DE10036056A1 - Polycarbonate composition, useful for molded articles or film, contains a graft rubber obtained by emulsion polymerization of styrene and acrylonitrile in the presence of at least two rubber lattices - Google Patents

Abstract

A polycarbonate composition comprises an aromatic polycarbonate, 1-50 pts.wt. of a graft rubber obtained by emulsion polymerization of styrene and acrylonitrile in a wt. ratio of 90:10-50:50 in the presence of at least two rubber lattices, and 0-50 pts.wt of at least one thermoplastic polymer of styrene, alpha -methylstyrene, acrylonitrile, methylmethacrylate and N-substituted maleimide. A polycarbonate composition (I) comprises (A) 5-95 pts.wt. of an aromatic polycarbonate (B) 1-50 pts.wt. of a graft rubber obtained by emulsion polymerization of styrene and acrylonitrile in a wt. ratio of 90:10-50:50 whereby styrene and acrylonitrile are optionally at least partially replaced by alpha -methylstyrene, methylmethacrylate or N-phenylmaleimide, in the presence of at least two rubber lattices of type (B1) and (B2) which contain 0-50 wt.% of a further copolymerized vinyl monomer and whereby the wt. ratio of added monomers to the rubber lattices is 25:75-70:30 and is characterized in that rubber latex (B1) has a particle diameter (d50) of no greater than 350 nm and particle size distribution (expressed as d90 - d10) as 30-100 nm and a gel content of no greater than 70 wt.% and latex (B2) has a d50 value of at least 350 nm, d90-d10 value of 50-500 nm and a gel content of at least 70 wt.% and the difference between the average diameter of (B1) and (B2) is at least 50 nm. (C) 0-50 pts.wt of at least one thermoplastic homo-, co- or terpolymer of styrene, alpha -methylstyrene, acrylonitrile, methylmethacrylate and N-substituted maleimide and optionally (D) 0.5-25 pts.wt. of at least one flame retardant and optionally other known additives. An Independent claim is also included for molded articles, sheet or film prepared using the polycarbonate composition (I).

Description

The present invention relates to thermoplastic polycarbonate / graft polymer Molding compounds with improved mechanical properties (especially impact ability and elongation at break) and improved processing behavior (flow behavior).

The particular graft rubbers according to the present invention are general known (EP-A 745 624 or US-A 5 741 853). They are characterized by good toughness quality, workability and surface quality (gloss, color impression). It will generally mentioned that the graft rubbers in thermoplastic resins such as aromatic Polycarbonates, polyesters, polyamides can be used, the proportion of Graft rubbers in the molding compositions preferably 10 to 80, in particular 20 to Is 75% by weight. There is no indication in the document as to which one possess such properties of molding compounds. EP-A 745 624 does not disclose the compositions according to the invention according to the present application.

From DE-A 196 39 821 polycarbonate-ABS mixtures are known, their ABS part from a mixture of graft polymers with different particle sizes exists and which are characterized by improved processing behavior. The achievable level of mechanical properties with such molding compositions, spe but the combination of notched impact strength and elongation at break is for many Applications insufficient.

The flame-retardant polycarbonate ABS molding compounds are also becoming increasingly popular higher demands are placed on the mechanical properties.

The use of organic phosphates such as oligophosphates as flame retardants agent for polycarbonate molding compositions is known and described, for example, in EP-A 0 363 608, EP-A 0 771 851 and EP-A 0 755 977. Problematic in use  of such oligophosphates as flame retardants is always associated with this ongoing deterioration in mechanical properties.

It was therefore the task of polycarbonate / graft polymer (especially from ABS type) molding compounds with improved mechanical properties, in particular a combination of impact strength and elongation at break and improved processing to provide processing behavior.

It has now been found that the use of special graft rubber systems with special bimodal particle size distribution and special gel contents in the Rubber bases in polycarbonate molding compounds give the desired Have property profile.

