenated flame retardants can be undesirable when exposed to heat
  • a common flame retardant in polycarbonate compositions is potassium perfluorobutane sulfonate (also called Rimar salt or C4 salt).
  • PFAS polyfluorinated alkyl substances
  • UBA Federal Environment Agency
  • WO2008/060714 A2 describes that flame-retardant polycarbonate compositions which simultaneously have good flow properties and good transparency can be obtained by terminating the polycarbonate used with cyanophenol end groups.
  • Example 16 of this document shows a composition containing 70 parts linear polycarbonate, 30 parts branched polycarbonate and 0.08 parts potassium perfluorobutanesulfonate. This composition has a UL94 rating of V-0 at 2.5mm. However, if the layer thickness is less than 1.57 mm, it is referred to as "dripping".
  • the use of cyanophenol end groups for the polycarbonate can also be disadvantageous.
  • the cyano group is a reactive group that can lead to secondary instabilities in the polycarbonate. Typically, such reactions result in undesirable changes in the color of the polycarbonate.
  • the use of cyanophenol is relatively expensive.
  • WO03/050176 A1 relates to translucent, flame-retardant polycarbonate compositions which, without the use of chlorinated or brominated flame retardants, nonetheless have good flame retardancy and at the same time have high transparency and low haze.
  • a composition comprising a branched polycarbonate, PTFE and, inter alia, potassium perfluorobutane sulfonate is proposed as a solution.
  • Comparative Example 13 of this document describes a composition containing 82 parts linear polycarbonate, 18 parts branched polycarbonate and 0.08 parts potassium perfluorobutanesulfonate.
  • the branched polycarbonate has a degree of branching of 0.3 mol, and this example also does not have good flame retardancy.
  • the document WO2012/06292 A1 describes polycarbonate compositions with good flame resistance at low layer thicknesses without the use of chlorinated or brominated flame retardants. To this end, the use of a linear phenyl-containing siloxane and a cyclic phenyl-containing siloxane is proposed.
  • the examples batches 1-3 to 1-7 in Table 3 of WO2012/06292 A1 describe compositions with 70 parts of linear polycarbonate, 30 parts of branched polycarbonate and 0.08 part of potassium perfluorobutanesulfonate. However, the Degree of branching of the polycarbonate used not explicitly stated, but appears to be relatively low.
  • DE60223842 T2 describes mixtures of a branched polycarbonate, linear polycarbonate, potassium perfluorobutanesulfonate and a cyclic siloxane. This document does not give any information about the end groups of the branched and/or linear polycarbonate. In addition, the degree of branching disclosed appears to be relatively low.
  • WO2015/140671 A1 describes flame-retardant compositions made from linear and branched polycarbonates, sodium dodecylbenzenesulfonate and a cyclic siloxane. The degree of branching is not disclosed in the examples.
  • KR20130124930A discloses polycarbonate compositions comprising linear and branched polycarbonate and a lactone-modified potassium perfluorobutane sulfonate. In this document, too, no statement is made about the end groups of the linear and/or branched polycarbonate. Likewise, this document also does not disclose a degree of branching in the examples.
  • WO01/83606A1 describes a composition of linear and branched polycarbonate, perfluoroalkane sulfonates and cyclic siloxanes. The end groups of the polycarbonates used are not mentioned. Likewise, the branched polycarbonate of the composition of Example 2 has a low degree of branching of 0.42 mol%. Proceeding from this prior art, the object of the present invention was to overcome at least one disadvantage of the prior art.
  • the object of the present invention was to provide a polycarbonate-containing composition which contains at most 0.095% by weight of a compound selected from the group of alkali metal, alkaline earth metal or ammonium salts of aliphatic or aromatic sulfonic acid, sulfonamide or sulfonimide derivatives and combinations contains from these and at the same time has at least one flame retardancy which corresponds to the UL94 classification of V-0 at 2.0 mm, preferably at 1.5 mm.
  • the thermal properties and / or the processability of the composition should not be negative compared to a composition with higher levels of compounds selected from the group of alkali, alkaline earth metal or ammonium salts of aliphatic or aromatic sulfonic acid, sulfonamide, or sulfonimide derivatives and Combinations of these are affected. At least one, preferably all of the above objects have been achieved by the present invention.
  • the composition preferably has at least a UL94 classification of V-0 with a layer thickness of 2.0 mm, preferably 1.5 mm, even without PFTE, without a halogenated flame retardant and/or also without a polysiloxane-polycarbonate block cocondensate.
  • compositions according to the invention have improved flowability and thus better processability than comparable compositions with a higher content of compounds selected from the group of alkali, alkaline earth metal or ammonium salts of aliphatic or aromatic sulfonic acid, sulfonamide or sulfonimide derivatives and combinations of these.
  • thermal properties of the composition according to the invention remain almost comparable to those with higher contents of said compound.
  • composition containing
  • each Y is independently a halogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, a
  • arylalkyl group having 7 to 12 carbon atoms, an alkylaryl group or a nitro group, y is 0 to 4 and c is 1 to 5, with the proviso that y+c is 1 to 5, and in which * represents the position with which the formula (1) the polycarbonate (B) terminates, (C) 0.040 to 0.095% by weight of a compound selected from the group consisting of alkali,
  • a linear polycarbonate is used as component (A).
  • the term “linear” is used in particular to differentiate it from the “branched” component (B).
  • Linear polycarbonates are known to those skilled in the art. He is also aware that many polycarbonates labeled "linear” have a may have a small proportion of branches. This is partly due to the manufacturing process of the polycarbonate. An example of these intrinsic branches are what are known as Fries structures, as are described for melt polycarbonates in EP 1 506249 A1.
  • the term “linear” preferably means that the polycarbonate has a degree of branching of ⁇ 0.4 mol %. The degree of branching is defined as explained below for component (B).
  • Component (A) is preferably an aromatic polycarbonate.
  • “Polycarbonate” in the sense of the invention is understood to mean both homopolycarbonates and copolycarbonates. Mixtures of polycarbonates can also be used according to the invention, but in this case each of the individual components is linear.
  • compositions according to the invention contain 3 to 85% by weight, in particular up to 84.96% by weight, of component (A), preferably 4 to 82% by weight, in particular up to 81.96% by weight, particularly preferably 14 to 81% % by weight, in particular up to 80.96% by weight, particularly preferably 19 to 80% by weight, in particular up to 79.96% by weight.
  • a proportion of 3 to 85% by weight of component (A), or the preferred % by weight described above, of the overall composition means, according to the invention, that the composition is based on polycarbonate.
