DE60206575T2 - Flame retardant aromatic polycarbonate resin composition and molding compositions prepared therefrom - Google Patents

Description

Territory of invention

The The present invention relates to a flame retardant aromatic polycarbonate resin composition and moldings made of it. In particular, the invention relates to a flame retardant aromatic Polycarbonate resin composition containing essentially no bromine compound or chlorine compound (halogen-based flame retardant) or contains no phosphorus compound as a flame retardant and excellent has drip-preventing properties, and existing therefrom Moldings. Furthermore, the present invention relates to a flame retardant aromatic Polycarbonate resin composition, the moldings of excellent transparency results.

description of the prior art

aromatic Polycarbonate resins and based on aromatic polycarbonates Resins such as aromatic polycarbonate resin / styrene based resin alloys and from aromatic polycarbonate resin / aromatic alloys Polyester resins are made by a processing method that is easy and of outstanding productivity, for example by injection molding, to different moldings shaped and used in a variety of commercial fields. In particular, aromatic polycarbonate resins and alloys of it in outer and internal parts of office automation equipment and household electrical appliances, such as personal computers, notebooks, laser printers, inkjet printers, copiers and fax machines. In these fields of application, the coloring properties of a resin composition when blended with a coloring agent of great importance get. These properties are found in the molding in terms of gloss, color, Clarity, uniformity and the like. The clarity can also be important of characters or markings by laser marking as a simple high speed method of marking with a desired character, symbol or pattern on the surface of a molding be printed with high reproducibility.

Currently become shaped bodies from aromatic polycarbonate resins on a variety of commercial Areas where excellent transparency and heat resistance arrives, used. Especially in application areas in which a high level of transparency is required, e.g. B. at illuminated covers and protective covers for Transmission type displays, they are widely used, taking advantage of their excellent transparency, d. H. the high-level light transmission and the extremely low turbidity of aromatic polycarbonate resins. In these fields of application resin materials their transparency, color and mechanical properties as well then retain it if it is a heat and moisture exposure, since a light source, such as Fluorescent light or a light bulb means very or a product made of the resin of high humidity is exposed when in a bathroom or outdoors is used. So there are cases those in a resin composition besides a transparent one Texture of constancy across from a damp heat a big Meaning.

On The above application is a flame-retardant nature big at the outbreak of fire Attention paid and it is now desired, a resin composition to provide, in addition to the above characteristic properties also has a highly flame retardant nature. When Means for providing a flame retardant condition an aromatic polycarbonate resin or an alloy thereof Flame retardant aromatic polycarbonate resin compositions proposed, which is a halogen compound, such as a bromine compound or a chlorine compound, or a phosphorus compound as a flame retardant. These Compositions are used in office automation equipment and household electrical appliances used where a strong need for a flame-retardant Texture exists. There were new flame retardant aromatic Polycarbonate resin compositions as substitutes for the above Resin compositions developed and such compositions are now used in the above products. The reason for this change of the flame retardant is at the time of molding to suppress the generation of a corrosive gas or to improve the recyclability of products.

flame retardant Means as substitutes for the above flame retardant can be used a silicone compound.

A flame-retardant resin composition obtained by mixing a silicone compound was obtained with an aromatic polycarbonate resin, was in detail examined and there were different in this regard proposals made.

It For example, the following procedures have been proposed: A procedure for mixing an alkali metal or alkaline earth metal salt perfluoroalkane and an organic siloxane having an alkoxy group, vinyl group and phenyl group with a polycarbonate resin (JP-A-6-306265) (the Expression "JP-A" means an "unaudited published Japanese Patent Application) and a method for mixing a Alkali metal salt or alkaline earth metal salt of a perfluoroalkanesulfonic acid and an organopolysiloxane having an organoxysilyl group, wherein Silicon atom bonded to a divalent hydrocarbon group with a polycarbonate resin (JP-A-6-336547).

Further, a method for blending a special petroleum-based heavy oil or pitch and a silicon compound with a resin component (JP-A-9-169914), and a method for blending a silicone resin having a unit represented by R ₂ SiO _1.0 and a through RSiO _{1.5 represented} unit and having a weight average molecular weight of 10,000 to 270,000, with a non-silicone resin having an aromatic ring proposed (JP-A-10-139964).

The let the above-proposed polycarbonate resin compositions but in terms of transparency, resistance to damp heat and Flame retardant texture not satisfactory. For example, if a shaped body from the polycarbonate resin composition is thin, the rating UL 94 Not reaching V-0 due to dripping, one formed from this moldings decreases due to unsatisfactory distribution of the silicone one cloudy texture or the transparency decreases after exposure from damp heat, because of the treatment with the moist heat of a silicone Agglomeration is subject.

JP-B-60-38419 (The term "JP-B" as used herein means a tested Japanese Patent Publication) describes a resin composition comprising an aromatic polycarbonate resin, an organic alkali metal salt and poly (methylhydrogensiloxane) includes. However, this resin composition can be understood in terms of the dyeing properties when mixing with a coloring agent not satisfactory (These properties are characterized by luster, color, clarity, uniformity and the like of a molded article reproduced), since the composition itself is a cloudy texture assumes and distribution errors, such as a chipping, on the surface of the molding occur.

Further becomes common Polytetrafluoroethylene with the ability used for fibril formation as anti-drip agent. If however, polytetrafluoroethylene with an aromatic polycarbonate resin is mixed, the transparency of the resulting molded article decreases, since polytetrafluoroethylene and the aromatic polycarbonate resin with each other not compatible are.

Tasks to be solved according to the invention

A The first object of the present invention is to provide a flame-retardant aromatic polycarbonate resin composition, the substantially no halogen compound, and further preferably also contains no phosphorus compound as a flame retardant. Especially it should be a flame retardant aromatic polycarbonate resin composition act, which has excellent coloring properties in the color, distinguished by laser marking in a clear way with a character or a mark can be printed and when burning Dripping of the resin is prevented.

A second object of the present invention is to provide a transparent to provide flame retardant aromatic polycarbonate resin composition, in terms of transparency, resistance to damp heat and Preventing the drop formation of the resin when burning as excellent proves.

A Third object of the present invention is to provide a flame-retardant aromatic polycarbonate resin composition, in terms of creep resistance, antistatic properties and preventing dripping of the resin upon burning as excellent.

Means of solving the tasks

The Inventors have made detailed investigations to solve the above objects performed and thereby found that a flame-retardant aromatic polycarbonate resin composition, the in terms of dyeing properties in the color scheme, the clarity of a laser mark printed on Character or mark and the prevention of dripping of the resin when burned proves to be excellent, and further a flame-retardant aromatic polycarbonate resin composition, in terms of transparency and resistance to damp heat as excellent, obtained by giving a predetermined Amount of a specific silicone compound having an aromatic Polycarbonate resin mixed.

• (1) 100 Gew.-teile Harzkomponenten, umfassend 50 bis 100 Gew.-% eines aromatischen Polycarbonatharzes (Komponente A-1), 0-50 Gew.-% eines Harzes auf Styrolbasis (Komponente A-2) und 0-50 Gew.-% eines aromatischen Polyesterharzes (Komponente A-3); und
• (2) 0,1 bis 10 Gew.-teile einer Siliconverbindung (B), die eine SiH-Gruppe und eine aromatische Gruppe im Molekül enthält, bezogen auf 100 Gew.-teile der Gesamtheit der Harzkomponenten, wobei es sich bei der Siliconverbindung um mindestens eine Verbindung handelt, die aus Siliconverbindungen ausgewählt ist, die (1) einen Gehalt an SiH-Gruppen (SiH-Gehalt) von 0,1 bis 1,2 mol/100 g und (2) einen Gehalt an aromatischen Gruppen der folgenden allgemeinen Formel (1) (Gehalt an aromatischen Gruppen) von 10 bis 70 Gew.-% aufweisen
  
  wobei die einzelnen Reste X unabhängig voneinander eine OH-Gruppe oder eine einwertige organische Gruppe mit 1 bis 20 Kohlenstoffatomen bedeuten und n den Wert 0 hat oder eine ganze Zahl mit einem Wert von 1 bis 5 bedeutet, mit der Maßgabe, dass dann, wenn n einen Wert von 2 oder mehr hat, die Reste X sich voneinander unterscheiden können.

Thus, according to the present invention, there is provided a flame retardant aromatic polycarbonate resin composition comprising:

• (1) 100 parts by weight of resin components comprising 50 to 100% by weight of an aromatic polycarbonate resin (component A-1), 0 to 50% by weight of a styrene-based resin (component A-2) and 0 to 50% by weight .-% of an aromatic polyester resin (component A-3); and
• (2) 0.1 to 10 parts by weight of a silicone compound (B) containing an SiH group and an aromatic group in the molecule, based on 100 parts by weight of the entirety of the resin components, wherein the silicone compound is is at least one compound selected from silicone compounds having (1) a content of SiH groups (SiH content) of 0.1 to 1.2 mol / 100 g, and (2) an aromatic group content of the following general Have formula (1) (content of aromatic groups) of 10 to 70 wt .-%
  
  wherein the individual radicals X independently of one another denote an OH group or a monovalent organic group having 1 to 20 carbon atoms and n has the value 0 or an integer with a value of 1 to 5, with the proviso that if n has a value of 2 or more, the radicals X may differ from each other.

Detailed description of the preferred embodiments

below is the flame retardant invention aromatic polycarbonate resin composition described in detail. First is a description of the resin components (components A) and the silicon compound (component B) as a flame retardant, which represents the composition, in the order given.

From the resin components (components A) in the resin composition the aromatic polycarbonate resin used as component A-1 in General, by passing a diphenol with a carbonate precursor an interfacial polycondensation process or an exchange process of molten esters by a carbonate prepolymer polymerized by a solid phase ester exchange method or by preparing a cyclic carbonate compound according to a ring-opening polymerization process polymerized.

Typical examples of the diphenol used include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, bis-4- (hydroxyphenyl) -methane, bis - {(4-hydroxy-3,5-dimethyl) -phenyl} -methane, 1 , 1-bis (4-hydroxyphenyl) ethane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, 2,2-bis (4-hydroxyphenyl) propane (so-called bisphenol A), 2, 2-bis - {(4-hydroxy-3-methyl) -phenyl} -propane, 2,2-bis - {(4-hydroxy-3,5-dimethyl) -phenyl} -propane, 2,2-bis- {(3-isopropyl-4-hydroxy) -phenyl} -propane, 2,2-bis - {(4-hydroxy-3-phenyl) -phenyl} -propane, 2,2-bis (4-hydroxyphenyl) - butane, 2,2-bis- (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,4-bis- (4-hydroxyphenyl) -2- methylbutane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- Bis (4-hydroxyphenyl) -4-isopropylcyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis- (4-hydroxyphenyl) -fluorene, 9,9- Bis - {(4-hydroxy-3-methyl) -phenyl} -fluorene, α, α'-bis (4-hydroxyphenyl) -od iisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene, α, α'-bis (4-hydroxyphenyl) -p-diisopropylbenzene, 1,3-bis (4-hydroxyphenyl) -5, 7-dimethyladamantane, 4,4'-dihydroxydiphenylsulfone, 4,4'-dihydroxydiphenylsulfoxide, 4,4'-dihydroxydiphenylsulfide, 4,4'-dihydroxydiphenyl ketone, 4,4'-dihydroxydiphenyl ether and 4,4'-dihydroxydiphenyl ester. These compounds may be used alone or in a combination of two or more compounds the.

among them are homopolymers or copolymers consisting of at least one bisphenol, that from the group consisting of bisphenol A, 2,2-bis - {(4-hydroxy-3-methyl) -phenyl} -propane, 2,2-bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4-hydroxyphenyl) -3,3-dimethylbutane, 2,2-bis (4-hydroxyphenyl) -4-methylpentane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 9,9-bis - {(4-hydroxy-3-methyl) phenyl} fluorene and α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene exists, preferably. A homopolymer of bisphenol A and a copolymer of 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane and bisphenol A, 2,2-bis - {(4-hydroxy-3-methyl) -phenyl} -propane or α, α'-bis (4-hydroxyphenyl) -m-diisopropylbenzene is particularly preferred.

At the carbonate it is a carbonyl halide, a carbonate ester Halogen formate or the like., For example, phosgene, diphenyl carbonate and dihaloformate of a diphenol. Below are phosgene and diphenyl carbonate for commercial purposes as beneficial.

to Preparation of a polycarbonate resin by reacting the above Diphenol with the above carbonate precursor by interfacial polycondensation or an ester-exchange process in the molten state can each a catalyst, endcapping agent, antioxidant as needed for diphenols and the like can be used. The polycarbonate resin may be a branched polycarbonate resin by copolymerization a polyfunctional aromatic compound having a functionality of 3 or more, a polyester-carbonate resin obtained by Copolymerization of an aromatic or aliphatic (or alicyclic) dicarboxylic acid a copolycarbonate resin obtained by copolymerization a bifunctional alcohol (including an alicyclic alcohol) has been obtained, a polyester-carbonate resin obtained by copolymerization both a dicarboxylic acid as also a bifunctional alcohol has been obtained, or to a mixture of two or more of the above-obtained polycarbonate resins act.

To explanatory Examples of the polyfunctional aromatic compound having a functionality of 3 or more belong Phloroglucinol, phloroglucide, trisphenols such as 4,6-dimethyl-2,4,6-tris- (4-hydroxydiphenyl) -hepten-2,2,4,6-trimethyl-2,4,6-tris (4- hydroxyphenyl) heptane, 1,3,5-tris- (4-hydroxyphenyl) -benzene, 1,1,1-tris (4-hydroxyphenyl) -ethane, 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane, 2,6-bis (2-hydroxy-5-methylbenzyl) -4-methylphenol and 4- {4- [1,1-bis (4-hydroxyphenyl) -ethyl] -benzene} -α, α-dimethylbenzylphenol, Tetra (4-hydroxyphenyl) methane, Bis (2,4-dihydroxyphenyl) ketone, 1,4-bis (4,4-dihydroxytriphenylmethyl) benzene, trimellitic acid, pyromellitic acid, benzophenonetetracarboxylic acid and acid chlorides from that. Among them are 1,1,1-tris (4-hydroxyphenyl) ethane and 1,1,1-tris (3,5-dimethyl-4-hydroxyphenyl) ethane prefers. Particularly preferred is 1,1,1-tris (4-hydroxyphenyl) ethane.

When the polyfunctional compound forming a branched polycarbonate resin is contained, the amount of the polyfunctional compound is 0.001 to 1 mol%, preferably 0.005 to 0.9 mol%, and more preferably 0.01 to 0.8 mol% on the total amount of aromatic polycarbonate. Although a branched structure may arise as a side reaction in the case of the ester interchange process in the molten state, the amount of the branched structure is 0.001 to 1 mole%, preferably 0.005 to 0.9 mole%, and more preferably 0.01 to 0.8 mole%. , based on the total amount of the aromatic polycarbonate. The amount can be calculated by ¹ H-NMR measurement.

at the reaction by the interfacial polycondensation process it is generally an implementation between one Diphenol and phosgene in the presence of an acid binder and an organic Solvent. Examples of the acid binding agent belong Alkali metal hydroxides, such as sodium hydroxide and potassium hydroxide, and Amine compounds, such as pyridine. Examples of the organic solvent belong halogenated hydrocarbons, such as methylene chloride and chlorobenzene. A catalyst, eg a tertiary one Amin, a quaternary Ammonium compound or a quaternary phosphonium compound, such as Triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide, can promote the implementation will be used. The reaction temperature is generally 0 to 40 ° C, the Reaction time is about 10 minutes to 5 hours and the pH during the reaction is preferably at 9 or above held.

wobei A ein Wasserstoffatom, eine lineare oder verzweigte Alkylgruppe mit 1 bis 9 Kohlenstoffatomen oder eine durch eine Phenylgruppe substituierte Alkylgruppe bedeutet und R eine ganze Zahl mit einem Wert von 1 bis 5 und vorzugsweise von 1 bis 3 bedeutet.An endcapping agent is generally used in the above interfacial polycondensation reaction. A monofunctional phenol can be used as the endcapping agent. The monofunctional phenol, which is generally used as an end-capping agent for molecular weight adjustment, is a phenol or a phenyl substituted with a lower alkyl group nol, z. B. a monofunctional phenol of the following general formula (5)

wherein A represents a hydrogen atom, a linear or branched alkyl group having 1 to 9 carbon atoms or an alkyl group substituted by a phenyl group, and R represents an integer having a value of 1 to 5, and preferably 1 to 3.

To Examples of the above monofunctional phenol includes phenol, p-tert-butylphenol, p-cumylphenol and isooctylphenol.

wobei X die Bedeutung -R-CO-O- oder -R-O-CO- hat (R bedeutet eine Einfachbindung oder eine zweiwertige aliphatische Kohlenwasserstoffgruppe mit 1 bis 10 Kohlenstoffatomen und vorzugsweise 1 bis 5 Kohlenstoffatomen) und n bedeutet eine ganz Zahl mit einem Wert von 10 bis 50.Other monofunctional phenols include phenols and benzoic acid chlorides having a long chain alkyl group or aliphatic polyester group as substituents, as well as long chain alkyl carboxylic acid chlorides. Among them, preferred are phenols having a long-chain alkyl group as a substituent of the following general formulas (6) and (7):

wherein X is -R-CO-O- or -RO-CO- (R is a single bond or a divalent aliphatic hydrocarbon group having 1 to 10 carbon atoms and preferably 1 to 5 carbon atoms) and n is an integer having a value of 10 to 50.