The invention relates to a composition

• A) 5 to 95 parts by weight, preferably 10 to 90 parts by weight, particularly preferably 20 to 80 parts by weight of aromatic polycarbonate,
• B) 1 to 50 parts by weight, preferably 2 to 40 parts by weight of at least one graft rubber, which is obtainable by emulsion polymerization of styrene and acrylonitrile in a weight ratio of 90: 10 to 50: 50, styrene and / or acrylonitrile entirely or can be partially replaced by α-methylstyrene, methyl methacrylate or N-phenylmaleimide, in the presence of at least two rubber latices of types (A) and (B), each containing 0 to 50 wt .-% of another vinyl monomer copolymerized, and wherein Mass ratio of monomers used to rubber latices used is 25: 75 to 70: 30, characterized in that the rubber latex (B1) has a particle diameter d ₅₀ ≦ 350 nm, preferably 260 to 310 nm, a width of the particle size distribution (measured as d ₉₀ - d ₁₀ from the integral particle size distribution) from 30 to 100 nm, preferably from 40 to 80 nm, and a gel content ≦ 70% by weight, preferably 40 to 65% by weight, and the K Autschuklatex (B2) a particle diameter d ₅₀ ≧ 350 nm, preferably 380 to 450 nm, a width of the particle size distribution (measured as d ₉₀ -d ₁₀ from the integral particle size distribution) from 50 to 500 nm, preferably from 100 to 400 nm, and one Gel content ≧ 70% by weight, preferably 75 to 90% by weight, and the difference in the average particle diameter is ≧ 50 nm, preferably ≧ 80 nm, particularly preferably ≦ 100 nm,
• C) 0 to 50 parts by weight, preferably 0 to 40 parts by weight and particularly preferably 0 to 30 parts by weight, at least one thermoplastic homo-, co- or Terpolymers containing styrene, α-methylstyrene, acrylonitrile, methyl methacrylate, N-substituted maleimide or mixtures thereof,

and if necessary

• A) 0.5 to 25 parts by weight, preferably 2 to 20 parts by weight and particularly be preferably 3 to 15 parts by weight (each per 100 parts by weight A + B + C + D) min at least a flame retardant and, where appropriate, conventional additives such as Lubricants, antistatic agents, mold release agents or mixtures thereof,

Component A

Thermoplastic aromatic polycarbonates according to component A which are suitable according to the invention are those based on the diphenols of the formula (I)

wherein
A is a single bond, C ₁ -C ₅ alkylene, C ₂ -C ₅ alkylidene, C ₅ -C ₆ cycloalkylidene, -S- or -SO ₂ -,
B chlorine, bromine,
q 0, 1 or 2 and
p are 1 or 0
or alkyl-substituted dihydroxyphenylcycloalkanes of the formula (II),

wherein
R ⁸ and R ⁹ independently of one another are hydrogen, halogen, preferably chlorine or bromine, C ₁ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl, C ₆ -C ₁₀ aryl, preferably phenyl, and C ₇ -C ₁₂ - Aralkyl, preferably phenyl-C ₁ -C ₄ -alkyl, in particular benzyl,
m is an integer of 4, 5, 6 or 7, preferably 4 or 5,
R ¹⁰ and R ^{11 can be} selected individually for each Z, independently of one another hydrogen or C ₁ -C ₆ alkyl
and
Z mean carbon, with the proviso that ZR ¹⁰ and R ¹¹ simultaneously mean alkyl on at least one atom.

Suitable diphenols of formula (I) are e.g. B. hydroquinone, resorcinol, 4,4-dihy hydroxydiphenyl, 2,2-bis (4-hydroxyphenyl) propane, 2,4-bis (4-hydroxyphenyl) -2- methyl butane, 1,1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (3-chloro-4-hydroxy phenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane.

Preferred diphenols of the formula (I) are 2,2-bis (4-hydroxyphenyl) propane, 2,2- Bis (3,5-dichloro-4-hydroxyphenyl) propane and 1,1-bis (4-hydroxyphenyl) cyclo hexane.

Preferred diphenols of the formula (II) are 1,1-bis (4-hydroxyphenyl) -3,3-dimethyl cyclohexane, 1,1-bis- (4-hydroxyphenyl-3,3,5-trimethylcyclohexane and 1,1-bis- (4- hydroxyphenyl) -2,4,4-trimethyl-cyclopentane.

Polycarbonates suitable according to the invention are both homopolycarbonates and Copolycarbonates.

Component A can also be a mixture of the thermoplastics defined above be polycarbonates.

Polycarbonates can be prepared in a known manner from diphenols with phosgene Phase boundary process or with phosgene according to the process in homogeneous Phase, the so-called pyridine process, the molecular weight in a known manner by a corresponding amount of known chains cancel can be set.

Suitable chain terminators are e.g. B. phenol, p-chlorophenol, p-tert-butylphenol or 2,4,6-tribromophenol, but also long-chain alkylphenols, such as 4- (1,3-tetramethyl butyl) phenol according to DE-OS 28 42 005 (Le A 19 006) or monoalkylphenol or  Dialkylphenol with a total of 8 to 20 carbon atoms in the alkyl substituents German patent application P 3 506 472.2 (Le A 23 654), such as 3,5-di-tert-butylphe nol, p-iso-octylphenol), p-tert-octylphenol, p-dodecylphenol and 2- (3,5-dimethyl heptyl) phenol and 4- (3,5-dimethylheptyl) phenol.