  • the linear polycarbonates contained in the compositions are prepared in a known manner from dihydroxyaryl compounds, carbonic acid derivatives, optionally chain terminators and branching agents.
  • the polycarbonates are produced, for example, by reacting dihydroxyaryl compounds with carbonic acid halides, preferably phosgene, and/or with aromatic dicarboxylic acid dihalides, preferably
  • Benzenedicarboxylic acid dihalides by the phase interface method, if appropriate using chain terminators and optionally using trifunctional or more than trifunctional branching agents. Production via a melt polymerization process by reacting dihydroxyaryl compounds with, for example, diphenyl carbonate is also possible.
  • dihydroxyaryl compounds suitable for producing the polycarbonates are resorcinol, dihydroxydiphenyls, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl) sulfides, bis(hydroxyphenyl) ethers, bis(hydroxyphenyl) -ketones, bis(hydroxyphenyl) sulfones, bis(hydroxyphenyl) sulfoxides, a-a'-bis(hydroxyphenyl)diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives, and their nuclear-alkylated and nuclear-arylated compounds.
  • Preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis- (4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propane,
  • dimethyl bisphenol A bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl- 4-hydroxyphenyl) sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene and l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and the bisphenols (Aa) to (Ca) in which R' is in each case C1- to C4-alkyl, aralkyl or aryl, preferably methyl or phenyl, very particularly preferably methyl.
  • bisphenols are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4 -hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl and dimethylbisphenol A and the bisphenols of the formulas (Aa), (Ba) and (Ca).
  • Bisphenol A is very particularly preferred.
  • These and other suitable dihydroxyaryl compounds are, for example, in US Pat. No. 3,028,635, US Pat. No. 2,999,825, US Pat. No. 3,148,172, US Pat.
  • Suitable carbonic acid derivatives are phosgene or diphenyl carbonate.
  • Suitable chain terminators that can be used in the production of the polycarbonates are monophenols. Examples of suitable monophenols are phenol itself, alkylphenols such as cresols, p-tert-butylphenol, cumylphenol and mixtures thereof. However, no cyanophenol is preferably used as a chain terminator.
  • the linear polycarbonate (A) does not comprise end groups of formula (1): in which Y, y and c are as defined above. It is preferred that in formula (1) in relation to component (A) y is 1 to 2 and c is 1 to 2. It is particularly preferred that y is 0 and c is 1 to 2 in formula (1).
  • Formula (1) is very particularly preferred as para-cyanophenyl or 3,4-dicyanophenyl.
  • linear polycarbonate (A) and/or optionally also the polycarbonate (B) described later comprises end groups of the formula (2a), (2b) and/or (2c):
  • the linear polycarbonate (A) preferably has end groups of the formula (2a) and/or (2b), particularly preferably of the formula (2a).
  • the amount of chain terminator to be used is preferably 0.1 to 5 mol %, based on moles of dihydroxyaryl compounds used in each case.
  • the chain terminators can be added before, during or after the reaction with a carbonic acid derivative.
  • Particularly preferred polycarbonates (A) are the homopolycarbonate based on bisphenol A, the copolycarbonates based on 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane and 4,4'-dihydroxydiphenyl, and the copolycarbonates Based on the two monomers bisphenol A and 1,1-bis-(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, and homo- or copolycarbonates derived from the dihydroxyaryl compounds of the formulas (Ia), (IIa) and (IIIa). , especially with bisphenol A.
  • the polycarbonates (A) preferably have weight-average molecular weights Mw from 15,000 g/mol to 40,000 g/mol, more preferably up to 34,000 g/mol, particularly preferably from 17,000 g/mol to 33,000 g/mol, in particular from 19,000 g/mol to 32,000 g/mol, determined by gel permeation chromatography, calibrated against bisphenol A polycarbonate standards using dichloromethane as eluent, calibration with linear polycarbonates (from bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany, calibration according to method 2301- 0257502-09D (from 2009 in German) from Currenta GmbH & Co. OHG, Leverkusen.
  • the eluent is dichloromethane.
  • melt volume flow rate determined according to ISO 1133-1:2012-03 at 300° C. and 1.2 kg load, is 3 to 40 cm 3 /(10 min), preferably 4 to 35 cm 3 /(10 min) .
  • component (A) is preferably used in the form of powders, granules or mixtures of powders and granules.
  • a polycarbonate with a degree of branching of 1.01 to 1.5 mol% is also used as component (B), which comprises no end groups of the formula (1): each Y is independently a halogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an alkylaryl group or a nitro group, y is 0 to 4 and c is 1 to 5 is, with the proviso that y+c is 1 to 5, and in which
  • component (B) makes it possible to reduce the amount of component (C) while still giving the resulting moldings of the composition good flame retardance, ie at least flame retardance according to the UL94 classification of V-0 at 2 0 mm, preferably 1.5 mm.
  • the thermal properties of the composition are almost retained compared to a composition which contains more (C) but no (B).
  • the flowability of the compositions according to the invention is better than that of comparable compositions with a higher amount of (C) and no (B).
  • y is 1 to 2 and c is 1 to 2. It is particularly preferred that y is 0 and c is 1 to 2 in formula (1).
  • Formula (1) is very particularly preferred as para-cyanophenyl or 3,4-dicyanophenyl.
  • the polycarbonate (B) and optionally also the linear polycarbonate (A) comprises end groups of the formula (2a), (2b) and/or (2c): where * stands for the position at which the formulas (2a), (2b) and (2c) terminate the respective polycarbonate (A) and/or (B).
  • the branched polycarbonate (B) preferably has end groups of the formula (2a) and/or (2b), particularly preferably of the formula (2b).
  • linear polycarbonate (A) and the branched polycarbonate (B) have end groups of the formula (2a) and/or (2b).
  • the linear polycarbonate (A) very particularly preferably has end groups of the formula (2a) and the branched polycarbonate (B) has end groups of the formula (2b).
  • branched polycarbonate is also used for component (B) or polycarbonate (B).
  • This preferably has a degree of branching of 0.8 to 1.5 mol %, preferably 0.9 to 1.3 mol %, very particularly preferably 1.00 to 1.25 mol %, particularly preferably 1.1 up to 1.2 mol %.
  • component (B), i.e. polycarbonate (B), has a degree of branching of from 1.01 to 1.5 mol %, preferably from 1.02 to 1.3 mol %, particularly preferably from 1.03 to 1.25 mol %, further particularly preferably from 1.04 to 1.20 mol %, further preferably from 1.05 to 1.15 mol %, further preferably from 1.06 to 1.13 mol % and very particularly preferably from 1.07 to 1.1 mol%.