At the substituted phenol of the general formula (6) is preferably a phenol, wherein n is an integer with a Value of preferably 10 to 30 and in particular from 10 to 26, for example, decylphenol, dodecylphenol, tetradecylphenol, Hexadecylphenol, octadecylphenol, eicosylphenol, docosylphenol and Triacontylphenol.

At the substituted phenol of the general formula (7) is preferably a compound in which X is -R-CO-O- (R means a single bond) and n has an integer with one Value of 10 to 30 and especially from 10 to 26 means, for. B. decyl hydroxybenzoate, dodecyl hydroxybenzoate, tetradecyl hydroxybenzoate, Hexadecyl hydroxybenzoate, eicosyl hydroxybenzoate, docosyl hydroxybenzoate and triacontyl hydroxybenzoate. The endcapping agents can be alone or in combination of two or more components.

The reaction carried out in the molten state according to the ester exchange process is generally an ester exchange reaction between a diphenol and a carbonate ester, in the presence of an inert gas, by mixing the diphenol and the carbonate ester with heating and distilling off the alcohol formed or phenol is carried out. The reaction temperature, which varies according to the boiling point or the like of the formed alcohol or phenol, is generally from 120 to 350 ° C. At the last stage of the reaction, the pressure of the reaction system is reduced to 1.33 x 10 ³ to 13.3 Pa to facilitate distilling off the alcohol or phenol formed. The reaction time is generally about 1 to 4 hours.

At the Carbonate ester is, for example, a carbonate ester with an aryl group or aralkyl group having 6 to 10 carbon atoms or an alkyl group having 1 to 4 carbon atoms substituted could be. Examples of include the carbonate ester Diphenyl carbonate, bis (chlorophenyl) carbonate, dinaphthyl carbonate, Bis (diphenyl) carbonate, Dimethyl carbonate, diethyl carbonate and dibutyl carbonate. among them Diphenyl carbonate is preferred.

To accelerate the rate of polymerization, a polymerization catalyst can be used. Examples of the polymerization catalyst include alkali metal compounds such as sodium hydroxide, potassium hydroxide and sodium salts and potassium salts of diphenol, alkaline earth metal compounds such as calcium hydroxide, barium hydroxide and magnesium hydroxide, nitrogen-containing basic compounds such as tetramethylammonium hydroxide, tetraethylammonium hydroxide, trimethylamine and triethylamine, alkoxides of alkali metals or alkaline earth metals, salts of organic acids with alkali metals or alkaline earth metals, zinc compounds, boron compounds , Aluminum compounds, silicon compounds, germanium compounds, organotin compounds, lead compounds, osmium compounds, antimony compounds, manganese compounds, titanium compounds and zirconium compounds, all of which are generally used for an esterification reaction or ester exchange reaction. These catalysts may be used alone or in combination of two or more products. The amount of the polymerization catalyst is preferably 1 × 10 ^-8 to 1 × 10 ^-3 equivalent, and preferably 1 × 10 ^-7 to 5 × 10 ^-4 equivalent, based on 1 mole of the diphenol as a starting material.

to Reduction in the number of phenolic terminal groups the polymerization reaction, a compound such as bis (chlorophenyl) carbonate, bis (bromophenyl) carbonate, Bis (nitrophenyl) carbonate, bis (phenylphenyl) carbonate, Chlorophenylphenyl carbonate, bromophenylphenyl carbonate, nitrophenylphenyl carbonate, Phenylphenyl carbonate, methoxycarbonylphenylphenyl carbonate or ethoxycarbonylphenylphenyl carbonate in the last stage of the polycondensation reaction or after the end be added to the polycondensation reaction. Be under it 2-chlorophenylphenyl carbonate, 2-Methoxycarbonylphenylphenylcarbonat and 2-Ethoxycarbonylphenylphenylcarbonat preferred. 2-methoxycarbonylphenylphenyl is particularly preferred.

One Deactivator for neutralizing the activity of a catalyst is preferably used in the polymerization reaction. To be explained Examples of belong to the deactivator Benzenesulfonic acid, p-toluenesulfonic acid, sulfonic acid esters, such as methylbenzenesulfonate, ethylbenzenesulfonate, butylbenzenesulfonate, octylbenzenesulfonate, Phenylbenzenesulfonate, methyl p-toluenesulfonate, ethyl p-toluenesulfonate, Butyl p-toluenesulfonate, octyl p-toluenesulfonate and phenyl p-toluenesulfonate; and Compounds such as trifluoromethanesulfonic acid, naphthalenesulfonic acid, sulfonated Polystyrene, methyl acrylate-sulfonated styrene copolymer, 2-phenyl-2-propyldodecylbenzenesulfonate, 2-phenyl-2-butyl-dodecylbenzenesulfonate, tetrabutylphosphonium octylsulfonate, tetrabutylphosphonium decylsulfonate, Tetrabutylphosphoniumbenzenesulfonate, tetraethylphosphonium dodecylbenzenesulfonate, Tetrabutylphosphonium dodecylbenzenesulfonate, tetrahexylphosphonium dodecylbenzenesulfonate, Tetraoctylphosphonium dodecylbenzenesulfonate, decylammonium butylsulfate, Decylammonium decyl sulfate, dodecylammonium methylsulfate, dodecylammonium ethylsulfate, Dodecylmethylammonium methylsulfate, dodecyldimethylammonium tetradecylsulfate, Tetradecyldimethylammonium methylsulfate, tetramethylammoniumhexylsulfate, Decyltrimethylammonium hexadecylsulfate, tetrabutylammonium dodecylbenzylsulfate, Tetraethylammoniumdodecylbenzylsulfat and Tetramethylammoniumdodecylbenzylsulfat. The deactivator is not limited to these compounds. These Connections can be used in a combination of two or more compounds.

Under the deactivators are those based on phosphonium and ammonium salts particularly preferred. The deactivator is used in an amount of preferably 0.5 to 50 mol, based on 1 mol of the residual catalyst, or preferably from 0.01 to 500 ppm, in particular from 0.01 to 300 ppm, and more preferably from 0.01 to 100 ppm, based on the polycarbonate resin after the polymerization, used.

The Molecular weight of the polycarbonate resin is not specific Restrictions. However, if the viscosity agent the molecular weight of the polycarbonate resin is less than 10,000 is, deteriorate its characteristic high temperature properties.

at a viscosity agent The molecular weight of more than 50,000 reduces the ductility. Therefore, amounts the viscosity agent of the molecular weight preferably 10,000 to 50,000, especially 19 000 to 30 000 and especially 14 000 to 24 000. There can be two or more polycarbonate resins are mixed together. In this Case it is naturally possible to Polycarbonate resin having a viscosity average molecular weight outside of the above range.

A mixture with a polycarbonate resin having a viscosity average molecular weight of more than 50,000 is preferred because it has a high degree of drop-preventing ability and effectively realizes the present invention. A mixture with a polycarbonate resin having a viscosity average molecular weight of 80,000 or more is particularly preferred. Most preferred is a mixture with a polycarbonate resin having a viscosity average molecular weight of 100,000 or more. In other words, it is preferable to use a product that a molecular weight distribution having two different peaks which occur in a measuring method such as GPC (gel permeation chromatography).

The viscosity average molecular weight M is obtained by first obtaining from the equation given below using a solution obtained by dissolving 0.7 g of a polycarbonate resin in 100 ml of methylene chloride at 20 ° C and using an Ostwald viscometer that calculates specific viscosity: specific viscosity (η sp ) = (t - t 0 ) / T 0 [t ₀ is the time (seconds) required to drop the methylene chloride, and t is the time (seconds) required for dropping the sample solution] using the resulting specific viscosity in the following equation: η sp / c = [η] + 0.45 × [η] 2 c ([η] means intrinsic viscosity) [η] = 1.23 × 10 4 M 0.83 c = 0.7.

At the aromatic polycarbonate resin as component A-1 of the present invention is is the above aromatic polycarbonate resin, which is substantially does not contain a halogen atom. The term "essentially no halogen atom "means that no halogen-substituted diphenol in the molecule is, except trace amounts of solvent residues (halogenated Hydrocarbon) and carbonate precursors in the process of preparation of the above aromatic polycarbonate.

Preferably shows the above aromatic polycarbonate resin (PC) as a component of the present invention A-1 an acid value from -0.5 to 5.0 (mg equivalent Acid / 10 kg PC). If the acid value is the Range of -0.5 to 5.0 (mg equivalent Acid / 10 kg PC) is fulfilled the silicone compound of the invention (Component B) effectively their function and leads easily to creep resistance, antistatic properties and a Prevent dripping of the resin when burning. One aromatic polycarbonate resin having an acid value of 0.0 to 3.0 (mg equivalent Acid / 10 kg PC) is particularly preferred. At an acid value of less than -0,5 (mg-eq acid / 10 kg PC), the aromatic polycarbonate resin itself becomes highly alkaline and the heat stability of the obtained Composition decreases. At an acid value of more than 5.0 (mg equivalent Acid / 10 kg PC) become free acid groups or terminal Phenol groups contained in the aromatic polycarbonate resin, to the Si-H group present in the silicone compound (component B) is bound, what the achievement of creep resistance, antistatic properties and prevention of dripping of the resin when burning difficult.

V:

Säurewert (mg-Äquivalent Säure/10 kg PC)

N:

Mol/Liter Natriummethylat (CH₃ONa)

k:

Faktor von 0,01 Mol/Liter CH₃ONa

X:

Titer mit der Probe (ml)

Y:

Titer ohne Probe (ml)

W:

Menge der Probe (g)

The acid value used here means the amount of acid or base contained per 10 kg of polycarbonate resin (10 kg of PC). 1 ml of C ₁₅ H ₁₇ CN ₄ -C ₁₆ H ₁₈ CIN ₃ S · nH ₂ O is added as indicator to a solution obtained by adding 3 ml of methanol to 100 ml of methylene chloride and dissolving 10.0 g of a polycarbonate resin in the resulting mixture was obtained at 20 ° C as a sample. The sample solution is titrated with 0.01 mol / liter of sodium methylate (CH ₃ ONa) to give an acid value by substituting the titer in the presence of the sample and the titer without the sample in the following equation. V = N × k × (X-Y) × 10000 / W

V:

Acid value (mg equivalent acid / 10 kg PC)

N:

Mol / liter sodium methylate (CH ₃ ONa)

k:

Factor of 0.01 mol / liter CH ₃ ONa

X:

Titre with the sample (ml)

Y:

Titers without sample (ml)

W:

Amount of sample (g)

Hydrochloric acid or the like for removing a catalyst such as triethylamine used for promoting the reaction can be used in the process for producing an aromatic polycarbonate resin by the interfacial polycondensation method. In this case, the acid value of the aromatic polycarbonate resin can be adjusted to a range of -0.5 to 5.0 (mg equivalent of acid / 10 kg of PC) by adding an appropriate amount of an alkali component to add a hydrochloric acid-derived acid component neutralize, or by a cleaning step, z. B. a washing process, intensified. In the process for producing an aromatic polycarbonate resin by the boundary A surface polycondensation process without using a catalyst, the acid value can be adjusted to a range of -0.5 to 5.0 (mg equivalent of acid / 10 kg of PC) by adding an appropriate amount of an acid component to form an alkali component which is from an acid binder, such as sodium hydroxide, to neutralize, or by passing a purification step, e.g. B. a washing process, intensified.

The Styrene-based resin in the context of component A-2, used as a resin component A in the resin composition of the present invention is obtained by adding a monomer Styrene-based and optionally at least one further constituent, from other vinyl monomers and rubber polymers with the styrene-based monomer is copolymerizable, is polymerized.

To Examples of the styrene-based monomer described in the above resin component styrene based, include styrene and styrene derivatives, such as α-methylstyrene, o-methylstyrene, p-methylstyrene, vinylxylene, Ethylstyrene, dimethylstyrene, p-tert-butylstyrene, vinylnaphthalene and methoxystyrene. Styrene is particularly preferred. These ingredients can be alone or in combination of two or more components.

To Examples of other vinyl monomers containing the above styrene-based monomer are copolymerizable belong Vinyl cyanide compounds, such as acrylonitrile and methacrylonitrile; Aryl esters of acrylic acid, such as Phenyl acrylate and benzyl acrylate; Alkyl esters of acrylic acid, such as Methyl acrylate, ethyl acrylate, propyl acrylate, butyl acrylate, amyl acrylate, Hexyl acrylate, 2-ethylhexyl acrylate, octyl acrylate, cyclohexyl acrylate and dodecyl acrylate; Aryl esters of methacrylic acid, such as peenyl methacrylate and benzyl methacrylate; Alkyl esters of methacrylic acid, such as methyl methacrylate, Ethyl methacrylate, propyl methacrylate, butyl methacrylate, amyl methacrylate, Hexyl methacrylate, 2-ethylhexyl methacrylate, Octyl methacrylate, cyclohexyl methacrylate and dodecyl methacrylate; Epoxy group-containing methacrylic acid esters such as glycidyl methacrylate; Maleimide-based monomers such as maleimide, N-methylmaleimide and N-phenylmaleimide; and α, β-unsaturated carboxylic acids and Anhydrides thereof, such as acrylic acid, methacrylic acid, maleic acid, maleic anhydride, phthalic and itaconic acid.

To Examples of the rubbery polymer copolymerized with the above-mentioned styrene-based monomer belong Polybutadiene, polyisoprene, diene-based copolymers, such as random Styrene · butadiene copolymers and block copolymers, Acrylonitrile · butadiene copolymers, Copolymers of an alkyl acrylate or alkyl methacrylate and butadiene and butadiene · isoprene copolymers; Copolymers of ethylene and an α-olefin, such as ethylene-propylene copolymers and block copolymers and ethylene-butene random copolymers and block copolymers; Copolymers of ethylene and an unsaturated carboxylic ester, such as ethylene ·· methacrylate copolymers and ethylene · butyl acrylate copolymers; Copolymers of ethylene and an aliphatic vinyl compound, such as ethylene · vinyl acetate copolymers; Terpolymers of ethylene, propylene and a non-conjugated diene, such as ethylene · propylene · hexadiene terpolymers; Acrylic rubbers such as polybutyl acrylate; and composite rubbers having such a structure that a polyorganosiloxane rubber component and a polyalkyl (meth) acrylate rubber component are so devoured with each other that they are not separated can be (Rubbers of the IPN type).

To explanatory Examples of the styrene-based resin (component A-2) includes polystyrene, styrene-butadiene-styrene copolymers (SBS resin), hydrogenated styrene · butadiene · styrene copolymers Hydrogenated Styrene Isoprene Styrene Copolymers (SEPS Resin), High impact polystyrene (HIPS), Acrylonitrile · styrene copolymers (AS resin), acrylonitrile · butadiene · styrene copolymers (ABS resin), methyl methacrylate · butadiene · styrene copolymers (MBS resin), methyl methacrylate · acrylonitrile · butadiene · styrene copolymers (MABS resin), acrylonitrile · acrylic rubber · styrene copolymers (AAS resin), acrylonitrile · ethylene-propylene rubber · styrene copolymers (AES resin), styrene · IPN rubber copolymers and mixtures thereof. The above-mentioned styrene-based resins may have a high stereoregularity such as syndiotactic polystyrene, indicating the use a catalyst, e.g. B. a metallocene catalyst in which Production is due. Furthermore, can depending on the circumstances Narrow molecular weight distribution polymers and copolymers, block copolymers and polymers and copolymers of high stereoregularity used be all by a method such as an anionic living Polymerization or radical living polymerization become. These include polystyrene (PS), high impact polystyrene (HIPS), Acrylonitrile · styrene copolymers (AS resin), methyl methacrylate · butadiene · styrene copolymers (MBS resin) and acrylonitrile · butadiene · styrene copolymers (ABS resin) is preferred. Particularly preferred is ABS resin. The resins based on styrene be used in combination of two or more components.

At the ABS resin is a mixture of a thermoplastic Graft copolymers obtained by graft polymerization of a vinyl cyanide compound and an aromatic vinyl compound on a rubber component obtained on diene basis, and a copolymer of a Vinyl cyanide compound and an aromatic vinyl compound. at the diene-based rubber component constituting this ABS resin, it is a rubber with a glass transition temperature of 10 ° C or less, such as polybutadiene, polyisoprene or styrene · butadiene copolymers. This component is used in an amount of preferably 5 to 80% by weight. and in particular from 10 to 50% by weight, based on 100% by weight of the ABS resin component, used. Examples of the vinyl cyanide compound which undergoes graft polymerization with the Diene-based rubber component to undergo include the listed above Compounds, among which acrylonitrile is particularly preferred. To Examples of the aromatic vinyl compound, the graft polymerization with The diene-based rubber component to be subjected to include the listed above Compounds of which styrene and α-methylstyrene are particularly preferred become. The total amount of components that the graft polymerization to be subjected to the diene-based rubber component is preferably 95 to 20 wt .-% and in particular 50 to 90 wt .-%, based on 100 Wt .-% of the ABS resin component. Preferably, the amount of the Vinyl cyanide compound 5 to 50 wt .-% and the amount of aromatic Vinyl compound 95 to 50 wt .-%, based on 100 wt .-% of the total amount from the vinyl cyanide compound and the aromatic vinyl compound. Methyl (meth) acrylate, ethyl acrylate, maleic anhydride or N-substituted maleimide can with the part of the components that the graft polymerization with the aforementioned Diene-based rubber component to undergo, mixed become. The total amount of the above substances is preferably 15% by weight or less, based on the ABS resin component. traditionally, known initiators, chain transfer agents, Emulsifiers and the like, for The implementation can be used as needed.