The amount of chain terminators is generally between 0.5 and 10 mol%, based on the sum of the diphenols of the formulas (I) and / or used in each case (II).

The polycarbonates A suitable according to the invention have average molecular weights (M _w , weight average, measured, for example, by ultracentrifugation or scattered light measurement) of 10,000 to 200,000, preferably 20,000 to 80,000.

The polycarbonates A which are suitable according to the invention can be ver be branched, preferably by incorporating 0.05 to 2 mol%, bezo to the sum of the diphenols used, at three or more than three functions nellen connections, e.g. B. those with three or more than three phenolic groups.

In addition to bisphenol A homopolycarbonate, preferred polycarbonates are the Co polycarbonates of bisphenol A with up to 15 mol%, based on the molar sums on diphenols, on 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane and the copoly Carbonates of bisphenol A with up to 60 mol%, based on the molar sums Diphenols, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane.

Preferred polycarbonates can also copolycarbonates with polysiloxane structures be.  

Component B

In the graft polymerization, a mixture of at least two rubber latices, one each of type B1 and B2. The weight ratio B1: B2 is based on the respective solids content of the latices, preferably 90:10 to 10:90, particularly preferably 60:40 to 30:70.

Suitable rubber latices are, for example and preferably selected from diene rubbers, EP (D) M rubbers, that is to say those based on ethylene / propylene and, if appropriate, dienes, and also acrylate rubbers. They generally have glass transition temperatures below 10 ° C., preferably 0 ° C., particularly preferably below -10 ° C. Diene rubbers are preferred. Particularly preferred are diene rubbers based on butadiene which, as comonomers, contain up to 50, preferably up to 30% by weight (based on the total amount of monomer used for the rubber latex production) of other monomers selected from the group consisting of isoprene, chloroprene, acrylonitrile, styrene, α Methylstyrene, C ₁ -C ₄ -alkylstyrenes, C ₁ -C ₈ -alkyl acrylates, C ₁ -C ₈ -alkyl methacrylates, alkylene glycol diacrylates, alkylene glycol dimethacrylates, divinylbenzene or mixtures thereof. Preferred comonomers are styrene, acrylonitrile or methyl (meth) acrylate or mixtures thereof. Polybutadiene is particularly preferred. The rubber patents B1 and B2 can be produced by emulsion polymerization of the corresponding monomers. This polymerization is known and z. B. in Houben-Weyl, Methods of Organic Chemistry, Macromolecular Substances, Part 1, p. 674 (1961), Thieme Verlag Stuttgart. It is also possible to first produce a finely divided rubber latex by known methods and then to agglomerate it in a known manner to adjust the required particle size.

Relevant techniques have been described (see EP-A 0 029 613; EP-A 0 007 810;

DD-A 144 415 DE-A 12 33 131; DE-A 12 58 076; DE-A 21 01 650; US-A 1,379,391).  

The so-called seed polymerization technique can also be used, in which a finely divided butadiene polymer is first produced and then through Further conversion with monomers containing butadiene to larger particles is polymerized.

The graft polymerization is preferably carried out by adding monomers to the mixture of the butadiene polymer latices B1 and B2 in such a way that within the first Half of the monomer runtime 55 to 90 wt .-%, preferably 60 to 80 wt .-% and 65 to 75% by weight of the monomers are particularly preferably metered in.

In principle, the butadiene polymer latices B1 and B2 can also be produced by Emulsification of finely divided butadiene polymers in aqueous media (cf. Japanese patent application JP-A 55 125 102).

The butadiene polymer latex B1 has an average particle diameter d ₅₀ ≦ 350 nm, preferably 260 to 310 nm, a width of the particle size distribution (measured as d ₉₀ -d ₁₀ from the integral particle size distribution) from 30 to 100 nm, preferably from 40 to 80 nm, and a gel content ≦ 70% by weight, preferably 40 to 65% by weight.

The rubber latex B2 has an average particle diameter d ₅₀ ≧ 350 nm, preferably 380 to 450 nm, a width of the particle size distribution (measured as d ₉₀ -d ₁₀ from the integral particle size distribution) from 50 to 500 nm, preferably from 100 to 400 nm, and a gel content ≧ 70% by weight, preferably 75 to 90% by weight.

The rubber latices according to the invention are characterized in that the Difference in average particle diameter ≧ 50 nm, preferably ≧ 80 nm and is particularly preferably ≧ 100 nm. They particularly preferred Rubber latices have a difference in average particle diameter of 80 to 350 nm, preferably 100 to 250 nm.  