  • the term "branched” is to be understood in such a way that the polycarbonate has several branching points or a degree of branching.
  • THPE is used as the branching agent and the dihydroxy compound is BPA.
  • mol % (degree of branching) is mol % (degree of branching)
  • the term “degree of branching” refers to the chemical structure of the branching agent/branching agent as it is present in the polycarbonate after the reaction. It is preferred that the polycarbonate (B) has branches which are selected from the group consisting of the formulas (IIa) to (IIf) and any mixtures thereof: , where * stands for the positions connecting the branches to the polycarbonate chain and
  • R each independently represents H and an alkyl, preferably H and methyl
  • X represents a linear or branched alkyl or a single bond, preferably C(CH 3 ) 2 or a single bond
  • R 1 each independently represents H and an alkyl, preferably H and methyl
  • R 2 each independently represents H and an alkyl, preferably H and methyl.
  • the branched polycarbonate (B) may have one kind of branches shown above or a mixture of two or more branches.
  • the polycarbonate (B) has branches of formula (IId). It is particularly preferred that R 1 and R 2 independently represent H or alkyl. R 1 is particularly preferably methyl and R 2 is H. Such a branching structure results when THPE is used as a branching agent.
  • the polycarbonate (B) can be preferably produced by the routes described above for polycarbonate (A). In this case, however, the polycarbonate (B) is preferably produced by the phase interface process. This makes it possible to precisely set the degree of branching.
  • dihydroxyaryl compounds suitable for preparing the polycarbonates (B) are resorcinol, dihydroxydiphenyls, bis(hydroxyphenyl)alkanes, bis(hydroxyphenyl)cycloalkanes, bis(hydroxyphenyl) sulfides, bis(hydroxyphenyl) ethers, bis (Hydroxyphenyl) ketones, bis(hydroxyphenyl) sulfones, bis(hydroxyphenyl) sulfoxides, a-a'-bis(hydroxyphenyl)diisopropylbenzenes, phthalimidines derived from isatin or phenolphthalein derivatives, and their nucleus-alkylated and nucleated compounds .
  • Preferred dihydroxyaryl compounds are 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, 1,1-bis- (4-hydroxyphenyl)-p-diisopropylbenzene, 2,2-bis(3-methyl-4-hydroxyphenyl)propane, dimethyl bisphenol A, bis(3,5-dimethyl-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, bis(3,5-dimethyl- 4-hydroxyphenyl) sulfone, 2,4-bis(3,5-dimethyl-4-hydroxyphenyl)-2-methylbutane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)-p-diisopropylbenzene and l,l-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane,
  • bisphenols are 2,2-bis(4-hydroxyphenyl)propane (bisphenol A), 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 1,1-bis(4 -hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)-3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl and dimethylbisphenol A and the bisphenols of the formulas (Aa), (Ba) and (Ca).
  • Bisphenol A is very particularly preferred.
  • branching agents/branching agents are used in the synthesis of the polycarbonate (B) in order to obtain the appropriate degree of branching.
  • Suitable branching agents are the trifunctional or more than trifunctional compounds known in polycarbonate chemistry, in particular those having three or more than three phenolic OH groups.
  • suitable branching agents are 1,3,5-tri-(4-hydroxyphenyl)benzene, 1,1,1-tri-(4-hydroxyphenyl)ethane, tri-(4-hydroxyphenyl)phenylmethane, 2,4- bis-(4-hydroxyphenylisopropyl)-phenol, 2,6-bis-(2-hydroxy-5'-methyl-benzyl)-4-methylphenol, 2-(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl) -propane, tetra-(4-hydroxyphenyl)-methane, tetra-(4-(4-hydroxyphenylisopropyl)-phenoxy)-methane and 1,4-bis-((4',4"-dihydroxytriphenyl)-methyl)-benzene and 3,3-bis(3-methyl
  • R each independently represents H and an alkyl, preferably H and methyl
  • X represents a linear or branched alkyl or a single bond, preferably C(CH 3 ) 2 or a single bond
  • R 1 each independently represents H and an alkyl, preferably H and methyl
  • R 2 each independently represents H and an alkyl, preferably H and methyl.
  • a branching agent of the formula (IId) is particularly preferably used. It is particularly preferred that R 1 and R 2 independently represent H or alkyl. R 1 is particularly preferably methyl and R 2 is H.
  • the branching agents can either be initially taken with the dihydroxyaryl compounds and the chain terminators in the aqueous-alkaline phase or, dissolved in an organic solvent, can be added before the phosgenation. In the case of the transesterification process, the branching agents are used together with the dihydroxyaryl compounds.
  • the polycarbonates (B) preferably have weight-average molecular weights Mw from 15,000 g/mol to 40,000 g/mol, more preferably from 18,000 to 34,000 g/mol, particularly preferably from 22,000 g/mol to 33,000 g/mol, in particular from 23,000 g/mol to 32,000 g/mol, determined by gel permeation chromatography, calibrated against bisphenol A polycarbonate standards using dichloromethane as eluent, calibration with linear polycarbonates (from bisphenol A and phosgene) of known molar mass distribution from PSS Polymer Standards Service GmbH, Germany, calibration according to the method 2301- 0257502-09D (from 2009 in German) from Currenta GmbH & Co. OHG, Leverkusen.
  • the eluent is dichloromethane.
  • the melt volume flow rate (MVR), determined according to ISO 1133-1:2012-03 at 300° C. and 1.2 kg load, is 3 to 40 cm 3 /(10 min), preferably 4 to 35 cm 3 /(10 min) .
  • the composition comprises 15 to 96% by weight of component (B), preferably 18 to 95% by weight, particularly preferably 19 to 85% by weight, very particularly preferably 20 to 80% by weight.
  • component (B) is more expensive than component (A). He will therefore try to optimize the ratio of (A) to (B) in such a way that good properties (e.g. sufficient flame retardancy, good processability, etc.) result, but economical compositions are nevertheless created for the desired applications.
  • the composition may also include blend partners that are different from component (A) and (B). These are preferably thermoplastic polymers.
  • the composition according to the invention further comprises as component (C) a compound selected from the group of alkali metal, alkaline earth metal or ammonium salts of aliphatic or aromatic sulfonic acid, sulfonamide or sulfonimide derivatives and combinations thereof.
  • derivatives are understood here and elsewhere to mean those compounds whose molecular structure has another atom or another atomic group in place of an H atom or a functional group, or in which one or more atoms/atomic groups have been removed. The parent connection is thus still recognizable.
  • the composition according to the invention comprises as component (C) a compound which is selected from the group of aliphatic or aromatic sulfonic acid derivatives.