The Weight average particle diameter of the rubber particles which contained in the ABS resin is preferably 0.1 to 5.0 μm, in particular 0.15 to 1.5 microns and especially 0.2 to 1 μm. One Rubber with a particle size distribution with a single peak or two or more peaks can be used become. It can also be used a rubber whose morphology is such that the rubber particles are a single phase or having a "salami" structure formed thereby that is an enclosed phase around each rubber particle is included.

It It is known that ABS resin is a vinyl cyanide compound and an aromatic one Contains vinyl compound, not the graft polymerization with a rubber component are diene-based. The ABS resin according to the invention can by a Polymerization formed free polymer component. The Molecular weight of the free copolymer of a vinyl cyanide compound and an aromatic vinyl compound is preferably 0.2 to 1.0 and in particular from 0.25 to 0.5, expressed as reduced viscosity (dl / g).

The graft the total amount of the grafted vinyl cyanide compound and the aromatic vinyl compound to the diene-based rubber component is preferably 20 to 200 wt .-% and in particular 20 to 70 wt .-%.

This ABS resin can be prepared by bulk polymerization, suspension polymerization or emulsion polymerization or by a one-stage or multi-stage Copolymerization can be produced. A product that is obtained by one by copolymerization of an aromatic vinyl compound and a vinyl cyanide component obtained vinyl polymer, with the ABS resin obtained by the above production method may also be used in a preferred manner.

At the aromatic polyester resin as component A-3, used as a resin component (A) in the resin composition of the present invention can be used, it is a polymer or copolymer, the one aromatic dicarboxylic acid or a reactive derivative thereof and a diol or ester derivative thereof as main components, wherein the polymers by a condensation reaction have been obtained.

To preferred examples of the aromatic dicarboxylic acid belong terephthalic acid, isophthalic acid, o-phthalic acid, 1,5-naphthalenedicarboxylic acid, 2,6-naphthalenedicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 4,4'-biphenyletherdicarboxylic acid, 4,4'-biphenylmethanedicarboxylic acid, 4,4'-biphenylsulfonedicarboxylic acid, 4,4'-biphenylisopropylidenedicarboxylic acid, 1,2 Bis (phenoxy) ethane-4,4'-dicarboxylic acid, 2,5-anthracenedicarboxylic acid, 2,6-anthracenedicarboxylic acid, 4,4'-p-terphenylendicarboxylic acid and 2,5-pyridinedicarboxylic acid. These include terephthalic acid and 2,6-naphthalenedicarboxylic acid particularly preferred.

These aromatic dicarboxylic acids can used in a combination of two or more components become. The dicarboxylic acid can with one or more aliphatic dicarboxylic acids, such as adipic acid, azelaic acid, sebacic and dodecanedioic acid and with alicyclic dicarboxylic acids, such as cyclohexanedicarboxylic acid, in be mixed in small quantities.

To Examples of the diol as a component of the aromatic polyester of the invention belong to aliphatic Diols, such as ethylene glycol, propylene glycol, butylene glycol, hexylene glycol, Neopentyl glycol, pentamethylene glycol, hexamethylene glycol, decamethylene glycol, 2-methyl-1,3-propanediol, Diethylene glycol and triethylene glycol; alicyclic diols such as 1,4-cyclohexanedimethanol; Diols containing an aromatic ring such as 2,2-bis-β-hydroxyethoxyphenyl) -propane; and mixtures thereof. One or more long chain diols with one Molecular weight of 400 to 6,000, such as polyethylene glycol, poly-1,3-propylene glycol and Polytetramethylene glycol, can be copolymerized in small quantities.

Of the aromatic according to the invention Polyester can be branched by adding a small amount of one Introduces branching agent. The branching agent has no restrictions on a specific one However, it is subject to trimesic acid, trimellitic acid, trimethylolethane, Trimethylolpropane and pentaerythritol selected. For illustrative examples of the aromatic Polyester resin (component A-3) include polyethylene terephthalate (PET), polypropylene terephthalate, polybutylene terephthalate (PBT), Polyexylene terephthalate, polyethylene naphthalate (PEN), polybutylene naphthalate (PBN), polyethylene-1,2-bis (phenoxy) ethane-4,4'-dicarboxylate and copolyesters such as polyethylene isophthalate / terephthalate and polybutylene terephthalate / isophthalate as well as mixtures thereof. Among them, polyethylene terephthalate and Polyethylene naphthalate containing ethylene glycol as a diol component, preferred when it comes to a good balance between thermal Properties and mechanical properties arrives. Products, the 50% by weight or more of polyethylene terephthalate or polyethylene naphthalate, based on 100% by weight of the aromatic polyester resin, are favored. Products containing 50% by weight or more of polyethylene terephthalate are particularly preferred. Polybutylene terephthalate and Polybutylene naphthalate containing butylene glycol as a diol component, are further preferred when it comes to a favorable balance between Deformability and mechanical properties arrives. The weight ratio of Polybutylene terephthalate to polyethylene terephthalate is preferably 2 to 10.

The Structure of terminal group of the obtained aromatic polyester resin is not subject to any special restrictions. The amount of terminal Hydroxyl group may be the same, greater or less less than the amount of the terminal carboxyl group. These terminal groups can be capped by doing a reaction with a compound, which is reactive with these terminal groups.

The aromatic polyester resin is obtained by polymerization of the above dicarboxylic acid and the diol component under heating in the presence of a polymerization catalyst containing on titanium, germanium or antimony and by removing it as a by-product formed water, lower alcohol or diol from the system according to one usually prepared processes. Containing germanium Polymerization catalyst is, for example, a Oxide, hydroxide, halide, alcoholate or phenolate of germanium, such as germanium oxide, germanium hydroxide, germanium tetrachloride and Tetramethoxygermanium.

A known compound of manganese, zinc, calcium, magnesium or the like, used in the ester interchange reaction prior to polycondensation is, can be used according to the invention become. The polycondensation can be achieved by deactivating the above Catalyst with a compound of phosphoric acid or phosphorous acid at the end the ester exchange reaction can be carried out.

The Molecular weight of the aromatic polyester resin is not subject to any special restrictions, however, is the intrinsic viscosity, measured at 35 ° C in o-chlorophenol as solvent 0.4 to 1.2 and preferably 0.6 to 1.15.

As for the ratio of the aromatic polycarbonate resin (component A-1), the styrene-based resin (component A-2) and / or the aromatic polyester resin (component A-3) in the aromatic polycarbonate resin composition (A) of the present invention Amount of the aromatic polycarbonate resin is 100 to 50% by weight, and preferably 99.5 to 50% by weight, and the total amount of the styrene-based resin and / or the aromatic polyester resin is 0 to 50% by weight, and preferably 0.5 to 50% % By weight based on 100% by weight of the total of the aromatic polycarbonate resin, the styrene-based resin and / or the aromatic polyester resin. When the amount of the aromatic polycarbonate resin (component A-1) is less than 50% by weight, that is, when the total amount of the resin is Sty rolbasis (component A-2) and / or the aromatic polyester resin (component A-3) is greater than 50 wt .-%, so there is an unsatisfactory flame retardant nature.

wobei die einzelnen Reste X unabhängig voneinander eine OH-Gruppe oder eine einwertige organische Gruppe mit 1 bis 20 Kohlenstoffatomen bedeuten und n den Wert 0 hat oder eine ganze Zahl mit einem Wert von 1 bis 5 bedeutet, mit der Maßgabe, dass dann, wenn n einen Wert von 2 oder mehr hat, die Reste X sich voneinander unterscheiden können.The silicone compound (component B) used as a flame retardant in the resin composition of the present invention are specific silicone compounds having Si-H bonds. That is, it is a silicone compound (component B) which contains an Si-H group and an aromatic group in the molecule and which is at least one compound selected from silicone compounds having (1) a Content of Si-H groups (Si-H content) of 0.1 to 1.2 mol / 100 g and (2) a content of aromatic groups represented by the following general formula (1) (content of aromatic groups) of 10 to 70% by weight:

wherein the individual radicals X independently of one another denote an OH group or a monovalent organic group having 1 to 20 carbon atoms and n has the value 0 or an integer with a value of 1 to 5, with the proviso that if n has a value of 2 or more, the radicals X may differ from each other.

wobei Z¹ bis Z³ jeweils unabhängig voneinander ein Wasserstoffatom, eine einwertige organische Gruppe mit 1 bis 20 Kohlenstoffatomen oder eine Verbindung der folgenden allgemeinen Formel (4) bedeuten, α1 bis α3 jeweils unabhängig voneinander den Wert 0 oder 1 haben und ml den Wert 0 hat oder eine ganze Zahl mit einem Wert von 1 oder mehr bedeutet, mit der Maßgabe, dass dann, wenn ml einen Wert von 2 oder mehr hat, die Struktureinheiten sich voneinander unterscheiden können,

wobei Z⁴ bis Z⁸ jeweils unabhängig voneinander ein Wasserstoffatom oder eine einwertige organische Gruppe mit 1 bis 20 Kohlenstoffatomen bedeuten, α4 bis α8 jeweils unabhängig voneinander einen Wert von 0 oder 1 haben und m2 den Wert 0 hat oder eine ganze Zahl mit einem Wert von 1 oder mehr bedeutet, mit der Maßgabe, dass dann, wenn m2 einen Wert von 2 oder mehr hat, die Struktureinheiten sich voneinander unterscheiden können.The silicone compound is preferably at least one compound selected from silicone compounds containing a structural unit represented by at least one of the following general formulas (2) and (3) as a Si-H bond-containing moiety:

wherein Z ¹ to Z ³ each independently represent a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms or a compound represented by the following general formula (4), α1 to α3 each independently have the value 0 or 1 and ml represents 0 has or means an integer having a value of 1 or more, with the proviso that when ml has a value of 2 or more, the structural units may be different from each other,

wherein Z ⁴ to Z ⁸ each independently represents a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, α4 to α8 each independently have a value of 0 or 1, and m2 has the value 0 or an integer of a value of 1 or more, with the proviso that when m2 has a value of 2 or more, the structural units may be different from each other.

at the silicone compound is in particular a silicone compound with an MD unit or an MDT unit, if M is a monofunctional siloxane unit, D is a bifunctional Siloxane unit and T is a trifunctional siloxane unit means.

Examples of the monovalent organic group having 1 to 20 carbon atoms in Z ¹ to Z ⁸ in the structural units of the above general formulas (2), (3) and (4) and X in the general formula (1) include alkyl groups such as methyl, ethyl, propyl, butyl, hexyl and decyl, cycloalkyl groups such as cyclohexyl, alkenyl groups such as vinyl and allyl, aryl groups such as phenyl and tolyl, and aralkyl groups. These groups may contain a functional group, e.g. Example, an epoxy group, carboxyl group, carboxylic anhydride group, amino group or mercapto group. The organic group is preferably an alkyl group having 1 to 8 carbon atoms, an alkenyl group or an aryl group. Particularly preferred is an alkyl group having 1 to 4 carbon atoms, such as methyl, ethyl or propyl, a vinyl group or a phenyl group.

If the silicone compound, which is a structural unit formed by at least one of the above general formulas (2) and (3) is, contains, contains several types of siloxane bonds in the structural unit can a random copolymerization, a block copolymerization or a conical copolymerization.

According to the invention must Si-H content of the silicone compound used as component B in Range of 0.1 to 1.2 mol / 100 g. When the Si-H content in Range of 0.1 to 1.2 mol / 100 g, it is found in the Burning easily the formation of the silicone structure. The silicone compound has in particular a Si-H content from 0.2 to 1.0 mol / 100 g. When the Si-H content is below 0.1 mol / 100 g, the formation of the silicone structure is difficult. At a content of more than 1.2 mol / 100 g, the heat stability of the obtained reduced Composition and the additional Proportion of Si-H groups reacts with water in the air to form of hydrogen gas when exposed to heat under humid conditions, with the result that the obtained Composition foams and a shaped body a cloudy Texture assumes. The term "silicone structure" means a network structure that by reaction between silicone compounds or by reaction formed between the resin and the silicone.

The term "Si-H content" as used herein means the number of moles of an Si-H structure contained per 100 g of the silicone compound. This value can be obtained by measuring the volume of hydrogen gas obtained per unit weight of the silicone compound by an alkaline cleavage method. For example, when developing 122 ml of hydrogen gas per 1 g of the silicone compound at 25 ° C., the Si-H content is 0.5 mol / 100 g according to the following calculation method. 122 × 273 / (273 + 25) ÷ 22400 × 100 = 0.5

to suppression the cloudiness a shaped body or the decrease in transparency caused by heat treatment under humid conditions of the resin composition by mixing the silicone compound with the resin components (A) and in particular with component A-1 the dispersion state of the silicone compound of importance. If the silicone compound is poorly dispersed, the resin composition becomes even cloudy and it is done additionally a replacement on the surface a shaped body or the silicone compound undergoes a shift and a poor distribution in the heat treatment in wet conditions with the result that there is a decrease the transparency comes, what makes it more difficult, a molding of to obtain excellent transparency. Important factors to Determination of the state of dispersion are the proportion of aromatic Groups in the silicone compound and the average degree of polymerization. The average degree of polymerization is in the transparent according to the invention Resin composition of particular importance.

in the In view of the above, the silicone compound of the present invention must have a proportion of aromatic groups of 10 to 70 wt .-%. The silicone compound preferably has a content of aromatic Groups of 15 to 60 wt .-% on. If the proportion of aromatic Groups in the silicone compound is less than 10 wt .-%, then yields a poor distribution of the silicone compound and no good Dispersion, which makes it difficult to form a molded article with excellent transparency to obtain. If the proportion of aromatic groups is more than 70% by weight, so also results in a poor distribution of the silicone compound and a lack of dispersion due to the rigidity of the corresponding ones molecules what makes it difficult, a molding to obtain excellent transparency.

Gehalt an aromatischen Gruppen = [A/M] × 100 (Gew.-%) The term "proportion of aromatic groups" used herein means the proportion of aromatic groups of the following general formula (1), which proportion can be determined by the following calculation.

Content of aromatic groups = [A / M] × 100 (wt%)

A

= Gesamtes Molekulargewicht sämtlicher aromatischer Gruppen der allgemeinen Formel (1), die im einem Molekül der Siliconverbindung enthalten sind

M

= Molekulargewicht der Siliconverbindung

A and M in the above expression represent the following numerical values.

A

= Total molecular weight of all the aromatic groups of the general formula (1) contained in one molecule of the silicone compound

M

= Molecular weight of the silicone compound

Further comprises the silicone compound according to the invention (Component B) preferably has a refractive index at 25 ° C of 1.40 to 1.60 on. The refractive index is in particular 1.42 to 1.59 and especially 1.44 to 1.59. When the refractive index in the aforementioned area falls, the silicone compound is finely dispersed in the aromatic polycarbonate, what is possible makes to obtain a resin composition having a low haze and excellent dyeing properties has.

Further comprises the silicone compound according to the invention (Component B) preferably one by a method under determination the heat loss Volatility measured on heating of 18% or less, with heating at 105 ° C for 3 hours. The volatility is especially 10% or less. With a volatility of more than 18% results in a high volatility the silicone compound in the preparation of the resin composition, which makes it difficult from the resin composition of the invention moldings to build.

The A silicone compound which is a structural unit of the above general Contains formula, can have a linear or branched structure if they have the above conditions. A compound with a Si-H group in the side chain with terminal or branched position of the molecular structure or a plurality of bodies can be used.

In general, the structure of the silicone compound is built up by arbitrarily combining the following four siloxane units.
M unit: monofunctional siloxane unit such as (CH ₃ ) ₃ SiO _1/2 , H (CH ₃ ) ₂ SiO _1/2 , H ₂ (CH ₃ ) SiO _1/2 , (CH ₃ ) ₂ (CH ₂ = CH ) SiO _1/2 , (CH ₃ ) ₂ (C ₆ H ₅ ) SiO _1/2 or (CH ₃ ) (C ₆ H ₅ ) (CH ₂ = CH) Si0 _1/2
D unit: bifunctional siloxane unit, such as (CH ₃ ) ₂ SiO, H (CH ₃ ) SiO, H ₂ SiO, H (C ₆ H ₅ ) SiO, (CH ₃ ) (CH ₂ = CH) SiO or (C ₆ H ₅ ) ₂ SiO
T unit: trifunctional siloxane unit, such as (CH ₃ ) SiO _3/2 , (C ₃ H ₇ ) SiO _3/2 , HSiO _3/2 , (CH ₂ = CH) SiO _3/2 or (C ₆ H ₅ ) SiO _3/2
Q unit: tetrafunctional siloxane unit, such as SiO ₂ .

The structure of the silicone compound used according to the invention is represented by the empirical formulas D _n , T _p , M _m D _n , M _m T _p , M _m Q _q , M _m D _n T _p , M _m D _n Q _q , M _m T _p Q _q , M _m D _n T _p Q _q , D _n T _p , D _n Q _q or D _n T _p Q _q reproduced. Of these, the structure of the silicone compound is preferably represented by the formulas M _m D _n , M _m T _p , M _m D _n T _p or M _m D _n Q _q and in particular by the formulas M _m D _n or M _m D _n T _p (The coefficients m, n, p and q in the above formulas indicate the degrees of polymerization of the corresponding siloxane units, and the sum of the coefficients indicates the average degree of polymerization of the silicone compound.) In the present invention, the average degree of polymerization is preferably in the range of 3 to 150, especially 3 to 80, and more particularly from 3 to 60. When one of the coefficients m, n, p and q has a numerical value of 2 or more, the number of siloxane units of the coefficient may be 2 or more, the units being different from each other with respect to the Hydrogen atoms or the organic radicals bonded to the silicon atoms).