  • This compound particularly preferably does not include any lactone-modified derivatives.
  • this compound does not include such derivatives as described in KR20130124930 A.
  • Compositions according to the invention particularly preferably comprise, as flame retardants, one or more compounds selected from the group consisting of sodium or potassium perfluorobutane sulfate, sodium or potassium perfluoromethanesulfonate, sodium or potassium perfluorooctane sulfate, sodium or potassium 2,5-dichlorobenzene sulfate, sodium or potassium 2,4,5-trichlorobenzene sulfate, sodium or
  • Potassium diphenyl sulfone sulfonate sodium or potassium 2-formylbenzene sulfonate, sodium or potassium (N-benzenesulfonyl) benzene sulfonamide, partially fluorinated sodium or potassium fluoroalkyl sulfonates, or mixtures thereof.
  • Sodium or potassium perfluorobutane sulfate, sodium or potassium perfluorooctane sulfate, sodium or potassium diphenylsulfonate or mixtures thereof are preferably used.
  • Potassium perfluoro-1-butanesulfonate which is commercially available, inter alia as Bayowet® C4 from Lanxess, Leverkusen, Germany, is very particularly preferred.
  • Potassium diphenyl sulfone sulfonate also known as KSS (CAS 63316-43-8), is also preferably used. Potassium perfluoro-1-butanesulfonate and/or potassium diphenylsulfonate is very particularly preferred.
  • compositions according to the invention contain 0.040 to 0.095% by weight, preferably 0.045 to 0.094% by weight, further preferably 0.050 to 0.093% by weight, further preferably 0.055 to 0.092% by weight, further preferably 0.060 to 0.091 % by weight, more preferably 0.065 to 0.090% by weight, further preferably 0.070 to 0.085% by weight of component (C).
  • compositions according to the invention also optionally contain a reinforcing fiber as component (D).
  • a reinforcing fiber as component (D).
  • These reinforcing fibers can preferably be selected from glass fibers or carbon fibers.
  • the glass fibers are usually based on a glass composition selected from the group of M, E, A, S, R, AR, ECR, D, Q or C glasses, with E, S or C glass are preferred.
  • the glass fibers can be used in the form of chopped glass fibres, both long fibers and short fibres, ground fibres, glass fiber fabrics or mixtures of the aforementioned forms, with the chopped glass fibers and ground fibers being preferably used. Cut glass fibers are particularly preferably used.
  • the preferred fiber length of the chopped glass fibers before compounding is 0.5 to 10 mm, more preferably 1.0 to 8 mm, very particularly preferably 1.5 to 6 mm.
  • Chopped glass fibers can be used with different cross sections. Round, elliptical, oval, 8-shaped and flat cross sections are preferably used, round, oval and flat cross sections being particularly preferred.
  • the diameter of the round fibers used before compounding is preferably 5 to 25 ⁇ m, more preferably 6 to 20 ⁇ m, particularly preferably 7 to 17 ⁇ m, determined by means of light microscopic analysis.
  • Preferred flat and oval glass fibers have a height to width cross-sectional ratio of about 1.0:1.2 to 1.0:8.0, preferably 1.0:1.5 to 1.0:6.0, more preferably 1.0:2.0 to 1.0:4.0 on.
  • Preferred flat and oval glass fibers have an average fiber height of 4 ⁇ m to 17 ⁇ m, more preferably 6 ⁇ m to 12 ⁇ m and particularly preferably 6 ⁇ m to 8 ⁇ m and an average fiber width of 12 ⁇ m to 30 ⁇ m, more preferably 14 ⁇ m to 28 ⁇ m and more preferably 16 ⁇ m to 26 ⁇ m.
  • the fiber dimensions are preferably determined by means of light microscopic analysis.
  • the glass fibers are preferably modified with a glass size on the surface of the glass fibers. Preferred glass sizes include epoxy-modified, polyurethane-modified and unmodified silane compounds and mixtures of the aforementioned silane compounds.
  • the glass fibers can also not be modified with a glass size.
  • the glass fibers used are characterized in that the choice of fiber is not limited by the interaction characteristics of the fiber with the polycarbonate matrix. Both for a strong connection to the polymer matrix and for a non-connecting fiber shows an improvement in the properties of the invention
  • a connection of the glass fibers to the polymer matrix is at the
  • carbon fibers can also be used as reinforcing fibers.
  • Carbon fibers are usually produced industrially from precursors such as e.g. B.
  • Polyacrylic fibers obtained by pyrolysis (carbonization) Long fibers and short fibers can be used in the compositions according to the invention. Short fibers are preferably used.
  • the length of the cut fibers is preferably between 3 mm and 125 mm. Fibers with a length of 3 mm to 25 mm are particularly preferably used.
  • fibers with a round cross-section fibers with a cubic dimension (flake-shaped) can also be used.
  • ground carbon fibers are preferably used as an alternative.
  • Preferred milled carbon fibers have sizes of 50 ⁇ m to 150 ⁇ m.
  • the carbon fibers are coated with organic sizings in order to enable special connections to the polymer matrix.
  • the preferred sizes correspond to those mentioned for glass fibers.
  • Short-cut fibers and ground carbon fibers are usually added to the polymeric base materials by compounding.
  • the reinforcing fibers (D) can contain from 0 to 40% by weight, preferably from 1 to 35% by weight, particularly preferably from 5 to 30% by weight and very particularly preferably from 9 to 25% by weight in the composition to be included.
  • the person skilled in the art knows that the presence of the reinforcing fibers in the composition according to the invention influences the flame resistance of the composition at a given melt viscosity. Should no V-0 be achieved at 2.00 mm, preferably 1.5 mm, the person skilled in the art is able to increase the amount of polycarbonate (B) in the composition, in particular by means of the present invention, so that a corresponding flame resistance with the same melt viscosity of V-0 at 2.0 mm, preferably 1.5 mm.
  • compositions without a reinforcing fiber (D) have a flame resistance of at least V-0 at 2.0 mm. It is also preferred that compositions containing a reinforcing fiber (D) have a flame retardancy of at least V-0 at 1.5 mm. Likewise preferred at the same time it is preferred that compositions with a reinforcing fiber (D) have a flame retardancy of at least 5VA at 3.0 mm.
  • compositions according to the invention comprise the components (A) to (D) in the stated percentages by weight, the percentages by weight always (unless otherwise stated) being based on the sum of components (A) to (D).
  • the component (E) is additionally present in the composition according to the invention.
  • composition according to the invention preferably comprises components (A) to (D) in the following amounts:
  • composition also additionally includes component (E).