The The above silicone compounds may be used alone or in combination from 2 or more compounds are used.

The above silicone compound having a Si-H bond can be prepared by a method known per se. For example, the compound of interest can be obtained by cohydrolysing an organochlorosilane corresponding to the structure of the silicone compound of interest and removing the by-produced hydrochloric acid and low boiling point components. When starting material is a silicone oil, a cyclic siloxane or an alkoxysilane having an Si-H bond, an aromatic Group of the general formula (1) and a further organic radical in the molecule is used, the silicone compound of interest can be obtained by promoting a polymerization reaction, using as appropriate an acid catalyst such as hydrochloric acid, sulfuric acid or methanesulfonic acid, or adding water for hydrolysis purposes and then removing the acid catalyst and low boiling components used.

The Component B serving as the silicone compound is in an amount from 0.1 to 10 parts by weight, preferably from 0.3 to 7 parts by weight and in particular from 0.5 to 5 parts by weight, based on 100 parts by weight of the Total amount of resin components (A) used.

At least a compound which is free radical generators, organic alkali metal salts and organic alkaline earth metal salts can be selected with the resin composition of the invention be mixed as component C. By mixing this component C leaves the flame-retardant nature continues to improve and in particular can be the properties to prevent dripping improve. According to the invention Component C as "agent for improving the flame retardant nature Amount of component C used as a means of improving the flame retardant Texture serves, amounts 0.001 to 0.3 parts by weight, preferably 0.005 to 0.3 parts by weight and in particular 0.005 to 0.2 parts by weight, based on 100 parts by weight the total amount of resin components (A).

To Examples of as the inventive component (C) used radical generators include organic peroxides, such as 2,5-dimethyl-2,5-di- (tert-butylperoxy) hexyne-3 and dicumyl peroxide and 2,3-dimethyl-2,3-diphenylbutane (so-called dicumyl). These products are sold by the NOF Corporation under the trade names Perhexyne 25B, Percumyl D and Nofmer BC are distributed and can be light be obtained. 2,3-dimethyl-2,3-diphenylbutane (dicumyl) becomes especially preferred because it hardly generates any radicals when kneading with melting, but at the time of combustion a stable radical formation effectively guaranteed.

At the according to the invention as a component (C) used alkali metal salt or alkaline earth metal salt can it be a metal salt, its use as a flame retardant ausrüstendes Funds for a polycarbonate resin is known, in particular a metal salt an organic sulfonic acid or a metal salt of a sulfuric acid ester. These products can be alone or used in a combination of two or more components become. In the case of the alkali metal according to the invention it is lithium, sodium, potassium, rubidium or cesium and in the alkaline earth metal to beryllium, magnesium, calcium, strontium or Barium. Of these, lithium, sodium and potassium are particularly preferred.

At the above metal salt of an organic sulfonic acid it is an alkali metal salt of an aliphatic sulfonic acid, a An alkaline earth metal salt of an aliphatic sulfonic acid, an alkali metal salt of a aromatic sulfonic acid or an alkaline earth metal salt of an aromatic sulfonic acid. To preferred examples of The metal salt of an aliphatic sulfonic acid includes alkali metal salts (alkaline earth metal salts) alkane sulfonic acid, Alkali metal salts (alkaline earth metal salts) of a sulfonic acid, the by substitution of at least one hydrogen atom on the alkyl groups the alkali metal salts (alkaline earth metal salts) of an alkanesulfonic acid a fluorine atom have been obtained, and alkali metal salts (alkaline earth metal salts) a perfluoroalkanesulfonic acid. These products can alone or in a combination of two or more components used (the "alkali metal salts (Alkaline earth metal salts) "include both alkali metal salts and alkaline earth metal salts).

To preferred examples of used in the alkali metal salts (alkaline earth metal salts) of an alkanesulfonic acid alkanesulfonic belong methane, ethanesulfonic, propane sulfonic acid, butane sulfonic acid, methylbutanesulfonic, hexane sulfonic acid, heptanesulfonic and octanesulfonic acid. These products can alone or in a combination of two or more components be used. It can Also metal salts are used by substitution of hydrogen atoms of the alkyl groups have been obtained by a fluorine atom.

To preferred examples of the perfluoroalkanesulfonic acid belong Perfluromethansulfonsäure, perfluoroethanesulfonic, Perfluorpropansulfonsäure, Perlfuorbutansulfonsäure, Perfluormethylbutansulfonsäure, Perfluoraexansulfonsäure, perfluoroheptanesulfonic and perfluorolanesulfonic acid. These include perfluoroalkanesulfonic acids having 1 to 8 carbon atoms particularly preferred. These products can be used alone or in combination be used from two or more components.

sodium salts of ethanesulfonic acid are preferred as the alkali metal salts (alkaline earth metal salts) of an alkanesulfonic acid and potassium salts of perfluorobutanesulfonic acid are used as alkali metal salts (Alkaline earth metal salts) of a perfluoroalkanesulfonic acid.

at as the alkali metal salt (alkaline earth metal salt) of an aromatic sulfonic acid used aromatic sulfonic acid it concerns at least one acid, which consists of the following Group selected is: sulfonic acid a monomeric or polymeric aromatic sulfide, sulfonic acid aromatic carboxylic acid or esters, sulfonic acid a monomeric or polymeric aromatic ether, sulfonic acid of an aromatic Sulfonates, monomeric or polymeric aromatic sulfonic acids, monomers or polymeric aromatic sulfonic sulfonic acids, sulfonic acids of a aromatic ketones, heterocyclic sulfonic acids, sulfonic acid aromatic sulfoxide and methylene-bound condensate of aromatic Sulfonic acids. These Products can alone or in a combination of two or more components be used.

The Alkali metal salts (alkaline earth metal salts) of a sulfonic acid of a monomeric or polymeric aromatic sulfides are disclosed in JP-A-50-98539 described. These include Disodium diphenyl sulfide-4,4'-disulfonate and Dikaliumdiphenylsulfid-4,4'-disulfonate.

The Alkali metal salts (alkaline earth metal salts) of a sulfonic acid aromatic carboxylic acid or esters are described in JP-A-50-98540. These include potassium 5-sulfoisophthalate, Sodium 5-sulfoisophthalate and polysodium polyethylene terephthalate polysulfonate.

The Alkali metal salts (alkaline earth metal salts) of a sulfonic acid of a monomeric or polymeric aromatic ethers are disclosed in JP-A-50-98542 described. These include Calcium 1-methoxynaphthalene-4-sulfonate, disodium 4-dodecylphenyl ether disulfonate, Polynatriumpoly- (2,6-dimethyl phenylene oxide) -polysulfonat, Polysodium poly (1,3-phenylene oxide) polysulfonate, polysodium poly (1,4-phenylene oxide) polysulfonate, Polypotassium poly (2,6-diphenylphenylene oxide) polysulfonate and lithium poly (2-fluoro-6-butylphenylene oxide) polysulfonate.

The Alkali metal salts (alkaline earth metal salts) of a sulfonic acid of a aromatic sulfonate are described in JP-A-50-98544. For this belong Potassium sulfonate of benzenesulfonate.

The Alkali metal salts (alkaline earth metal salts) of a monomeric or polymeric aromatic sulfonic acid are described in JP-A-50-98546. These include sodium benzenesulfonate, Strontium benzenesulfonate, magnesium benzenesulfonate, dipotassium p-benzenedisulfonate, Dikaliumnaphthalin-2,6-disulfonate and calcium biphenyl 3,3'-disulfonate.

The Alkali metal salts (alkaline earth metal salts) of a monomeric or polymeric aromatic sulfonic acid are described in JP-A-52-54746. These include sodium diphenylsulfone-3-sulfonate, Potassium diphenylsulfone-3-sulfonate, dipotassium diphenylsulfone-3,3'-disulfonate and dipotassium diphenylsulfone-3,4'-disulfonate.

The Alkali metal salts (alkaline earth metal salts) of a sulfonic acid of a aromatic ketones are described in JP-A-50-98547. These include sodium α, α, α-trifluoroacetophenone-4-sulfonate and dipotassium benzophenone 3,3'-disulfonate.

The Alkali metal salts (alkaline earth metal salts) of a heterocyclic sulfonic acid are described in JP-A-50-116542. These include disodium thiophene-2,5-disulfonate, Dipotassium thiophene-2,5-disulfonate, calcium thiophene-2,5-disulfonate and sodium benzothiophenesulfonate.

The Alkali metal salts (alkaline earth metal salts) of a sulfonic acid of a aromatic sulfoxide are described in JP-A-52-54745. For this belongs Kaliumdiphenylsulfoxid-4-sulfonate.

The methylene-bonded condensates of alkali metal salts (alkaline earth metal salts) of aromatic sulfonic acids include a condensate of formalin and sodium naphthalenesulfonate and a condensate of formalin and sodium anthracene sulfonate.

The alkali metal salts (alkaline earth metal salts) of a sulfuric acid ester are alkali metal salts (alkaline earth metal salts) of a sulfuric acid ester of one or more monohydric and / or polyhydric alcohols, such as methylsulfuric acid ester, ethylsulfuric acid ester, laurylsulfuric acid ester, hexadecylsulfuric acid ester, sulfuric acid ester of a polyoxyethylenealkylphenyl ether, mono-, di- or tri-acid. and tetrasulfuric acid ester of pentaerythritol, sulfuric acid ester of monoglyceride laurate, sulfuric acid ester of monoglyceride palmitate and sulfuric acid ester of monoglyceride stearate. alkali metal Salts (alkaline earth metal salts) of a laurylsulfuric acid ester are particularly preferred as alkali metal salts (alkaline earth metal salts) of a sulfuric acid ester.

To Other alkali metal salts (alkaline earth metal salts) include alkali metal salts (Alkaline earth metal salts) of an aromatic sulfonamide, such as alkali metal salts (Alkaline earth metal salts) of saccharin, N- (p-tolylsulfonyl) -p-toluenesulfonamide, N- (N'-benzylaminocarbonyl) -sulfanilimide and N- (phenylcarboxyl) sulfanilimide.

From the above alkali metal salts (alkaline earth metal salts) Alkali metal salts (alkaline earth metal salts) of an aromatic sulfonic acid and Alkali metal salts (alkaline earth metal salts) of a perfluoroalkanesulfonic acid are preferred.

The Flame retardant according to the invention Composition is made by adding a special silicone compound (Component B) as a flame retardant agent with resin components (A) containing an aromatic polycarbonate resin as a main component, in a special relationship mixed.

Consequently is a flame retardant according to the invention aromatic polycarbonate resin composition provided when burning excellent properties in terms of one Prevent dripping and no flame retardant Halogen-based agents, e.g. B. a bromine compound as a flame retardant Contains funds (hereinafter simply referred to as "halogen-free") by the resin components (A) including an aromatic Polycarbonate resin as the main component, a silicone compound (component B) and optionally an agent for improving the flame retardant Texture (component C) combined. Other resins, fillers and other additives can the resin composition of the invention like a usual one Polycarbonate resin composition are admixed. The others Resins, fillers and additional Additives are detailed below described.

The The following description refers to a typical preferred one embodiment of the present invention.

at this preferred embodiment is a halogen-free flame retardant aromatic polycarbonate resin composition, the one shaped body of excellent transparency and resistance to heat under humid conditions.

So far is in practice no halogen-free flame retardant aromatic Polycarbonate resin composition used, whose composition is relatively simple and has an excellent texture in it Reference to transparency and resistance to heat under humid conditions.

wobei die einzelnen Reste X unabhängig voneinander eine OH-Gruppe oder eine einwertige organische Gruppe mit 1 bis 20 Kohlenstoffatomen bedeuten und n den Wert 0 hat oder eine ganze Zahl mit einem Wert von 1 bis 5 bedeutet, mit der Maßgabe, dass dann, wenn in der Formel (1) n einen Wert von 2 oder mehr hat, die Reste X sich voneinander unterscheiden können.According to the present invention, there is provided a transparent flame-retardant aromatic polycarbonate resin composition comprising 100 parts by weight of an aromatic polycarbonate resin (component A-1) and 0.1 to 10 parts by weight of a silicone compound (component B) having an Si-H group and an aromatic group in the molecule, wherein the silicone compound is at least one compound selected from silicone compounds having (1) a content of Si-H groups (Si content) of 0.1 to 1 , 2 mol / 100 g and (2) has an aromatic group content of the formula (1) (aromatic group content) of 10 to 70% by weight

wherein the individual radicals X independently of one another are an OH group or a monovalent organic group having 1 to 20 carbon atoms and n has the value 0 or an integer with a value of 1 to 5, with the proviso that when in of the formula (1) n has a value of 2 or more, the radicals X may differ from each other.

These transparent flame-retardant aromatic polycarbonate resin composition also referred to as "transparent resin composition" in the following description. In the Description will be both a transparent composition as Also, an opaque composition simply referred to as "resin composition" or as "flame retardant resin composition".

at the above transparent resin composition of the present invention Invention is a halogen-free resin composition, which has a simple composition in that it is 100 Parts by weight of an aromatic polycarbonate resin (component A-1) as a resin component and 0.1 to 10 parts by weight of a silicone compound contains and having a flame retardant texture and transparent and against heat resistant to damp conditions is.

These Transparent resin composition includes an aromatic polycarbonate resin (Component A-1) as the essential main resin component. she can in small amounts other resins (components A-2, A-3 and the like) provided they do not affect the transparency. For the silicone compound as component B in the transparent Resin composition is a silicone compound whose Structure, average degree of polymerization, Si-H content, content to aromatic groups and refractive index above are. The preferred examples given above also become for the Silicone compound preferred. Specifically, the average degree of polymerization is preferably 3 to 80, especially 3 to 60, especially 4 to 40 and more preferably 4 to 20.

Further can the relationship of the aromatic polycarbonate resin (component A-1) to the silicone compound (Component B) be the same size like the relationship the total amount of the above resin components (components A) to the silicone compound (component B). The above-mentioned agent for improving the flame-retardant nature (component C) can be used in the above transparent resin composition become. If the means of improving the flame-retardant texture (Component C) is used in the aforementioned small amount, she practices their Impact and impaired in most cases Transparency of resin not.

The transparent according to the invention Although resin composition can with other resins and fillers within the limits that do not affect the transparency have to be mixed, however taking into account the types and quantities the transparency selected since most resins and fillers are transparent affect.

The transparent resin composition of the present invention provides a molded article of excellent transparency and heat resistance under humid conditions. As stated below, the haze of a 2 mm thick molded article is 0.3 to 20%, and preferably 0.5 to 15%. As further explained below, the difference ΔH (H ₁ -H ₀ ) is between the haze (H ₁ ) of a 2 mm thick molding which has been left at a temperature of 65 ° C and a humidity of 85% for 300 hours, and the original haze (H ₀ ) of the molded article 0.01 to 10% and preferably 0.02 to 7%. The transparent resin composition of the present invention is suitable for producing a molded article of excellent transparency and heat resistance under humid conditions.

There it is the transparent according to the invention Resin composition around a halogen-free, flame-retardant resin composition is, it can be used advantageously for the production of a shaped body be, in the transparency and resistance to heat under moist conditions are required.

There furthermore, the transparent according to the invention Resin composition a superior see-through texture may have a shaped body be obtained from excellent clarity and light color, by adding a pigment or a dye with the resin composition mixed.

The Components A, B and C of the resin composition of the invention were described above. A filler, another resin and additives mixed with this composition can be are described below.

Of the filler can with the resin composition of the invention be mixed as component (D). The mechanical strength a shaped body let yourself by mixing with this filler (component D) improve. fillers, which serve to improve the strength of a resin molding, can as filler be used. The amount of component D is 1 to 100 parts by weight, preferably 3 to 80 parts by weight and in particular 5 to 60 parts by weight, based on 100 parts by weight of the total amount of the resin components (A).

Examples of the component D include talcum, mica, clay, wollastonite, calcium carbonate, glass fibers, glass beads, glass balloons, ground fibers, glass flakes, carbon fibers, carbon flakes, carbon beads, ground carbon fibers, metal flakes, metal fibers, metal-plated glass fibers, metal coated carbon fibers, metal coated glass flakes, silica, ceramic particles, ceramic fibers, aramid particles, aramid fibers, polyarylate fibers, graphite, conductive carbon black and whiskers.

One thermoplastic resin which differs from the components A can with the resin composition of the invention be mixed to the mechanical, chemical and electrical Properties of a molding to improve. The amount of thermoplastic resin that is varies depending on the type and task, is 1 to 30 parts by weight and preferably 2 to 20 parts by weight, based on 100 parts by weight of the Total amount of resin components (A).

To Examples of include the thermoplastic resin Plastics for general purposes such as polyethylene resin, polypropylene resin and polyalkyl methacrylate resin; engineering plastics, such as polyphenylene ether resin, polyacetal resin, Polyamide resin, cyclic polyolefin resin and polyarylate resin (non-crystalline Polyarylate, liquid crystalline polyarylate); and high quality engineering plastics, such as polyetheretherketone, polyetherimide, polysulfone, polyethersulfone and polyphenylene sulfide. Furthermore, a thermoplastic elastomer, z. B. a thermoplastic elastomer based on olefin, a thermoplastic Polyamide-based elastomer or a thermoplastic elastomer based on polyurethane.