  • composition according to the invention comprises components (A) to (C) in the following amounts:
  • (A) 3 to 85% by weight of (A), particularly preferably 5 to 83% by weight, very particularly preferably 6 to 80% by weight
  • composition also additionally includes component (E).
  • composition is preferably to be understood as “essentially consisting of” and very particularly preferably as “consisting of”. If the composition consists of the specified components and the wt. % do not add up to 100, the person skilled in the art is able to convert them accordingly so that 100 wt.% results.
  • the composition according to the invention is preferably characterized in that it is free from polytetrafluoroethylene (PTFE).
  • PTFE is known as an anti-drip agent and is widely used in polycarbonate compositions to improve the UL94 rating. According to the invention, it was found that the use of PTFE in the compositions is not necessary and that a UL94 classification of V-0 at 2.00 mm, preferably 1.5 mm, can nevertheless be achieved.
  • PTFE is known to those skilled in the art.
  • PTFE is commercially available in various product qualities. These include Hostaflon® TF2021 or PTFE blends such as Blendex® B449 (approx. 50% by weight PTFE and approx.
  • composition according to the invention is free from halogenated flame retardants. This, too, is frequently added as a flame retardant to polycarbonate compositions to improve their flame resistance. It has been found according to the invention that the use of halogenated flame retardants in the compositions is not necessary and that a UL94 classification of V-0 at 2.00 mm, preferably 1.5 mm, can nevertheless be achieved. According to the invention, all chemical compounds which have at least one halogen atom are preferably dispensed with. One of the most common halogenated flame retardants is tetrabromobisphenol-A oligocarbonate (TBBOC).
  • the composition according to the invention is free from a polysiloxane-polycarbonate block co-condensate.
  • polysiloxane-polycarbonate block cocondensates have intrinsically good flame retardant properties and are therefore frequently used in polycarbonate compositions. According to the invention, it was found that the use of polysiloxane-polycarbonate block cocondensates in the compositions is not necessary and that a UL94 classification of V-0 at 2.00 mm, preferably 1.5 mm, can nevertheless be achieved.
  • Polysiloxane-polycarbonate block co-condensates are known to those skilled in the art. These are often also referred to as SiCoPC. They usually contain siloxane blocks that are condensed with bisphenols to form the corresponding polymers.
  • the composition is free from polytetrafluoroethylene and a halogenated flame retardant. It is also preferred that the composition is free from polytetrafluoroethylene and a polysiloxane-polycarbonate block co-condensate. It is also preferred that the composition is free from a halogenated flame retardant and a polysiloxane-polycarbonate block co-condensate.
  • the composition according to the invention is very particularly preferably free from polytetrafluoroethylene, a halogenated flame retardant and a polysiloxane-polycarbonate block co-condensate.
  • composition additionally comprises
  • each R 1 independently represents a monovalent aliphatic or aromatic hydrocarbon group or a fluorinated hydrocarbon group each having 1 to 18 carbon atoms and y is a number from 3 to 12, respectively wherein each R 2 is independently hydrogen, a monovalent aliphatic or aromatic hydrocarbon group each having 1 to 18 carbon atoms, or a monovalent alkoxy group having 1 to 18 carbon atoms.
  • (E) is a siloxane of the formula (R 1 2 SiO) y
  • the fluorinated hydrocarbon group which R 1 can represent is selected from the group consisting of 3-fluoropropyl, 3 ,3,3-trifluoropropyl, 5,5,5,4,4,3,3-heptafluoropentyl, fluorophenyl, difluorophenyl and trifluorotolyl.
  • the cyclic siloxane of the formula (R 1 2 SiO) y is particularly preferably octamethylcyclotetrasiloxane, 1,2,3,4-tetramethyl-1,2,3,4-tetravinylcyclotetrasiloxane, 1,2,3,4- T etramethyl- 1 ,2,3 ,4- tetraphenylcyclotetrasiloxane, octaethylcyclotetrasiloxane, octypropylcyclotetrasiloxane, octybutylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, tetradecamethylcycloheptasiloxane, hexadecamethylcyclooctasiloxane,
  • (E) is a siloxane which comprises a trifunctional siloxane unit of the formula R 2 Si0 3/2 , it is preferred that this siloxane has this formula to an extent of at least 90 mol %, particularly preferably at least 95 mol %. % and very particularly preferably 100 mol %, based on the total of the moles of siloxane units (M unit, D unit, T unit, Q unit).
  • the formula R 2 Si0 3/2 represents a T unit.
  • an M unit represents the formula T3S1O1/2 (where R represents hydrogen or a monovalent organic group)
  • D represents a bifunctional unit of the formula R 2 represents SiO (where R represents hydrogen or a monovalent organic group)
  • a Q unit represents a tetrafunctional siloxane unit of formula S1O2.
  • This trifunctional siloxane unit of the formula R 2 Si0 3/2 is also known as polysilsequioxane. In addition to the T units, it can also have M units.
  • the structures are known to those skilled in the art. They can have bridging structures or cage structures.
  • R 2 is preferably selected from hydrogen, C 1 -C 12 alkyl, C 1 -C 12 alkenyl, C 1 -C 12 alkoxy, C 1 -C 12 acyl, C 3 -C 8 cycloalkyl or phenyl.
  • R 2 is particularly preferably selected from C 1 -C 6 alkyl, C 1 -C 6 alkenyl, C 1 -C 6 alkoxy and phenyl.
  • R 2 is selected from methyl, ethyl, propyl, butyl and hexyl.
  • R 2 is particularly preferably methyl.
  • Polymethylsilsesquioxane and octymethylsilsesquioxane are particularly preferred. It is preferred that (E) is present in the composition according to the invention in amounts of from 0.5 to 2.5% by weight, particularly preferably from 0.75 to 2.15% by weight and very particularly preferably from 0.9 to 1.5% by weight is used.
  • the composition according to the invention does not contain any linear siloxanes with phenyl groups.
  • the composition does not contain any linear siloxanes with phenyl groups, as disclosed in WO2012/065292 A1.
  • Such siloxanes are typically oils since they are oligomers. On the one hand, these are difficult to add to the composition and, on the other hand, they cannot have the desired influence on the properties of the composition.
  • the composition additionally
  • At least one further additive selected from the group consisting of heat stabilizers, mold release agents, UV absorbers,
  • transesterification stabilizers include laser marking additives, impact modifiers, light-scattering diffusion additives, and colorants.