At known additives can with the resin composition of the invention be mixed in small amounts to a shaped body different To give features and to the characteristic features of the molding to improve. The amount of each additive corresponds to the normal one Quantities, provided they do not affect the objectives of the invention.

To Additives belong a deviating from the component B flame retardant (phosphoric acid ester, red phosphorus, metal hydrates and the like), anti-corrosive agents drop formation (fluorine-containing polymers with fibril-forming ability and Dergl.), heat stabilizers, UV light absorbers, light stabilizers, release agents, lubricants, Lubricants (PTFE particles and the like), coloring agents (pigments or dyes, such as carbon black, Titanium oxide and the like), optical diffusers (crosslinked acrylic particles, crosslinked silicone particles, thin Glass flakes, calcium carbonate particles and the like), fluorescent Brightener, luminescent pigments, fluorescent dyes, antistatic ausrüstende Agents, flow modifiers, crystal nucleating agents, inorganic or organic antifungal agents, stain protectors based on optical catalysts (fine particles of titanium oxide, fine particles of zinc oxide and the like), means for modification impact resistance, such as grafted rubber, IR light absorber and photochromic agents.

The Inventive resin composition comprises an aromatic polycarbonate resin as a resin component in in an amount of 50 to 100% by weight. Therefore be in an advantageous Way additives for improving heat stability, antioxidant properties, the optical stability (UV stability) and the mold release properties of the aromatic polycarbonate resin used to the above properties of the resin composition to improve. These additives will be described in detail below.

One Phosphorus-containing stabilizer can with the resin composition of the invention as a heat stabilizer be mixed. The phosphorus-containing stabilizer may be a phosphite compound, a phosphonite compound or a Act phosphate compound.

wobei R⁸ ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, eine Arylgruppe oder Alkylarylgruppe mit 6 bis 20 Kohlenstoffatomen, eine Aralkylgruppe mit 7 bis 30 Kohlenstoffatomen oder eine halogen-, alkylthio- (Alkylgruppe bis 1 bis 30 Kohlenstoffatomen) oder hydroxylsubstituierte Gruppe davon bedeutet, mit der Maßgabe, dass die drei Gruppen R⁸ gleich oder verschieden sein können und eine cyclische Struktur, die sich von einem Diphenol ableitet, gebildet werden kann.Various phosphite compounds can be used as heat stabilizers. For example, a phosphite compound of the following general formula (8) can be used

wherein R ^{8 represents} a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a halogeno, alkylthio (alkyl group to 1 to 30 carbon atoms) or hydroxyl-substituted group thereof with the proviso that the three R ⁸ groups can be the same or different and can form a cyclic structure derived from a diphenol.

wobei R⁹ und R¹⁰ jeweils unabhängig voneinander ein Wasserstoffatom, eine Alkylgruppe mit 1 bis 20 Kohlenstoffatomen, eine Arylgruppe oder eine Alkylarylgruppe mit 6 bis 20 Kohlenstoffatomen, eine Aralkylgruppe mit 7 bis 30 Kohlenstoffatomen, eine Cycloalkylgruppe mit 4 bis 20 Kohlenstoffatomen oder eine 2-(4-Oxyphenyl)-propyl-subst.-arylgruppe mit 15 bis 25 Kohlenstoffatomen bedeuten, mit der Maßgabe, dass die Cycloalkylgruppe und die Arylgruppe unsubstituiert oder durch eine Alkylgruppe substituiert sein können.Also, a phosphite compound represented by the following general formula (9) can be used

wherein R ⁹ and R ¹⁰ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group or an alkylaryl group having 6 to 20 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, a cycloalkyl group having 4 to 20 carbon atoms or a 2- (4-Oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms, provided that the cycloalkyl group and the aryl group may be unsubstituted or substituted by an alkyl group.

wobei R¹¹ und R¹² jeweils unabhängig voneinander eine Alkylgruppe mit 12 bis 15 Kohlenstoffatomen bedeuten und gleich oder verschieden sein können.Also, a phosphite compound represented by the following general formula (10) can be used

wherein R ¹¹ and R ¹² each independently represent an alkyl group having 12 to 15 carbon atoms and may be the same or different.

wobei Ar¹ und Ar² jeweils unabhängig voneinander eine Arylgruppe oder eine Alkylarylgruppe mit 6 bis 20 Kohlenstoffatomen oder eine 2-(4-Oxyphenyl)-propyl-subst.-arylgruppe mit 15 bis 25 Kohlenstoffatomen bedeuten, mit der Maßgabe, dass die vier Reste Ar¹ gleich oder verschieden sein können und die zwei Reste Ar² gleich oder verschieden sein können.The phosphonite compound as a heat stabilizer is a phosphonite compound of the general formulas (11) or (12)

wherein Ar ¹ and Ar ² each independently represent an aryl group or an alkylaryl group having 6 to 20 carbon atoms or a 2- (4-oxyphenyl) propyl-substituted aryl group having 15 to 25 carbon atoms, provided that the four groups Ar ^{1 may be the} same or different and the two radicals Ar ^{2 may be the} same or different.

To preferred examples of those represented by the above formula (8) Include phosphite compound Diphenyl isooctyl phosphite, 2,2'-methylenebis (4,6-di-tert-butylphenyl) octyl phosphite, Diphenylmono- (tridecyl) phosphite, Phenyldiisodecyl phosphite and phenyldi (tridecyl) phosphite.

To preferred examples by the general formula above (9) phosphite compound represented include distearyl pentaerythritol diphosphite, Bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite, bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite, Phenylbisphenol A-pentaerythritol diphosphite and dicyclohexylpentaerythritol diphosphite. Among them are distearyl pentaerythritol diphosphite, bis (2,4-di-tert-butylphenyl) pentaerythritol diphosphite and bis (2,6-di-tert-butyl-4-methylphenyl) pentaerythritol diphosphite is particularly preferred. The above phosphite compounds may be used alone or in combination be used from two or more compounds.

To preferred examples of the above general formula (10) The phosphite compound shown includes 4,4'-isopropylidenediphenol tetratridecyl phosphite.

Hereinafter, preferred examples of the phosphite compound represented by the above formula (11) are shown.
Tetrakis- (2,4-diisopropylphenyl) -4,4'-biphenylene diphosphonite,
Tetrakis- (2,4-di-n-butylphenyl) -4,4'-biphenylene diphosphonite,
Tetrakis- (2,4-di-tert-butylphenyl) -4,4'-biphenylene diphosphonite,
Tetrakis- (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphosphonite,
Tetrakis- (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite,
Tetrakis (2,6-di-isopropyl-phenyl) 4,4'-biphenylene,
Tetrakis (2,6-di-n-butyl-phenyl) 4,4'-biphenylene,
Tetrakis (2,6-di-tert-butylphenyl) 4,4'-biphenylene,
Tetrakis (2,6-di-tert-butylphenyl) -4,3'-biphenylenediphosphonite and
Tetrakis (2,6-di-tert-butylphenyl) -3,3'-biphenylene.

among them For example, tetrakis (di-tert-butylphenyl) biphenylene diphosphonite is preferred and tetrakis (2,4-di-tert-butylphenyl) biphenylene diphosphonite particularly preferred. Tetrakis- (2,4-di-tert-butylphenyl) -biphenylene diphosphonite is preferably in a combination of two or more compounds used. In particular, one, two or more of the components become Tetrakis- (2,4-di-tert-butylphenyl) -4,4'-biphenylene (Component E2-1), tetrakis (2,4-di-tert-butylphenyl) -4,3'-biphenylene diphosphonite (component E2-2) and tetrakis (2,4-di-tert-butylphenyl) -3,3'-biphenylene diphosphonite (Component E2-3) is used, but in particular a mixture the three components are preferred. The weight ratio of Components E2-1, E2-2 and E2-3 in the mixture preferably 100: 37 to 64: 4 to 14 and especially 100: 40 to 60: 5 to 11.

The following are preferred examples of the phosphonite compound represented by the above general formula (12):
Bis (2,4-diisopropylphenyl) -4-phenylphenylphosphonite, bis (2,4-di-n-butylphenyl) -3-phenylphenylphosphonite, bis (2,4-di-tert-butylphenyl) -4 phenylphenylphosphonite, bis (2,4-di-tert-butylphenyl) -3-phenylphenylphosphonite, bis (2,6-diisopropylphenyl) -4-phenylphenylphosphonite, bis (2,6-di-n-butylphenyl ) -3-phenylphenylphosphonite, bis (2,6-di-tert-butylphenyl) -4-phenylphenylphosphonite and bis (2,6-di-tert-butylphenyl) -3-phenylphenylphosphonite. Among them, bis (di-tert-butylphenyl) phenylphenylphosphonite is preferable, and bis (2,4-di-tert-butylphenyl) phenylphenylphosphonite is particularly preferable. The bis (2,4-di-tert-butylphenyl) -phenylphenylphosphonite is preferably used in a combination of two or more compounds. In particular, one or both of the constituents bis (2,4-di-tert-butylphenyl) -4-phenylphenylphosphonite and bis (2,4-di-tert-butylphenyl) -3-phenylphenylphosphonite can be used, but a mixture of the two components is preferred. The weight ratio of the two components in the mixture is preferably 5: 1 to 4 and in particular 5: 2 to 3.

To Examples of the phosphate compound as a heat stabilizer belong Tributyl phosphate, trimethyl phosphate, tricrehyl phosphate, triphenyl phosphate, Trichlorophenyl phosphate, triethyl phosphate, diphenylcresyl phosphate, Diphenylmonoorthoxenylphosphate, tributoxyethylphosphate, dibutylphosphate, Dioctyl phosphate and diisopropyl phosphate. Including trimethyl phosphate prefers.

wobei R¹³ und R¹⁴ jeweils unabhängig voneinander eine Alkylgruppe, Cycloalkylgruppe, Arylgruppe oder Aralkylgruppe mit 1 bis 12 Kohlenstoffatomen bedeuten,

worin R¹⁵, R¹⁶, R¹⁷, R¹⁸, R²¹, R²² und R²³ jeweils unabhängig voneinander ein Wasserstoffatom, eine Alkylgruppe, Cycloalkylgruppe, Arylgruppe oder Aralkylgruppe mit 1 bis 12 Kohlenstoffatomen bedeuten, R¹⁹ ein Wasserstoffatom oder eine Alkylgruppe mit 1 bis 4 Kohlenstoffatomen bedeutet und R²⁰ ein Wasserstoffatom oder eine Methylgruppe bedeutet.The phosphorus-containing stabilizer is in particular a compound of the following general formulas (13) or (14)

wherein R ¹³ and R ¹⁴ each independently represent an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms,

wherein R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ , R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, R ^{19 represents} a hydrogen atom or an alkyl group 1 to 4 carbon atoms and R ^{20 represents} a hydrogen atom or a methyl group.

In the formula (13), R ¹³ and R ^{14 are} preferably an alkyl group having 1 to 12 carbon atoms, and more preferably an alkyl group having 1 to 8 carbon atoms. Specific examples of the compound of formula (13) include tris (dimethylphenyl) phosphite, tris (diethylphenyl) phosphite, tris (diisopropylphenyl) phosphite, tris (di-n-butylphenyl) phosphite, tris (2,4-di-tert-butylphenyl) phosphite and tris (2,6-di-tert-butylphenyl) phosphite. Of these, tris (2,4-di-tert-butylphenyl) phosphite is particularly preferred.

The Phosphorus compound of formula (14) can be after a per se produce known methods. For example, a bisphenol compound the following general formula (15) and phosphorus trichloride reacted together to give a chlorinated phosphoric acid, the subsequently with a phenol represented by the following general formula (16) becomes.

In the above formula (15), R ¹⁵ , R ¹⁶ , R ¹⁷ and R ¹⁸ each independently represent a hydrogen atom, an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms, R ^{19 means} a hydrogen atom or an alkyl group having 1 to 4 Carbon atoms and R ^{20 is} a hydrogen atom or a methyl group.

In the above formula (16), R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group, cycloalkyl group, aryl group or aralkyl group having 1 to 12 carbon atoms.

below are preferred examples of the compound represented by the general formula (15) listed: 2,2'-methylene bisphenol, 2,2'-methylenebis (4-methylphenol), 2,2'-methylenebis (6-methylphenol), 2,2'-methylenebis (4,6-dimethylphenol), 2,2'-ethylidenebisphenol, 2,2'-ethylidenebis (4-methylphenol), 2,2'-isopropylidene, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-dihydroxy-3,3'-di- (α-methylcyclohexyl) -5,5'-dimethylphenylmethane, 2,2'-methylenebis (6-α-methylbenzyl-p-cresol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol) and 2,2'-butylidenebis (4-methyl-6-tert-butylphenol).

Among the above compounds of the general formula (15), 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol) , 2,2'-methylenebis (4,6-di-tert-butylphenol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol) and 2,2'-butylidenebis (4 -methyl-6-tert-butylphenol) especially prefers.

To preferred examples of the compound represented by the general formula (16) include phenol, 2-methylphenol, 3-methylphenol, 4-methylphenol, 2,4-dimethylphenol, 2,6-dimethylphenol, 2-tert-butyl-4-methylphenol, 2,4-di-tert-butylphenol, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-methylphenol, 2,4-dimethyl-6-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,4,6-tri-tert-butylphenol and 2,6-di-tert-butyl-4-s-butylphenol. Among the above compounds of general formula (16) compounds with two or more alkyl substituents become particular prefers.

At the Antioxidant mixed with the resin composition of the present invention can be, is a phenol-based antioxidant. The phenol-based antioxidant can suppress discoloration when the resin composition of a heat is exposed, and it causes some improvement the flame-retardant texture. There may be different antioxidants be used on a phenol basis.

To preferred examples of the phenol-based antioxidant includes vitamin E, n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) -propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate, 2,6-di-tert-butyl-4- (N, N-dimethylaminomethyl) -phenol, Diethyl 3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,2'-methylenebis (4-methyl-6-tert-butylphenol), 2,2'-methylenebis (4-ethyl-6-tert-butylphenol), 4,4'-methylenebis (2,6-di-tert-butylphenol), 2,2'-methylenebis (4-methyl-6-cyclohexylphenol), 2,2'-Dimethylenbis- (6-α-methylbenzyl-p-cresol), 2,2'-ethylidenebis (4,6-di-tert-butylphenol), 2,2'-butylidenebis (4-methyl-6-tert-butylphenol), 4,4'-butylidenebis (3-methyl-6-tert-butylphenol), Triethylene glycol N-bis-3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionate, 1,6-hexanediol bis [3- (3,5-di-tert-butyl-4-) hydroxyphenyl) propionate, bis [2-tert-butyl-4-methyl-6- (3-tert-butyl-5-methyl-2-hydroxybenzyl) phenyl] terephthalate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5 , 5] undecane, 4,4'-thiobis (6-tert-butyl-m-cresol), 4,4'-thiobis (3-methyl-6-tert-butylphenol), 2,2'-thiobis (4-methyl-6-tert-butylphenol), bis (3,5-di-tert-butyl-4-hydroxybenzyl) sulfide, 4,4'-dithiobis (2,6-di-tert-butylphenol), 4,4'-trithiobis (2,6-di-tert-butylphenol), 2,4-bis (n-octylthio) -6- (4-hydroxy-3 ', 5'-di-tert. butylanilino) -1,3,5-triazine, N, N'-hexamethylene bis (3,5-di-tert-butyl-4-hydroxyhydrocinnamide), N, N'-bis [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyl] hydrazine, 1,1,3-tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) -butane, 1,3,5-trimethyl-2,4,6-tris (3,5-di- tert-butyl-4-hydroxybenzyl) benzene, tris (3,5-di-tert-butyl-4-hydroxyphenyl) isocyanurate, Tris (3,5-di-tert-butyl-4-hydroxybenzyl) isocyanurate, 1,3,5-tris (4-tert-butyl-3-hydroxy-2,6-dimethylbenzyl) isocyanurate, 1,3,5-tris-2- [3- (3,5-di-tert-butyl-4-hydroxyphenyl) propionyloxy] -ethylisocyanurat and tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) -propionate] -methane.

among them are n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate, 2-tert-butyl-6- (3'-tert-butyl-5'-methyl-2'-hydroxybenzyl) -4-methylphenylacrylate, 3,9-bis {2- [3- (3-tert-butyl-4-hydroxy-5-methylphenyl) propionyloxy] -1,1-dimethylethyl} -2,4,8,10-tetraoxaspiro [5 , 5] undecane and tetrakis- [methylene-3- (3 ', 5'-di-tert-butyl-4-hydroxyphenyl) -propionate] -methane particularly preferred. Particularly preferred is n-octadecyl-β- (4'-hydroxy-3 ', 5'-di-tert-butylphenyl) propionate.

When Antioxidant may be a sulfur-containing antioxidant be used. This agent is particularly preferred when the Resin composition for a rotary molding or press molding is used. To explanatory Examples of the sulfur-containing antioxidant include dilauryl-3,3'-thiodipropionic acid ester, ditridecyl-3,3'-thiodipropionic acid ester, Dimyristyl 3,3'-thiodipropionic acid ester, Distearyl 3,3'-thiodipropionic acid ester, Lauryl-3,3'-thiodipropionic acid ester, Pentaerythritol tetra- (β-laurylthiopropionate) ester, Bis [2-methyl-4- (3-laurylthiopropionyloxy) -5-tert-butylphenyl] sulfide, Octadecyl disulfide, mercaptobenzimidazole, 2-mercapto-6-methylbenzimidazole and 1,1'-thiobis- (2-naphthol). Below is Pentaerythritol tetra (β-laurylthiopropionate) ester is particularly preferred.