  • additives as are usually added to polycarbonates are described, for example, in EP-A 0 839623, WO-A 96/15102, EP-A 0500496 or “Plastics Additives Handbook”, Hans Zweifel, 5th Edition 2000, Hanser Verlag, Kunststoff . These additives can be added individually or as a mixture. It goes without saying that only such additives and only in such amounts may be added if they do not have a significant adverse effect on the inventive effect of good flame retardancy.
  • Suitable thermal stabilizers are preferably triphenylphosphine, tris-(2,4-di-tert-butylphenyl)phosphite (Irgafos® 168), tetrakis-(2,4-di-tert-butylphenyl)-[1,1-biphenyl]-4 ,4'-diylbisphosphonite, octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)-propionate (Irganox® 1076), bis-(2,4-dicumylphenyl)-pentaerythritol diphosphite (Doverphos® S-9228 PC), bis
  • ADK STAB PEP-36 (2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite
  • Irganox® B900 mixture of Irgafos® 168 and Irganox® 1076 in a ratio of 4:1
  • Doverphos® S-9228 PC with Irganox® B900 or Irganox® 1076
  • Pentaerythritol tetrastearate (PETS) or glycerol monostearate (GMS) are particularly suitable as mold release agents.
  • the UV absorbers have the lowest possible transmission below 400 nm and the highest possible transmission above 400 nm.
  • Particularly suitable ultraviolet absorbers according to the composition according to the invention are benzotriazoles, triazines, benzophenones and/or arylated cyanoacrylates.
  • Particularly suitable ultraviolet absorbers are hydroxy-benzotriazoles, such as 2-(3',5'-bis-(1,1-dimethylbenzyl)-2'-hydroxy-phenyl)-benzotriazole (Tinuvin® 234, BASF SE, Ludwigshafen), 2-(2'-Hydroxy-5'-(tert.-octyl)-phenyl)-benzotriazole (Tinuvin® 329, BASF SE, Ludwigshafen), bis-(3-(2H-benzotriazolyl)-2-hydroxy-5- tert.-octyl)methane (Tinuvin® 360, BASF SE, Ludwigshafen), 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-(hexyloxy)-phenol (Tinuvin® 1577 , BASF SE, Ludwigshafen), as well as benzophenones such as 2,4-dihydroxybenzophenone (Chimasorb® 22, BASF SE
  • Particularly preferred special UV stabilizers are Tinuvin® 360, Tinuvin® 329, Tinuvin® 312, Tinuvin® 326 and/or Tinuvin® 1600, Tinuvin® 329, Tinuvin® 326 and/or Tinuvin® 360 are very particularly preferred.
  • the composition preferably contains ultraviolet absorbers in an amount of up to 0.8% by weight, preferably 0.05% by weight to 0.5% by weight.
  • Customary light-scattering diffusion additives such as polyacrylates, copolyacrylates or polysilsesquioxanes, are also known to those skilled in the art.
  • the colorants are known to those skilled in the art. They preferably include both pigments, in particular titanium dioxide, and/or organic colorants. If titanium dioxide is contained in the composition, it is preferably contained in up to 15% by weight, very particularly preferably up to 3% by weight and also preferably up to 2% by weight, based on the overall composition. Alternatively, the titanium dioxide can also be contained from 3 to 15% by weight, preferably 7 to 15% by weight, based on the total composition. Those skilled in the art know that titanium dioxide can affect the flame resistance of the composition.
  • paints obtained by containing inter alia titanium dioxide are particularly challenging to achieve at least V-0 at 2.00 mm, preferably 1.50 mm.
  • the composition according to the invention comprises the component(s) (E) and/or (F)
  • the stated amounts relate in each case to the sum of the components (A) to (E) and/or (F) present.
  • composition according to the invention preferably comprises, preferably consists of, components (A) to (F) in the following amounts:
  • (A) 4 to 75% by weight of (A), particularly preferably 7 to 70% by weight, very particularly preferably 8 to 65% by weight
  • (B) 15 to 85% by weight of (B), particularly preferably 20 to 82% by weight, very particularly preferably 25 to 81% by weight
  • C 0.050 to 0.095% by weight (C), more preferably 0.065 to 0.093% by weight, very preferably 0.075 to 0.091% by weight
  • composition according to the invention also preferably comprises, preferably consists of, components (A) to (F) in the following amounts:
  • (A) 3 to 85% by weight of (A), particularly preferably 5 to 70% by weight, very particularly preferably 6 to 65% by weight
  • C 0.050 to 0.095% by weight (C), more preferably 0.065 to 0.093% by weight, very preferably 0.075 to 0.091% by weight
  • % by weight refers to the sum of components (A) to (F).
  • composition according to the invention consists of components (A) to (F).
  • composition according to the invention also particularly preferably comprises, preferably consists of, components (A) to (F) in the following amounts:
  • component (A) is a polycarbonate based on bisphenol A, 14 to 96% by weight % (B), particularly preferably 20 to 94% by weight, very particularly preferably 25 to 93% by weight, where component (B) is a polycarbonate based on bisphenol A,
  • component (C) is potassium perfluoro-1-butanesulfonate and/or potassium diphenylsulfonate, 0, 5 to 2.5% by weight (E), particularly preferably 0.5 to 2.2% by weight (E), very particularly preferably 0.75 to 1.5% by weight (E), where component (E) is selected from octaphenylcyclotetrasiloxane, polymethylsilsesquioxane and octymethylsilsesquioxane, and
  • component (F) is selected is from the group consisting of heat stabilizers, mold release agents, UV absorbers, compatibilizers, antioxidants, IR absorbers, flow improvers, transesterification stabilizers, additives for laser marking, impact modifiers, light-scattering diffusion additives and colorants, with the % by weight based on the sum of Obtain components (A) to (F).
  • the person skilled in the art is familiar with the UL94 test method and the corresponding classification. In one case, this is fire behavior UL94 V at 50 W, 20 mm vertical. This test method is used to determine the flammability classes UL 94 V-0, V1, V-2. The other case is in class UL 5V described.
  • the classification into flammability classes is carried out by evaluating the afterflame and afterglow times as well as the flaming droplets of the test specimen.
  • test specimen thickness is classified into the levels V-0, V-1, V-2, 5 VA and 5VB (vertical burning test). These stand - arranged according to the level of the requirement - in detail for:
  • V-2 Extinction of a vertically clamped specimen within 30 seconds. Flaming droplets of plastic melt permitted.
  • V-l like V-2, but no flaming droplets of plastic melt permitted. Maximum 60 seconds afterglow.
  • V-0 like V-l, but the flame goes out within 10 seconds. Maximum 30 seconds afterglow.
  • Plastics that meet at least classification V-2 can also be tested with the 500 watt flame (125 mm flame height):
  • test bars for UL94V are pretreated as follows:
  • Flaming time 2 x 10 s
  • the second flaming of the sample begins immediately after the end of the 1st afterburning time.
  • the subject of the present invention is the use of 15 to 96% by weight of a polycarbonate (B) with a degree of branching of 1.01 to 1.5 mol%, which comprises no end groups of the formula (1): each Y is independently a halogen, an alkyl group having 1 to 3 carbon atoms, an alkoxy group having 1 to 3 carbon atoms, an arylalkyl group having 7 to 12 carbon atoms, an alkylaryl group or a nitro group, y is 0 to 4 and c is 1 to 5 with the proviso that y+c is 1 to 5, and wherein * represents the position at which formula (1) terminates the polycarbonate (B), in a composition containing
  • each R 1 is independently a monovalent aliphatic or aromatic hydrocarbon group or a fluorinated hydrocarbon group each having 1 to 18 carbon atoms and y is a number from 3 to 12, or wherein each R 2 is independently hydrogen, a monovalent aliphatic or aromatic hydrocarbon group each having 1 to 18 carbon atoms or a monovalent alkoxy group with 1 to 18 carbon atoms, to achieve a V-0 classification according to UL94 at a layer thickness of 2.00 mm, preferably 1.5 mm, the content of component (C) in the composition being 0.05 to 0.095% by weight and where the % by weight is based on the sum of components (A) to (D).
  • the specified components (A) to (D) and (E) are preferably the components (A) to (D) and (E) according to the invention already described above.
  • the composition is particularly preferably the composition according to the invention in all the preferences and combinations of preferences described above, in particular in the quantitative ratios mentioned above.
  • the addition of the branched polycarbonate (B) could reduce the amount of component (C) in the composition, but still at least one UL94 classification of V-0 with a layer thickness of 2.0 mm, preferably 1 .5 mm resulted.
  • the compositions according to the invention with component (B) have improved flowability and thus better processability than comparable compositions with a higher content of (C).
  • the thermal properties of the composition according to the invention with component (B) remain almost comparable to those with higher contents of (C).
  • the linear polycarbonate (A) does not include any end groups of the formula (1): in which Y, y and c are as defined above. examples
  • the polycarbonate-based compositions described in the following examples were produced by compounding on a ZE 25 extruder from Berstorff with a throughput of 10 kg/h.
  • the melt temperature was 275 - 350°C.
  • Component PC-Al Linear polycarbonate based on bisphenol A and phenol as a chain terminator with a melt volume flow rate MVR of 9 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and 1.2 kg load). Contains small amounts of TPP.
  • Component PC-A2 Linear polycarbonate in powder form based on bisphenol A and phenol as chain terminator with a melt volume flow rate MVR of 6 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and 1.2 kg load).
  • Component PC-A3 Linear polycarbonate in powder form based on bisphenol A and phenol as chain terminator with a melt volume flow rate MVR of 19 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and 1.2 kg load).
  • Component PC-A4 Linear polycarbonate based on bisphenol A and phenol as chain terminator with a melt volume flow rate MVR of 9 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and 1.2 kg load). Contains no TPP.
  • Component PC-B branched polycarbonate based on bisphenol A and 1,1,1-tri-(4-hydroxyphenyl)-ethane (THPE) as branching agent (1.3% by weight, corresponds to 1.08 mol%) and p-tert-butylphenol (BUP) as a chain terminator with a melt volume flow rate MVR of 6 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and a load of 1.2 kg).
  • THPE 1,1,1-tri-(4-hydroxyphenyl)-ethane
  • BUP p-tert-butylphenol
  • Component PC-Bl branched polycarbonate based on bisphenol A and 1,1,1-tri-(4-hydroxyphenyl)ethane (THPE) as branching agent (1.3% by weight, corresponds to 1.08 mol%) and p-tert-butylphenol (BUP) as a chain terminator with a melt volume flow rate MVR of 6 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and a load of 1.2 kg).
  • THPE 1,1,1-tri-(4-hydroxyphenyl)ethane
  • BUP p-tert-butylphenol
  • Component PC-B2 branched polycarbonate based on bisphenol A and 1,1,1-tri-(4-hydroxyphenyl)-ethane (THPE) as branching agent (0.381% by weight, corresponds to 0.32 mol%) and p- tert-butylphenol (BUP) as a chain terminator with a melt volume flow rate MVR of 13 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and a load of 1.2 kg).
  • THPE 1,1,1-tri-(4-hydroxyphenyl)-ethane
  • BUP p- tert-butylphenol
  • Component PC-B3 branched polycarbonate based on bisphenol A and 1,1,1-tri-(4-hydroxyphenyl)ethane (THPE) as branching agent (0.82% by weight, corresponds to 0.68 mol%) and p-tert-butylphenol (BUP) as a chain terminator with a melt volume flow rate MVR of 12 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and a load of 1.2 kg).
  • THPE 1,1,1-tri-(4-hydroxyphenyl)ethane
  • BUP p-tert-butylphenol
  • Component PC-B4 branched polycarbonate based on bisphenol A and 1,1,1-tri-(4-hydroxyphenyl)-ethane (THPE) as branching agent (1.06% by weight, corresponds to 0.88 mol%) and p-tert-butylphenol (BUP) as a chain terminator with a melt volume flow rate MVR of 12 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and a load of 1.2 kg).
  • THPE 1,1,1-tri-(4-hydroxyphenyl)-ethane
  • BUP p-tert-butylphenol
  • Component PC-B5 branched polycarbonate based on bisphenol A and 1,1,1-tri-(4-hydroxyphenyl)ethane (THPE) as branching agent (1.2% by weight, corresponds to 1.0 mol%) and p-tert-butylphenol (BUP) as a chain terminator with a melt volume flow rate MVR of 10.3 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and 1.2 kg
  • Component PC-B6 branched polycarbonate based on bisphenol A and 1,1,1-tri-(4-hydroxyphenyl)-ethane (THPE) as branching agent (1.3% by weight, corresponds to 1.08 mol%) and p-tert-butylphenol (BUP) as a chain terminator with a melt volume flow rate MVR of 4.2 cm 3 /(10 min) (according to ISO 1133:2012-03, at a test temperature of 300°C and a load of 1.2 kg) .
  • Component CI potassium perfluorobutanesulfonate (also called Rimar salt or C4 salt) from Lanxess AG, Germany.
  • Component D1 Chopped strand non-bonding glass fiber CS108F-14P from 3B-Fibreglass sprl Belgium.
  • Component D2 Chopped strand non-bonding glass fiber CS13720 from 3B-Fibreglass sprl Belgium.