The above phosphorus-containing stabilizers, antioxidants Phenol-based and sulfur-containing antioxidants can be used alone or used in a combination of two or more components become. A phosphorus-containing stabilizer is particularly preferred. Particularly preferred is a phosphorus-containing stabilizer which a compound of the above general formula (13).

What the amount of stabilizer in the composition, the amount of one phosphorus-containing stabilizer, an antioxidant Phenolbasis or a sulfur-containing antioxidant is concerned, so is these preferably 0.0001 to 1 part by weight, in particular 0.0005 to 0.5 parts by weight and most preferably 0.001 to 0.2 parts by weight, based to 100 parts by weight of the total amount of the resin components (A).

ever If necessary, a release agent may be used with the resin composition of the present invention be mixed. Since the component B according to the invention a flame retardant Texture, leaves itself an excellent flame-retardant texture even then Achieve when a release agent that tends to be a bad one To exert influence on the flame retardant condition, mixed becomes. It can Any known release agents are used, for example Esters of saturated aliphatic acids, Esters of unsaturated aliphatic acids, Polyolefin-based waxes (polyethylene wax, 1-alkene polymers and Products obtained by modifying these products with a functional group-containing compound (typically by Acid modification) have been obtained), silicone compounds (from the component of the invention B, such as linear and cyclic polydimethylsiloxane oils, polymethylphenylsilicone oils and products, by substituting these products with a functional one Group-containing compound, for. As an acid compound are), fluorine compounds (such as fluorine oils, typically polyfluoroalkyl ethers) and paraffin waxes and beeswax. These include esters of saturated aliphatic acids, linear and cyclic polydimethylsiloxane oils, polymethylphenylsilicone oils and fluoro oils are preferred. The amount of release agent is preferably 0.01 to 0.3 parts by weight, based on 100 parts by weight the total amount of resin components (A).

At the Release agent is preferably an ester of a saturated aliphatic acid, e.g. For example, a monoglyceride such as monoglyceride stearate, a polyglycerol ester an aliphatic acid, z. B. Decaglycerindecastearat or Decaglycerintetrastearat, a Esters of a lower fatty acid, such as stearyl stearate, a higher fatty acid ester such as behenyl sebacate, or an erythritol ester such as pentaerythritol tetrastearate.

There the resin composition of the invention often in housings of office automation equipment is used contains they preferably have a UV light absorber. When UV light absorber can it is a benzophenone-based UV light absorber, typically 2,4-dihydroxybenzophenone, 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-n-octoxybenzophenone, 4-, 2-hydroxy-4-n-dodecyloxybenzophenone, 2-hydroxy-4-benzyloxybenzophenone, 2,2'-dihydroxy-4-methoxybenzophenone, 2-hydroxy-4-methoxy-2'-carboxybenzophenone, 2-hydroxy-4-methoxy-5-sulfoxybenzophenone, 2,2'-dihydroxy-4,4'-dimethoxybenzophenone, 2,2 ', 4,4'-tetrahydroxybenzophenone, 2,2'-dihydroxy-4,4'- dimethoxy-5-natriumsulfoxybenzophenon and bis (5-benzoyl-4-hydroxy-2-methoxyphenyl) methane.

At the UV light absorber may be a benzotriazole based UV light absorber typically, 2- (2'-hydroxy-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-5'-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-5'- tert-octylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-amylphenyl) benzotriazoles, 2- (2'-hydroxy-3'-dodecyl-5'-methylphenyl) benzotriazole, 2- (2'-hydroxy-3 ', 5'-bis (α, α'-dimethylbenzyl) phenylbenzotriazole, 2- [2'-hydroxy-3 '- (3' ', 4' ', 5' ', 6' '- tetraphthalimidmethyl) -5'-methylphenyl] benzotriazole, 2- (2'-hydroxy-3'-tert-butyl-5'-methylphenyl) -5-chlorobenzotriazole, 2- (2'-hydroxy-3 ', 5'-di-tert-butylphenyl) -5- chlorobenzotriazole 2,2'-methylenebis [4- (1,1,3,3-tetramethylbutyl) -6- (2H-benzotriazol-2-yl) phenol] and a condensate of methyl 3- [3-tert-butyl-5- (2H-benzotriazol-2-yl) -4-hydroxyphenylpropionate and polyethylene glycol.

At the UV light absorber can also be based on a compound of hydroxyphenyltriazine, such as 2- (4,6-diphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol and 2- (4,6-bis (2,4-dimethylphenyl-1,3,5-triazin-2-yl) -5-hexyloxyphenol.

A light stabilizer may also be mixed with the resin composition of the present invention. The light stabilizer can be a light stabilizer based on a sterically hindered amine, for example bis (2,2,6,6-tetramethyl-4-piperidyl) sebacate, bis (1,2,2,6, 6-pentamethyl-4-piperidyl) sebacate, bis (1,2,2,6,6-pentamethyl-4-piperidyl) -2- (3,5-di-tert-butyl-4-hydroxybenzyl) - 2-n-butylmalonate, a condensate of 1,2,3,4-butanecarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and tridecyl alcohol, a condensate of 1,2,3,4-butanedicarboxylic acid, 1, 2,2,6,6-pentamethyl-4-piperidinol and tridecyl alcohol, tetrakis (2,2,6,6-tetramethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, tetrakis (1,2 , 2,6,6-pentamethyl-4-piperidyl) -1,2,3,4-butanetetracarboxylate, poly - {[6- (1,1,3,3-tetramethylbutyl) amino-1,3,5- triazine-2,4-diyl] - [(2,2,6,6-tetramethyl-piperidyl) -imino] -hexamethylene - [(2,2,6,6-tetramethyl-piperidyl) -imino], poly (6- morpholino-s-triazine-2,4-diyl] - [(2,2,6,6-tetramethylpiperidyl) imino] hexamethylene - [(2,2,6,6-tetramethylpiperidyl) -imino]}, a condensate of 1,2,3,4-Bu tantetracarboxylic acid, 2,2,6,6-tetramethyl-4-piperidinol and β, β, β ', β'-tetramethyl-3,9- (2,4,8,10-tetraoxa-spiro [5,5] undecane) - diethanol, a condensate of N, N'-bis (3-aminopropyl) ethylenediamine and 2,4-bis [N-butyl-N- (1,2,2,6,6-pentamethyl-4-piperidyl) -amino] -chloro-1,3,5-triazine, a condensate of 1,2,3,4-butanetetracarboxylic acid, 1,2,2,6,6-pentamethyl-4-piperidinol and β, β, β ', β'-tetramethyl thyl-3,9- (2,4,8,10-tetraoxaspiro [5,5] undecane) -diethanol and polymethylpropyl-3-oxy- [4- (2,2,6,6-tetramethyl) -piperidinyl] - siloxane.

The Quantities of the above UV light absorber and light stabilizer amount in each case preferably 0.01 to 5 parts by weight and in particular 0.02 to 1 part by weight, based on 100 parts by weight of the total amount of Resin components (A).

One bluing can with the resin composition of the invention be mixed to a yellow hue, that of the UV light absorber or the like. to eliminate. Any bluing agents are acceptable, provided for a polycarbonate resin can be used. An anthraquinone based dye let yourself easily obtained and is preferred. Examples of the blueing agent belong Solvent Violet 13 [CA. No. (Color Index No.) 60725; Macrolex Violet B from Bayer AG, Diaresin Blue G from Mitsubishi Chemical Corporation, Sumiplast Violet B from Sumitomo Chemical Co., Ltd.], Solvent Violet 31 [CA. No. 68210; Diaresin Violet D from the company Mitsubishi Chemical Corporation], Solvent Violet 33 [CA. No. 60725; Diaresin Blue J from Mitsubishi Chemical Corporation], Solvent Blue 94 [CA. No. 61500; Diaresin Blue N from Mitsubishi Chemical Corporation], Solvent Violet 36 [CA. No. 68210; Macrolex Violet 3R from Bayer AG], Solvent Blue 97 [Macrolex Blue RR from Bayer AG] and Solvent Blue 45 [CA. No. 61110; Telasol Blue RLS from Sandoz Ltd.]. among them become Macrolex Blue RR, Macrolex Violet B and Telasol Blue RLS particularly preferred.

The Inventive resin composition has excellent properties to prevent dripping on. However, to further enhance these properties a common one Means are used to prevent dripping. In a transparent resin composition according to a preferred embodiment of the present invention the amount of the agent for preventing the drop formation suitably 0.1 part by weight or less, preferably 0.08 part by weight or less and in particular 0.05 parts by weight or less, based on 100 parts by weight the component A, the transparency of the composition is not to impair.

At the For example, means for preventing dripping are a fluorine-containing polymer capable of fibril formation. Polytetrafluoroethylene (hereinafter also abbreviated as PTFE) is particularly preferred.

PTFE with fibril-forming capacity has an extremely high Molecular weight and tends to form a fibrous texture by bonding to further PTFE due to an external action, e.g. B. one Shear force. The number average molecular weight of PTFE, the from a product with usual relative Density is obtained is preferably 1 000 000 to 10 000 000 and in particular 2 000 000 to 9,000,000. PTFE may be as a solid or as an aqueous dispersion be used. PTFE with fibrillating power can be used with another Resin to be mixed in a resin improve and excellent texture in terms of flame retardant To achieve effect and transparency. To commercially available Products for PTFE mixtures include Metablen A3000 from Mitsubishi Rayon Co., Ltd. and BLENDEX B449 of the Fa. GE Specialty Chemicals.

to Preparation of the resin composition of the invention can Any method can be used. For example, the Components A and B and other optional components completely together using a premixing device, e.g. B. a V-shaped mixer, a Henschel mixer, a mechanochemical device or an extrusion type mixer, mixed, after which the resulting mixture through an extrusion granulator or a briquetting machine is granulated as needed. The The mixture obtained is melted by a melt kneader kneaded, typically with a vented twin screw extruder. Subsequently it is with a device, for. B. a pelletizer, pelletized.

Alternative methods include a method wherein components A and B and other optional components are each independently fed to a melt kneader, for example, a vented twin screw extruder, a method in which component A and some other components are premixed together, and then regardless of the rest of the components, and a method in which the component B is diluted with water or an organic solvent and fed to a melt-kneading apparatus or in which the diluted mixture is previously mixed with other components and fed to a melt extruder. When the components to be mixed together comprise a liquid component, a so-called liquid injection device or liquid addition may be employed tion are used to supply the liquid component of the Schmelzknetvorrichtung.

Moldings can be in general by injection molding of pellets of the resin composition of the present invention become. In injection molding not just a common one Cold runner, but also a hot runner be used, which makes it possible in the production of the moldings on channels to renounce. In injection molding it can be a usual one Shaping, a gas-assisted Spritzgießformgebung, an injection compression molding, ultra high speed injection molding, transfer molding, a two-color molding, a sandwich molding, a shaping under coating in the mold, insert molding, foam molding (including using a supercritical fluid), a shaping with rapid heating / cooling, a Shaping under heat insulation, a shaping by remelting the mold or a combination act on it.

The Inventive resin composition can be formed into various extrusion moldings, for. B. to plates, foils or profiles. For molding a plate or a Films can also be used in a blow molding or casting process. The resin composition can be made by a special stretching process to a heat shrink tube be formed. moldings can be made from the resin composition of the invention Rotational molding obtained without melt kneading.

Out Moldings formed of the resin composition may be surface-treated be subjected. The surface treatment may be a decorative coating, a hard coating, a water-repellent / oil-repellent coating, a hydrophilic coating, a UV absorbing coating, a IR absorption coating, a coating for absorbing electromagnetic waves, a heat generation coating, an antistatic coating, a coating of controlled low conductivity, a conductive Coating or metallization (plating, chemical vapor deposition (CVD), physical vapor deposition (PVD), thermal spraying) act. A transparent plate / foil covered with a transparent conductive layer is coated is preferred.

Effect of invention

The Flame retardant according to the invention aromatic polycarbonate resin composition comprises a silicone compound (component B) as flame retardant Means, it has excellent properties for preventing the Drop formation on and shows the dyeing excellent dyeing properties and lets by laser marking with clear characters or markings print. These characteristic features could be with conventional flame retardant aromatic polycarbonate resin compositions to reach. The above resin composition exhibits melting at high temperatures, eg. As in injection molding, a high thermal stability. Therefore It is particularly suitable for different commercial applications, eg. B. for office automation devices and electrical and electronic devices.

According to one preferred aspect of the present invention is a flame retardant aromatic polycarbonate resin composition having excellent Transparency provided. As the flame retardant resin composition a special silicone compound (component B) as a flame retardant contains it has a texture to prevent dripping on, is transparent and shows resistance to heat under humid conditions. The flame retardant resin composition with the above characteristic properties is under the polycarbonate resin compositions of the prior art not to find. The resin composition of excellent transparency let yourself form a transparent sheet / foil and is suitable for applications, like covers of lights, protective covers for displays transmission type, optical fiber parts, covers and substrates of solar cells, lenses, lens arrangements, coupling devices, Touch panels, resin windows, parts of playground equipment (like front cover of "Pachinko", circuit covers and the like), prisms and mirrors. Thus, the composition of the invention extremely valuable in various commercial fields, eg. In office automation equipment, electrical and electronic devices, Motor vehicles, in agriculture, fisheries and in construction.

Examples

The The following examples serve to further illustrate the present invention. but are in no way to be considered restrictive. The following Facts were evaluated.

(1) Characteristic Properties of materials

(1-I) Properties for Prevention of dripping

One UL standard 94 test was performed on a 1.6 mm thick test specimen according to UL standards had been made. At the same time the period from primary inflammation and secondary inflammation became measured for drop formation. As a value for the prevention of dripping became the shortest Time span (seconds) taken.

(1-II) Dyeing properties

O:

zufriedenstellend; kein Ablösungen, glänzend, hochwertige Farbe und gleichmäßiges Erscheinungsbild

X:

unbefriedigend; Ablösungen, kein Glanz, mangelhafte Farbe oder ungleichmäßiges Erscheinungsbild.

A plate-like shaped article in the form of a square having an edge length of 150 mm and a thickness of 2.0 mm was divided into 9 pieces. The L values of the 9 pieces were measured by the TCM-1800 color computer of Tokyo Denshoku Co., Ltd. The value (ΔL) obtained by subtracting the smallest L value from the largest L value of the 9 pieces and the appearance after visual inspection of the molded article were evaluated on the basis of the following criteria.

O:

satisfactory; no peeling, shiny, high-quality color and uniform appearance

X:

unsatisfactory; Detachment, no gloss, poor color or uneven appearance.

(1-III) Laser marking properties

O:

zufriedenstellend, klar erkennbares Schriftzeichen

X:

unbefriedigend, verschwommenes Schriftzeichen.

A 2.0 mm thick test specimen, which had been prepared according to UL standards, was marked with the SL475E laser marker from NEC Corporation at a scanning speed of 100 mm / sec and a "bite" size of 30 μm. The minimum current value at which marking was possible and the clarity of a mark as determined by visual inspection were evaluated on the basis of the following criteria.

O:

satisfactory, clearly recognizable character

X:

unsatisfactory, blurry character.

(1-IV) Transparency

The Transparency of a square plate-like shaped body of 150 mm edge length with a thickness of 2.0 mm was calculated on the basis of the haze value, in accordance with JIS K7105 and the visually tested color of the molded article.

(1-V) resistance against heat under humid conditions

Of the for the Measurement (1-IV) was used square, plate-like shaped body 500 hours at a temperature of 65 ° C and a humidity of Leave 85%. Then, the haze value of the molded article was determined according to JIS K7105 measured. The difference (ΔH) between the obtained turbidity value and the initial one haze value was determined. The color of the molding before the heat treatment under humid conditions was visually evaluated (the term "cloudy" means that the Light transmission visually confirmed can be. The term "opaque" means that the Light transmission can not be visually confirmed, with in In this case, the turbidity was not measured).

Examples 1 to 25 and Comparative Examples 1 to 18

The listed in Tables 1 to 9 Resin compositions were prepared according to the following Process produced. The symbols used in the tables are explained below.

The Quantities of the components indicated in Tables 1 to 9 were balanced. 0.01 part by weight of a phosphite-based antioxidant (IRGAFOS168 from Nippon Ciba Geigy Co., Ltd.), 0.01 part by weight a phenol-based antioxidant (IRGANOX1076 Fa. Nippon Ciba Geigy Co., Ltd.), 0.3 parts by weight of a UV light absorber (Chemisorb 79 from CHEMIPRO KASEI KAISHA, LTD.) And 0.3 parts by weight a release agent (Rikemal SL900 from Riken Vitamin Co., Ltd.) were balanced and even in one Mixed tumble mixer. The resulting mixture was used for the preparation the resin compositions fed to an extruder.

The extruder was a vented twin screw extruder with a diameter 30 mm (KTX-30 from Kobe Steel, Ltd.). As for the screw configuration, a first kneading zone (consisting of 2 feed kneading discs, 1 feed rotor, 1 return rotor and 1 return kneading disc) was formed in front of the venting point and a second kneading zone (consisting of 1 feed rotor and 1 return rotor) after the venting point. A strand was extruded at a cylinder temperature and a mold temperature of 280 ° C and at a vent suction degree of 3,000 Pa, cooled in a water bath and cut for pelletization with a pelletizer. The obtained pellets were dried at 110 ° C for 5 hours in a hot-air circulating-drying machine. A test sample was molded from the pellets with an injection molding machine (T-150D made by FANUC Ltd.) at a cylinder temperature of 290 ° C and a mold temperature of 70 ° C.

below are the symbols represented by symbols in Tables 1 to 9 Starting materials explained (the symbols are in the rest Tables for the same starting materials).

Components (A)

(Component A-1)

• PC-1: linear polycarbonate resin (aromatic polycarbonate resin, comprising bisphenol A and p-tert-butylphenol as endcapping agent, prepared by the phosgene method. This aromatic polycarbonate resin was prepared without using an amine-based catalyst, contained 10 mol% of terminal hydroxyl groups, based on the total amount the terminal groups, and 25 ppm of an antioxidant Phosphonite base (sand rod P-EPQ from Clariant K.K.). It pointed a viscosity agent molecular weight of 22,500).
• PC-2: Branched aromatic polycarbonate resin (Toughlon IB2500 Fa. Idemitsu Petrochemical Co., Ltd.).
• PC-3: Polycarbonate resin having a viscosity average molecular weight of 15,500 obtained by reaction of bisphenol A, p-tert-butylphenol as endcapping agent and phosgene in the presence of methylene chloride, a 10% aqueous solution of sodium hydroxide and triethylamine according to the usual method among such Conditions had been established that the mole ratio of p-tert-butylphenol to bisphenol A was 0.058.
• PC-4: Polycarbonate resin having a viscosity average molecular weight of 121,000, prepared by reaction of bisphenol A, p-tert-butylphenol as endcapping agent and phosgene in the presence of methylene chloride, a 10% aqueous solution of sodium hydroxide and triethylamine according to the commonly used Procedure for such conditions that the molar ratio of p-tert-butylphenol to bisphenol A was 0.0004.

(Component A-2).

• SECTION:

  Styrene-butadiene-acrylonitrile copolymer (Santac UT-61 from Nippon A & L Inc.).

  AS:

  Styrene-acrylonitrile copolymer (Stylac-AS 767 R27 from Asahi Kasei Corporation).

  MBS:

  Methyl methacrylate-butadiene-styrene copolymer (Kan-Ace B-56 from Kaneka Corporation).

(Component A-3)

• PET:

  polyethylene terephthalate (TR-8580 from Teijin Limited with an intrinsic viscosity of 0.8).

  PBT:

  polybutylene terephthalate (TRB-H from Teijin Limited with an intrinsic viscosity of 1.07).

Component B

Production Example 1

15.9 g of hexamethyldisiloxane, 147.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 14.5 g of octamethylcyclotetrasiloxane and 395.1 g of diphenyldimethoxysilane were added to a 1 liter flask equipped with a stirrer, condenser and thermometer , fed. Further, 25.0 g of concentrated sulfuric acid was added with stirring. After lowering the internal temperature of the flask to 10 ° C, 29.7 g of water were added dropwise within 30 minutes with stirring in the flask. The internal temperature of the flask was kept at 20 ° C or below. After the addition, the agitation was continued at an internal temperature of 10 to 20 ° C for 5 hours to carry out aging. 8.5 g of water and 300 g of toluene were added. After stirring for 30 minutes, the water phase deposited on standing was removed. Then, the residue was washed with a 5% aqueous solution of sodium sulfate 4 times. It was confirmed that the toluene phase was neutral. This toluene solution was heated under reduced pressure to an inner temperature of 120 ° C to remove toluene and low-boiling components. The undissolved product was removed by filtration. The silicone compound B-1 was obtained.

Synthesis Example 2

538.2 g of water and 120 g of toluene were added to a 1 liter flask, the one with a stirrer, a cooler and a thermometer was, fed and cooled to an internal temperature of 5 ° C. A mixture of 22.6 g Trimethylchlorosilane, 119.6 g of methyldichlorosilane and 34.2 g of diphenyldichlorosilane was placed in a dropping funnel and within 2 hours with stirring dropped into the flask. This was still a cooling on an internal temperature of 20 ° C or below. After the addition, the stirring was done for aging at an internal temperature of 20 ° C continued for 4 hours. The on standing, separated hydrochloric acid-water phase was removed. After addition of a 10% aqueous sodium and 5 minutes stir the water phase separated off on standing was removed. thereupon became the backlog Washed 3 times with ion exchange water. It was confirmed that the Toluene phase had become neutral. This toluene solution was concentrated under reduced pressure Pressure heated to an internal temperature of 120 ° C, to toluene and low to remove boiling components. The undissolved product was filtered off. The silicone compound B-2 was obtained.

Synthesis Example 3

The Silicone compound B-3 was prepared in the same manner as in Synthesis Example 2, with the exception that 452.8 g of water and 120 g of toluene supplied to the piston and a mixture of 21.7 g of trimethylchlorosilane, 23.0 g of methyldichlorosilane, Added dropwise 80.0 g of dimethyldichlorosilane and 32.9 g of diphenyldichlorosilane has been.

Synthesis Example 4

The Silicone compound B-4 was prepared in the same manner as in Synthesis Example 1, with the exception that 100.7 g of 1,1,3,3-tetramethyldisiloxane, 60.1 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 129.8 g of octamethylcyclotetrasiloxane, 143.8 g of octaphenylcyclotetrasiloxane and 99.1 g of phenyltrimethoxysilane supplied to the piston 25.0 g of concentrated sulfuric acid were added and 13.8 g of water were added dropwise.

Synthesis Example 5

The Silicone compound B-5 was prepared in the same manner as in Synthesis Example 2, with the exception that 454.9 g of water and 140 g of toluene supplied to the piston and a mixture of 47.3 g dimethylchlorosilane, 34.5 g methyldichlorosilane, 1.4 g of dimethyldichlorosilane, 11.3 g of diphenyldichlorosilane and 63.5 g g phenyltrichlorosilane was added dropwise.

Synthetic Example 6

The Silicone compound B-6 was prepared in the same manner as in Synthesis Example 1, with the exception that 26.0 g of hexamethyldisiloxane, 57.7 g 1,3,5,7-tetramethylcyclotetrasiloxane, 26.1 g of octamethylcyclotetrasiloxane and 456.3 g of diphenyldimethoxysilane were fed to the flask, 25.0 g concentrated sulfuric acid were added and 34.3 g of water was added dropwise.

Synthesis Example 7

The Silicone Compound B-7 was prepared in the same manner as in Synthesis Example 1, with the exception that 81.2 g of hexamethyldisiloxane, 30.1 g 1,3,5,7-tetramethylcyclotetrasiloxane, 129.8 g octamethylcyclotetrasiloxane and 317.7 g of diphenyldimethoxysilane were fed to the flask, 25.0 g concentrated sulfuric acid were added and 23.9 g of water were added dropwise.

Synthesis Example 8

Silicone compound B-8 was obtained in the same manner as in Synthesis Example 2 except that 511.3 g of water and 120 g of toluene were supplied to the flask and a mixture of 14.8 g of dimethylchlorosilane, 17.9 g of methyldichlorosilane, 112.7 g of dimethyldichlorosilane and 19.7 g of diphenyldichlorosilane added were dripping.

Synthetic Example 9

• B-1: Siliconverbindung mit einem Si-H-Gehalt von 0,49 mol/100 g, einem Gehalt an aromatischen Gruppen von 50 Gew.-% und einem Brechungsindex von 1,5313, hergestellt in Synthesebeispiel 1.
• B-2: Siliconverbindung mit einem Si-H-Gehalt von 1,00 mol/100 g, einem Gehalt an aromatischen Gruppen von 20 Gew.-% und einem Brechungsindex von 1,4480, hergestellt in Synthesebeispiel 2.
• B-3: Siliconverbindung mit einem Si-H-Gehalt von 0,20 mol/100 g, einem Gehalt an aromatischen Gruppen von 20 Gew.-% und einem Brechungsindex von 1,4502, hergestellt in Synthesebeispiel 3.
• B-4: Siliconverbindung mit einem Si-H-Gehalt von 0,50 mol/100 g, einem Gehalt an aromatischen Gruppen von 30 Gew.-% und einem Brechungsindex von 1,4750, hergestellt in Synthesebeispiel 4.
• B-5: Siliconverbindung mit einem Si-H-Gehalt von 0,80 mol/100 g, einem Gehalt an aromatischen Gruppen von 30 Gew.-% und einem Brechungsindex von 1,4770, hergestellt in Synthesebeispiel 5.
• B-6: Siliconverbindung mit einem Si-H-Gehalt von 0,20 mol/100 g, einem Gehalt an aromatischen Gruppen von 60 Gew.-% und einem Brechungsindex von 1,5583, hergestellt in Synthesebeispiel 6.
• B-7: Siliconverbindung mit einem Si-H-Gehalt von 0,10 mol/100 g, einem Gehalt an aromatischen Gruppen von 40 Gew.-% und einem Brechungsindex von 1,4970, hergestellt in Synthesebeispiel 7.
• B-8: Siliconverbindung mit einem Si-H-Gehalt von 0,31 mol/100 g, einem Gehalt an aromatischen Gruppen von 12 Gew.-% und einem Brechungsindex von 1,4188, hergestellt in Synthesebeispiel 8.
• B-9: Siliconverbindung mit einem Si-H-Gehalt von 0,22 mol/100 g, einem Gehalt an aromatischen Gruppen von 67 Gew.-% und einem Brechungsindex von 1,5839, hergestellt in Synthesebeispiel 9.

Silicone compound B-9 was obtained in the same manner as in Synthesis Example 1 except that 6.7 g of 1,1,3,3-tetramethyldisiloxane, 60.1 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 533 , 9 g of diphenyldimethoxysilane were added to the flask, 40.0 g of concentrated sulfuric acid were added and 40.2 g of water were added dropwise.

• B-1: Silicone compound having an Si-H content of 0.49 mol / 100 g, an aromatic group content of 50% by weight and a refractive index of 1.5313 prepared in Synthesis Example 1.
• B-2: Silicone compound having an Si-H content of 1.00 mol / 100 g, an aromatic group content of 20 wt% and a refractive index of 1.4480, prepared in Synthesis Example 2.
• B-3: Silicone compound having an Si-H content of 0.20 mol / 100 g, an aromatic group content of 20 wt% and a refractive index of 1.4502, prepared in Synthesis Example 3.
• B-4: Silicone compound having an Si-H content of 0.50 mol / 100 g, an aromatic group content of 30% by weight and a refractive index of 1.4750, prepared in Synthesis Example 4.
• B-5: Silicone compound having an Si-H content of 0.80 mol / 100 g, an aromatic group content of 30% by weight and a refractive index of 1.4770, prepared in Synthesis Example 5.
• B-6: Silicone compound having a Si-H content of 0.20 mol / 100 g, an aromatic group content of 60% by weight and a refractive index of 1.5583, prepared in Synthesis Example 6.
• B-7: Silicone compound having an Si-H content of 0.10 mol / 100 g, an aromatic group content of 40% by weight and a refractive index of 1.4970, prepared in Synthesis Example 7.
• B-8: Silicone compound having a Si-H content of 0.31 mol / 100 g, an aromatic group content of 12 wt% and a refractive index of 1.4188, produced in Synthesis Example 8.
• B-9: Silicone compound having a Si-H content of 0.22 mol / 100 g, an aromatic group content of 67% by weight and a refractive index of 1.5839, prepared in Synthetic Example 9.

Other components B

Synthetic Example 10

The Silicone compound B-10 was prepared in the same manner as in Synthesis Example 1, with the exception that 97.4 g of hexamethyldisiloxane, 180.4 g 1,3,5,7-tetramethylcyclotetrasiloxane and 222.5 g of octamethylcyclotetrasiloxane supplied to the piston 25.0 g of concentrated sulfuric acid were added and no Water was added dropwise.

Synthetic Example 11

The Silicone compound B-11 was prepared in the same manner as in Synthesis Example 1, with the exception that 39.9 g of hexamethyldisiloxane, 14.8 g 1,3,5,7-tetramethylcyclotetrasiloxane, 200.6 g of octamethylcyclotetrasiloxane and 300.6 g of diphenyldimethoxysilane were fed to the flask, 25.0 g concentrated sulfuric acid were added and 22.6 g of water were added dropwise.

Synthetic Example 12

• B-10 (Vergleich): Siliconverbindung mit einem Si-H-Gehalt von 0,60 mol/100 g, einem Gehalt an aromatischen Gruppen von 0 Gew.-% und einem Brechungsindex von 1,3956, hergestellt in Synthesebeispiel 10.
• B-11 (Vergleich): Siliconverbindung mit einem Si-H-Gehalt von 0,05 mol/100 g, einem Gehalt an aromatischen Gruppen von 38 Gew.-% und einem Brechungsindex von 1,4915, hergestellt in Synthesebeispiel 11.
• B-12 (Vergleich): Siliconverbindung mit einem Si-H-Gehalt von 1,31 mol/100 g, einem Gehalt an aromatischen Gruppen von 16 Gew.-% und einem Brechungsindex von 1,4419, hergestellt in Synthesebeispiel 12.

Silicone compound B-12 was obtained in the same manner as in Synthesis Example 2 except that 560.6 g of water and 140 g of toluene were supplied to the flask and a mixture of 18.9 g of dimethylchlorosilane, 126.5 g of methyldichlorosilane and 25.3 g of diphenyldichlorosilane were added dropwise.

• B-10 (comparative): Silicone compound having a Si-H content of 0.60 mol / 100 g, an aromatic group content of 0 wt% and a refractive index of 1.3956, prepared in Synthetic Example 10.
• B-11 (comparative): Silicone compound having an Si-H content of 0.05 mol / 100 g, an aromatic group content of 38% by weight and a refractive index of 1.4915, prepared in Synthetic Example 11.
• B-12 (comparative): Silicone compound having a Si-H content of 1.31 mol / 100 g, an aromatic group content of 16 wt% and a refractive index of 1.4419, prepared in Synthesis Example 12.

empirical formulas the individual silicone compounds

• B-1: M ₂ D ^H ₂₅ D ₂ D ^φ2 _16.5
• B-2: M ₂ D ^H ₁₀ D ^φ2 _1.3
• B-3: M ₂ D ^H ₂ D _6.2 D ^φ2 _1.3
• B-4: M ^H ₃ D ^H ₂ D _3.5 D ^φ2 _1.45 T ^φ ₁
• B-5: M ^H ₅ D ^H ₃ D _0,107 D ^φ2 _0,445 T ^φ ₃
• B-6: M ₂ D ^H ₆ D _2.2 D ^φ2 _11.67
• B-7: M ₂ D ^H ₁ D _3.5 D ^φ2 _2.6
• B-8: M ^H ₂ D ^H ₂ D _11.2 D ^φ2 ₁
• B-9: M ^H ₂ D ^H ₂₀ D ^φ2 _43.7
• B-10: M ₂ D ^H ₅ D ₅ (comparative)
• B-11: M ₂ D ^H ₁ D ₁₁ D ^φ2 ₅ (Comparative)
• B-12: M ^H ₂ D ^H ₁₁ D ^φ2 ₁ (comparison)

M:

(CH₃)₃SiO_1/2

M^H:

H(CH₃)₂SiO_1/2

D:

(CH₃)₂SiO

D^H:

H(CH₃)SiO

D^ϕ2:

(C₆H₅)₂SiO

T^ϕ:

(C₆H₅)SiO_3/2

The symbols in the above formulas each represent the following siloxane units. The coefficient of each symbol means the degree of polymerization of a siloxane unit in a molecule.

M:

(CH ₃ ) ₃ SiO _1/2

M ^H :

H (CH ₃ ) ₂ SiO _1/2

D:

(CH ₃ ) ₂ SiO

D ^H :

H (CH ₃ ) SiO

D ^φ2 :

(C ₆ H ₅ ) ₂ SiO

T ^φ :

(C ₆ H ₅ ) SiO _3/2

Component C

• C-1: 2,3-dimethyl-2,3-diphenylbutane (so-called dicumyl, Nofmer BC from the company NOF Corporation).
• C-2: Potassium salt of perfluorobutanesulfonic acid (Megafac F-114P of the company.
• Dainippon Ink & Chemicals, Incorporated).
• C-3: Potassium salt of diphenylsulfone sulfonic acid (KSS from UCB Japan Co., Ltd.)

Examples 26 to 38 and Comparative Examples 19 to 24

On the same manner as in Example 1, resin compositions and test samples formed by the methods described in Tables 10 to 14 specified quantities of the components and otherwise the same Quantities of the rest Components as in Example 1, not specified in the tables are balanced.

below are the starting materials used in Tables 10 to 14 specified.

Component B

Synthetic Example 13

Silicone compound B-13 was obtained in the same manner as in Synthesis Example 2 except that 301.9 g of water and 150 g of toluene were supplied to the flask and a mixture of 21.7 g of trimethylchlorosilane, 23.0 g of methyldichlorosilane, 12.9 g of dimethyldichlorosilane and 76.0 g of diphenyldichlorosilane was dropped.

Synthetic Example 14

The Silicone compound B-14 was prepared in the same manner as in Synthesis Example 1, with the exception that 16.2 g of hexamethyldisiloxane, 61.0 g 1,3,5,7-tetramethylcyclotetrasiloxane, 103.8 g of octamethylcyclotetrasiloxane and 391.0 g of diphenyldimethoxysilane were fed to the flask, 25.0 g concentrated sulfuric acid were added and 29.4 g of water were added dropwise.

Synthetic Example 15

The Silicone compound B-15 was prepared in the same manner as in Synthesis Example 1, with the exception that 167.9 g of 1,1,3,3-tetramethyldisiloxane, 92.7 g of octamethylcyclotetrasiloxane, 49.6 g of octaphenylcyclotetrasiloxane and 297.4 g of phenyltrimethoxysilane were fed to the flask, 25.5 g concentrated sulfuric acid were added and 41.3 g of water were added dropwise.