  • Component El octaphenylcycloterasiloxane (OPCTS) from Shin-Etsu Co, Ltd. Japan.
  • OCTS octaphenylcycloterasiloxane
  • Component F1 mold release agent pentaerythritol tetrastearate (PETS, Loxiol P 861/3.5 Special) from Emery Oleochemicals GmbH Germany.
  • PETS pentaerythritol tetrastearate
  • Component F2 Yellow dye MACROLEX YELLOW 3G GRAN from Lanxess, Germany.
  • Component F3 Red dye COLORTHERM RED 130 M from Lanxess, Germany.
  • Component F4 black pigment carbon black LAMP BLACK 101 from Evonik, Germany.
  • Component F5 KRONOS 2230 titanium dioxide white pigment from Kronos Titan GmbH, Germany.
  • Component F6 triphenylphosphine (TPP) from BASF SE, Germany.
  • Component F7 UV absorber Tinuvin 329 from BASF SE, Germany.
  • Component F8 Disflamoll TOF (tris-isooctyl phosphate) from Lanxess, Germany.
  • Component F9 Heucodur Yellow 3R yellow pigment from Heubach GmbH, Germany.
  • Component F10 Bayferrox 110 M iron oxide red pigment from Lanxess, Germany.
  • Component F1 1 UV absorber Irganox 1076 from BASF, Germany
  • the melt volume flow rate (MVR) was determined according to ISO 1133:2012-03 (mainly at a test temperature of 300° C., mass 1.2 kg) using the Zwick 4106 device from Zwick Roell.
  • MVR value was measured after 20 minutes of preheating (IMVR20') This is a measure of the melt stability under increased thermal stress.
  • the shear viscosity (melt viscosity) was determined in accordance with ISO 11443:2005 using the Visco-Robo 45.00 device from Göttfert.
  • the fire behavior was determined according to UL 94 V (50 W, 20 mm vertical). Pre-treatment of the test bars: 2 days / 23 °C / 50 % rel. humidity
  • the second flaming of the sample begins immediately after the end of the 1st afterburning time
  • This method is used to determine the flammability classes UL 94-5VA and -5VB. Here, the burning behavior of rods and any hole formation on plates are assessed
  • the Vicat softening point VST/B50 or VST/B 120 as a measure of heat resistance was determined in accordance with ISO 306:2014-3 on test specimens measuring 80 mm x 10 mm x 4 mm with a stamp load of 50 N and a heating rate of 50° C./h or 120° C./h using the Coesfeld Eco 2920 device from Coesfeld Materialtest.
  • the Heat Deflection Temperature (HDT) as a measure of the
  • Heat deflection temperature was measured according to DIN EN ISO 75-1:2013-08 on test specimens measuring 80 mm x 10 mm x 4 mm with a load of 1.8 MPa (HDT A) or 0.45 MPa (HDT B) using the HDT device Fully automatic machine from Coesfeld measured. The ash content was determined in accordance with DIN 51903:2012-11 (850°C, hold for 30 minutes).
  • a composition containing (B) but containing no more than 0.09% by weight of component (C) can have at least the same, if not better, flame retardancy than a composition without (B), but with an increased amount of (C). At the same time, the thermal properties are essentially the same. The flowability is even improved with the composition according to the invention.
  • compositions according to the invention containing up to 20% by weight of a glass fiber also have a flame resistance of at least V-0 at a layer thickness of 1.5 mm.
  • the retention of thermal properties and an improvement in flowability can also be observed here.
  • compositions without glass fibers also have good flame retardancy with almost unchanged thermal properties.
  • a V-0 can only be achieved with a layer thickness of 1.50 mm and even 1.20 mm with a degree of branching of the branched polycarbonate (component (B)) in the range according to the invention.
  • Other degrees of branching result in classification as V-2.
  • the thermal properties of the compositions according to the invention are almost the same.
  • the table shows that a composition with component B) (branched polycarbonate) and the claimed amount of component C) (e.g. example E29) in contrast to a composition without component B) but with component C) in the same quantity (VI 5) does not achieve the V-0 classification at 1.5 mm or 1.2 mm.
  • component B) branched polycarbonate
  • component C e.g. example E29

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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)
  • Inorganic Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Manufacturing & Machinery (AREA)
  • Materials Engineering (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

La présente invention concerne des compositions qui contiennent un polycarbonate linéaire, un polycarbonate ramifié et une petite quantité de sels des dérivés d'acide sulfonique, de sulfonamide ou de sulfonimide. L'invention concerne également l'utilisation d'un polycarbonate ramifié dans une composition de polycarbonate pour obtenir une cote UL94 V-0 à une épaisseur de couche de 2,00 mm, de préférence de 1,5 mm.
EP22727195.4A 2021-05-17 2022-05-16 Composition ignifuge contenant de 0,040 à 0,095 % en poids d'un retardateur de flamme Pending EP4341339A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
EP21174020.4A EP4092075A1 (fr) 2021-05-17 2021-05-17 Composition ininflammable comprenant entre 0,040 et 0,095 % en poids d'un ignifuge
PCT/EP2022/063136 WO2022243222A1 (fr) 2021-05-17 2022-05-16 Composition ignifuge contenant de 0,040 à 0,095 % en poids d'un retardateur de flamme

Publications (1)

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EP4341339A1 true EP4341339A1 (fr) 2024-03-27

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EP21174020.4A Withdrawn EP4092075A1 (fr) 2021-05-17 2021-05-17 Composition ininflammable comprenant entre 0,040 et 0,095 % en poids d'un ignifuge
EP22727195.4A Pending EP4341339A1 (fr) 2021-05-17 2022-05-16 Composition ignifuge contenant de 0,040 à 0,095 % en poids d'un retardateur de flamme
EP22727196.2A Pending EP4341340A1 (fr) 2021-05-17 2022-05-16 Composition ignifuge contenant de 0,040 à 0,095 % en poids d'un retardateur de flamme

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US (1) US20240247144A1 (fr)
EP (3) EP4092075A1 (fr)
KR (2) KR20240009405A (fr)
CN (2) CN117337319A (fr)
WO (2) WO2022243222A1 (fr)

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CN117337319A (zh) 2024-01-02
CN117321128A (zh) 2023-12-29
EP4092075A1 (fr) 2022-11-23
US20240247144A1 (en) 2024-07-25
EP4341340A1 (fr) 2024-03-27
WO2022243222A1 (fr) 2022-11-24
KR20240009406A (ko) 2024-01-22
KR20240009405A (ko) 2024-01-22
WO2022243223A1 (fr) 2022-11-24

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