Synthetic Example 16

The Silicone compound B-16 was prepared in the same manner as in Synthesis Example 2, with the exception that 903.2 g of water and 120 g of toluene supplied to the piston and a mixture of 48.3 g of dimethylchlorosilane, 43.9 g of dimethyldichlorosilane, 21.5 g diphenyldichlorosilane and 36.0 g phenyltrichlorosilane was added dropwise has been.

Synthesis Example 17

The Silicone compound B-17 was prepared in the same manner as in Synthesis Example 1, with the exception that 70.5 g of 1,1,3,3-tetramethyldisiloxane, 126.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 243.8 g of diphenyldimethoxysilane supplied to the piston 25.0 g of concentrated sulfuric acid were added and 18.3 g of water were added dropwise.

Synthetic Example 18

The Silicone compound B-18 was prepared in the same manner as in Synthesis Example 1, with the exception that 87.3 g of 1,1,3,3-tetramethyldisiloxane, 211.1 g of hexamethyldisiloxane, 31.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane and 257.8 g phenyltrimethoxysilane were added to the flask, 25.0 g of concentrated sulfuric acid was added and 35.8 g of water were added dropwise.

Synthesis Example 19

The Silicone compound B-19 was prepared in the same manner as in Synthesis Example 2, with the exception that 447.2 g of water and 200 g of toluene supplied to the piston and a mixture of 22.2 g of trimethylchlorosilane, 39.1 g of methyldichlorosilane, 21.9 g of dimethyldichlorosilane, 93.0 g of diphenyldichlorosilane, 12.7 g Methyltrichlorosilane and 18.0 g phenyltrichlorosilane was added dropwise.

Synthesis Example 20

• B-13: Siliconverbindung mit einem Si-H-Gehalt von 0,21 mol/100 g, einem Gehalt an aromatischen Gruppen von 49 Gew.-% und einem durchschnittlichen Polymerisationsgrad von 8,0, hergestellt in Synthesebeispiel 13.
• B-14: Siliconverbindung mit einem Si-H-Gehalt von 0,20 mol/100 g, einem Gehalt an aromatischen Gruppen von 50 Gew.-% und einem durchschnittlichen Polymerisationsgrad von 42,0, hergestellt in Synthesebeispiel 14.
• B-15: Siliconverbindung mit einem Si-H-Gehalt von 0,50 mol/100 g, einem Gehalt an aromatischen Gruppen von 31 Gew.-% und einem durchschnittlichen Polymerisationsgrad von 11,0, hergestellt in Synthesebeispiel 15.
• B-16: Siliconverbindung mit einem Si-H-Gehalt von 0,52 mol/100 g, einem Gehalt an aromatischen Gruppen von 27 Gew.-% und einem durchschnittlichen Polymerisationsgrad von 6,5, hergestellt in Synthesebeispiel 16.
• B-17: Siliconverbindung mit einem Si-H-Gehalt von 0,80 mol/100 g, einem Gehalt an aromatischen Gruppen von 39 Gew.-% und einem durchschnittlichen Polymerisationsgrad von 7,9, hergestellt in Synthesebeispiel 17.
• B-18: Siliconverbindung mit einem Si-H-Gehalt von 0,37 mol/100 g, einem Gehalt an aromatischen Gruppen von 20 Gew.-% und einem durchschnittlichen Polymerisationsgrad von 4,4, hergestellt in Synthesebeispiel 18.
• B-19: Siliconverbindung mit einem Si-H-Gehalt von 0,34 mol/100 g, einem Gehalt an aromatischen Gruppen von 33 Gew.-% und einem durchschnittlichen Polymerisationsgrad von 62,0, hergestellt in Synthesebeispiel 19.
• B-20: Siliconverbindung mit einem Si-H-Gehalt von 0,50 mol/100 g, einem Gehalt an aromatischen Gruppen von 31 Gew.-% und einem durchschnittlichen Polymerisationsgrad von 88,0 hergestellt in Synthesebeispiel 20.

Silicone compound B-20 was obtained in the same manner as in Synthesis Example 1 except that 8.1 g of hexamethyldisiloxane, 120.3 g of 1,3,5,7-tetramethylcyclotetrasiloxane, 111.2 g of octamethylcyclotetrasiloxane and 195.5 g g diphenyldimethoxysilane were added to the flask, 20.0 g of concentrated sulfuric acid were added and 14.7 g of water were added dropwise.

• B-13: Silicone compound having an Si-H content of 0.21 mol / 100 g, an aromatic group content of 49% by weight and an average polymerization degree of 8.0, produced in Synthetic Example 13.
• B-14: Silicone compound having a Si-H content of 0.20 mol / 100 g, an aromatic group content of 50% by weight and an average polymerization degree of 42.0, produced in Synthetic Example 14.
• B-15: Silicone compound having an Si-H content of 0.50 mol / 100 g, an aromatic group content of 31% by weight and an average polymerization degree of 11.0, produced in Synthetic Example 15.
• B-16: Silicone compound having a Si-H content of 0.52 mol / 100 g, an aromatic group content of 27% by weight and an average polymerization degree of 6.5, produced in Synthesis Example 16.
• B-17: Silicone compound having an Si-H content of 0.80 mol / 100 g, an aromatic group content of 39% by weight and an average polymerization degree of 7.9, produced in Synthesis Example 17.
• B-18: Silicone compound having an Si-H content of 0.37 mol / 100 g, an aromatic group content of 20% by weight and an average degree of polymerization of 4.4, produced in Synthesis Example 18.
• B-19: Silicone compound having an Si-H content of 0.34 mol / 100 g, an aromatic group content of 33% by weight and an average polymerization degree of 62.0, produced in Synthesis Example 19.
• B-20: Silicone compound having an Si-H content of 0.50 mol / 100 g, an aromatic group content of 31% by weight and an average polymerization degree of 88.0 prepared in Synthesis Example 20.

Other components 8

Synthetic Example 21

The Silicone compound B-21 was prepared in the same manner as in Synthesis Example 1, with the exception that 39.0 g of 1,1,3,3-tetramethyldisiloxane and 566.9 g of diphenyldimethoxysilane were fed to the flask, 25.0 g concentrated sulfuric acid were added and 42.6 g of water was added dropwise.

Synthetic Example 22

• B-21 (Vergleich): Siliconverbindung mit einem Si-H-Gehalt von 0,12 mol/100 g, einem Gehalt an aromatischen Gruppen von 72 Gew.-% und einem durchschnittlichen Polymerisationsgrad von 10,0, hergestellt in Synthesebeispiel 21.
• B-22 (Vergleich): Siliconverbindung mit einem Si-H-Gehalt von 0,45 mol/100 g, einem Gehalt an aromatischen Gruppen von 5 Gew.-% und einem durchschnittlichen Polymerisationsgrad von 21,0, hergestellt in Synthesebeispiel 22.

Silicone compound B-22 was obtained in the same manner as in Synthesis Example 2 except that 560.6 g of water and 130 g of toluene were supplied to the flask and a mixture of 21.2 g of trimethylchlorosilane, 52.3 g of methyldichlorosilane, 83.9 g of dimethyldichlorosilane and 13.8 g of phenyltrichlorosilane was added dropwise.

• B-21 (comparative): Silicone compound having an Si-H content of 0.12 mol / 100 g, an aromatic group content of 72% by weight and an average polymerization degree of 10.0, produced in Synthesis Example 21.
• B-22 (comparative): A silicone compound having an Si-H content of 0.45 mol / 100 g, an aromatic group content of 5% by weight and an average polymerization degree of 21.0, produced in Synthesis Example 22.

Sum formulas of the individual silicone compounds

• B-13: M ₂ D ^H ₂ D ₁ D ^φ2 ₃
• B-14: M ₂ D ^H ₁₀ D ₁₄ D ^φ2 ₁₆
• B-15: M ^H ₅ D _2.5 D ^φ2 _0.5 T ^φ ₃
• B-16: M ^H ₃ D ₂ D ^φ2 _0.5 T ^φ ₁
• B-17: M ^H ₂ D ^H ₄ D ^φ2 _1.9
• B-18: M ₂ M ^H ₁ D ^H _0.4 T ^φ ₁
• B-19: M ₁₂ D ^H ₂₀ D ₁₀ D ^φ2 ₁₀ T ₅ Tφ ₅
• B-20: M ₂ D ^H ₄₀ D ₃₀ D ^φ2 ₁₆
• B-21: M ^H ₂ D ^φ2 ₈ (comparison)
• B-22: M ₃ D ^H ₇ D ₁₀ T ^φ ₁ (comparison)

M:

(CH₃)₃SiO_1/2

M^H:

H(CH₃)₂SiO_1/2

D:

(CH₃)₂SiO

D^H:

H(CH₃)SiO

D^ϕ2:

(C₆H₅)₂SiO

T:

(CH₃)SiO_3/2

T^ϕ:

(C₆H₅)SiO_3/2

The symbols in the above formulas each represent the following siloxane units. The coefficient of each symbol means the degree of polymerization of a siloxane unit in a molecule.

M:

(CH ₃ ) ₃ SiO _1/2

M ^H :

H (CH ₃ ) ₂ SiO _1/2

D:

(CH ₃ ) ₂ SiO

D ^H :

H (CH ₃ ) SiO

D ^φ2 :

(C ₆ H ₅ ) ₂ SiO

T:

(CH ₃ ) SiO _3/2

T ^φ :

(C ₆ H ₅ ) SiO _3/2

Examples 39 to 42

The the amounts of the components given in Table 15 were 0.01 part by weight of a phosphite-based antioxidant (IRGAFOS168 Nippon Ciba Geigy Co., Ltd.), 0.05 part by weight of an antioxidant phenol-based (IRGANOX 1076 from Ciba Specialty Chemicals), 0.3 parts by weight of a release agent (Loxiol VPG861 Fa. Cognis Japan Co., Ltd.) and 0.00005 parts by weight of Macrolex Violet B of the Fa. Bayer AG were weighed and mixed evenly in a tumble mixer. In the same manner as in Example 1, resin compositions prepared and test samples formed from the resulting mixtures.

below the starting materials used in Table 15 are given.

Component D

• D-1: Talcum (UPN HS-T0.8 from Hayashi Kasei Co., Ltd.)

Example 43

The The amounts of components given in Table 16 were weighed out, 0.01 part by weight of a phosphite-based antioxidant (IRGAFOS168 Nippon Ciba Geigy Co., Ltd.), 0.05 part by weight of an antioxidant phenol-based (IRGANOX 1076 from Ciba Specialty Chemicals), 0.3 parts by weight of a release agent (Loxiol VPG861 Fa. Cognis Japan, Ltd.), 2 parts by weight of a master pellet made of a polycarbonate resin containing 2.5% by weight of polytetrafluoroethylene having a fibrillating power (97.5 Wt .-% of the above PC-1 and 2.5 wt .-% POLYFLON MPA FA500 the Fa. Daikin Industries, Ltd., pelletized with the above-described Twin-screw extruder) and 0.00003 parts by weight Macrolex Violet B of the company Bayer AG were weighed and evenly with a tumble mixer mixed. In the same manner as in Example 1, a resin composition prepared and a test sample formed from the resulting mixture.

Example 44

A 10 wt% methylene chloride solution was prepared by dissolving the above PC-1 and the above B-20 in a weight ratio of 100:10 in methylene chloride. This methylene chloride solution was atomized with the GS-310 organic solvent spray drier from Yamato Lab-tech Co., Ltd.) to prepare a mixed powder of a polycarbonate resin and an organic siloxane. This operation was carried out using nitrogen as a heating medium at an inlet temperature of the chamber of the heating medium of 70 ° C, a flow rate of the hot medium of 0.5 m ³ / min, a sputtering pressure of 100 kPa, a feed rate of the methylene chloride solution of 40 g / min and a bottom temperature of the chamber of 70 ° C performed.

The Mixed powder and PC-1 were weighed in the ratio shown in Table 16. The remaining Components according to example 39, which are not listed in the table, were also weighed. In the same manner as in Example 39, a resin composition prepared and molded a specimen.

Table 16

The Examples leaves see the following.

The Flame retardant according to the invention aromatic polycarbonate resin composition proves to be outstanding in terms of clarity of one Laser marking on printed characters or markings as well in terms of the properties for preventing dripping when burning, since the time from the time after the inflammation to for droplet formation according to the invention the addition of the silicone compound is prolonged.

Furthermore, the following facts arise. The flame-retardant aromatic polycarbonate resin composition of the present invention is excellent in transparency and heat resistance under humid conditions, and in the properties for preventing the formation of dripping when burned, since the time from the time point after the ignition until is extended to drop formation by the addition of the silicone compound according to the invention. In particular, when the degree of polymerization of the silicone compound satisfies the above condition, excellent transparency and anti-dropping ability are achieved.

Example 45

The Pellets of Example 39 were dried with a hot air circulation dryer at 120 ° C for 5 hours and then with a single screw extruder of 40 mm diameter, which had a slot die for the film production at the end area, at a screw speed of 40 rev / min to an extrusion molding in Form of a film extruded with a thickness of 100 microns, wherein a contact roller has been used. The film had excellent transparency up and owned one smooth surface. The film was cut into square pieces of 50 mm edge length. These foil moldings were used in a DC magnetron sputtering device for training a 40 nm thick metal oxide layer of indium oxide and tin oxide, a 9 nm thick layer of a silver-gold alloy and a 40 nm thick Metal oxide layer of the abovementioned oxides in the specified Order inserted to a transparent conductive film to create.

Claims (18)

A flame-retardant aromatic polycarbonate resin composition comprising: (A) 100 parts by weight of resin components comprising: (A-1) 50 to 100% by weight of an aromatic polycarbonate resin, (A-2) 0 to 50% by weight of a resin styrene-based, (A-3) 0 to 50% by weight of an aromatic polyester resin; and (B) 0.1 to 10 parts by weight of a silicone compound having (1) a content of Si-H groups of 0.1 to 1.2 mol / 100g and (2) an aromatic group content of the formula (1) from 10 to 70% by weight

wherein the individual radicals X, which may be identical or different, denote an OH group or a monovalent organic group having 1 to 20 carbon atoms and n has the value 0 or an integer having a value of 1 to 5. A composition according to claim 1 comprising 100 parts by weight of an aromatic polycarbonate resin A-1 and 0.1 to 10 parts by weight the silicone compound B, wherein the composition is transparent is. A composition according to claim 1 or claim 2, wherein the silicone compound has an average degree of polymerization from 3 to 150. A composition according to claim 3, wherein the silicone compound has an average degree of polymerization of from 3 to 80. A composition according to claim 4, wherein the silicone compound has an average degree of polymerization of from 3 to 60. A composition according to any one of the preceding claims, wherein the content of Si-H groups is 0.2 to 1.0 mol / 100 g. A composition according to any one of the preceding claims, wherein the content of aromatic groups is 15 to 60% by weight. A composition according to any one of the preceding claims, wherein the silicone compound has a refractive index at 25 ° C of 1.40 to 1.60. A composition according to any one of the preceding claims, wherein the silicone compound is a Struk unit of the formulas (2) and / or (3) has:

wherein Z ¹ to Z ³ , which may be the same or different, represent a hydrogen atom, a monovalent organic group having 1 to 20 carbon atoms or a compound of the formula (4)

wherein Z ⁴ to Z ⁸ , which may be the same or different, represent a hydrogen atom or a monovalent organic group having 1 to 20 carbon atoms, α4 to α8 each independently have the value 0 or 1, and m2 has the value 0 or an integer with the value of 1 or more, with the proviso that when m2 in the formula (4) is 2 or more, the structural units may be different from each other; and α1 to α3 are each independently 0 or 1 and ml is 0 or an integer of 1 or more, provided that when ml in the formula (2) is 2 or more means that the structural units can differ from each other. A composition according to any one of the preceding claims, wherein the silicone compound comprises an MD unit or MDT unit, where M is a monofunctional siloxane unit, D is a difunctional Siloxane unit and T is a trifunctional siloxane unit means. A composition according to any one of the preceding claims, further full: (C) 0.001 to 0.3 parts by weight of a radical generator, an organic alkali metal salt or an organic alkaline earth metal salt, based on 100 parts by weight of the total amount of all resin components (A). A composition according to any one of the preceding claims, further full: (D) 1 to 100 parts by weight of a filler, based on 100 Parts by weight of the total of all Resin components (A). A composition according to any one of the preceding claims, wherein the component A comprises: (A-1) 50 to 99.5% by weight an aromatic polycarbonate resin, (A-2) 0 to 50% by weight a styrene-based resin, (A-3) 0 to 50% by weight of an aromatic Polyester resin; wherein the total amount of components A-2 and A-3 is 0.5 to 50% by weight. A composition according to any one of the preceding claims which contains no halogen compound as a flame retardant. A composition according to any one of the preceding claims which is transparent and a haze value of 0.3 to 20% for a 2 mm thick molded article measured in accordance with JIS K7105. A composition according to any one of the preceding claims which is transparent and has a difference (ΔH) of 0.01 to 10% for one 2 mm thick molded body between the initial one turbidity, measured according to JIS K7105, and the cloudiness after a residence time of the composition for 300 hours at a temperature of 65 ° C and a humidity of 85%. Moldings, formed from a composition according to any one of the preceding claims. Transparent film, which is a composition according to one of the claims 1 to 16 contains.