The mean particle diameter d ₅₀ and the d ₁₀ and d ₉₀ values can be determined by ultracentrifuge measurement (cf. W. Scholtan, H. Lange: Kolloid Z. and Z. Polymer 250, pp. 782 to 796 (1972) ), the values for the gel content refer to the determination according to the wire cage method in toluene (cf.Houben-Weyl, Methods of Organic Chemistry, Macromolecular Substances, Part 1, p. 307 (1961), Thieme Verlag Stuttgart).

The gel contents of the rubber latices B1 and B2 can be adjusted in a manner known in principle by using suitable reaction conditions (e.g. high reaction temperature and / or polymerization up to high conversion and optionally addition of crosslinking substances to achieve a high gel content or e.g. low Reaction temperature and / or termination of the polymerisation reaction before the occurrence of excessive crosslinking and, if appropriate, addition of molecular weight regulators such as, for example, n-dodecyl mercaptan or t-dodecyl mercaptan in order to achieve a low gel content). The usual anionic emulsifiers such as alkyl sulfates, alkyl sulfonates, aralkyl sulfonates, soaps of saturated or unsaturated fatty acids and alkaline disproportionated or hydrogenated abietic or tall oil acids can be used as emulsifiers; emulsifiers with carboxyl groups (e.g. salts of C ₁₀ -C ₁₈ fatty acids) are preferred , disproportionated abietic acid).

The graft polymerization can be carried out so that the monomer mixture continuously added to the mixture of rubber latices B1 and B2 and is polymerized.

Special monomers are preferred: rubber ratios and one The defined procedure for adding monomer to the rubber latex was followed.

To produce the products according to the invention, preferably 25 to 70 parts by weight Parts, particularly preferably 30 to 60 parts by weight, of a mixture of styrene and  Acrylonitrile, optionally up to 50 wt .-% (based on the total amount in the graft polymerization used monomers) of one or more comonomers may contain, in the presence of preferably 30 to 75 parts by weight, particularly preferably 40 to 70 parts by weight (in each case based on solids) of the butadiene poly merisate latex mixture of B1 and B2 polymerized.

The monomers used in this graft polymerization are preferred Mixtures of styrene and acrylonitrile in a weight ratio of 90:10 to 50:50, especially preferably in a weight ratio of 65:35 to 80:20, with styrene and / or acrylonitrile in its entirety or partially by copolymerizable monomers, preferably by a-methyl styrene, methyl methacrylate or N-phenylmaleimide can be replaced.

In addition, molecular weight regulators can be used in the graft polymerization are, preferably in amounts of 0.05 to 2 wt .-%, particularly preferably in Amounts of 0.1 to 1 wt .-% (each based on the total amount of monomer in the Graft polymerization stage). Suitable molecular weight regulators are, for example, n- Dodecyl mercaptan, t-dodecyl mercaptan, dimeric α-methylstyrene, terpinolene.

As initiators come inorganic and organic peroxides, e.g. B. H ₂ O ₂ , di-tert-butyl peroxide, cumene hydroperoxide, dicyclohexyl percarbonate, tert-butyl hydroperoxide, p-menthane hydroperoxide, azo initiators such as. B. azobisisobutyronitrile, inorganic persalts such as ammonium, sodium or potassium persulfate, potassium perphosphate, sodium perborate and redox systems, which are composed of a generally organic oxidizing agent and a reducing agent, with heavy metal ions also being present in the reaction medium (see H Logemann in Houben-Weyl, Methods of Organic Chemistry, Volume 14/1, pp. 263 to 297).

The reaction temperature is 25 ° C to 160 ° C, preferably 40 ° C to 90 ° C. As an emul gators, the above compounds can be used.  

Graft polymerization is used to produce the products according to the invention preferably be carried out by monomer feed such that within the first half of the total monomer metering time 55 to 90 wt .-%, preferably 60 to 80 wt .-% and particularly preferably 65 to 75 wt .-% of the total at Monomers to be used for graft polymerization; the remaining Monomer content is within the second half of the total monomer metering time added.

Finally, the graft polymer so produced is at least one thermo plastic resin (component C) mixed. There are several ways to do this. If the thermoplastic resin itself was produced by emulsion polymerization, then the latices are mixed and precipitated and processed together. Was that Thermoplastic resin produced by solution or bulk polymerization, it must Graft polymer by known methods, for example by spray drying or by adding salts and / or acids, washing the precipitated products and Drying the powder isolated and then with the preferably in granular form existing thermoplastic resin are mixed (preferably on multiple rollers chairs, mixing extruders or internal kneaders); this method is preferred applied.

Component C

Component C comprises one or more thermoplastic vinyl (co) polymers sate.

Suitable as vinyl (co) polymers C are polymers of at least one monomer from the group of vinyl aromatics, vinyl cyanides (unsaturated nitriles), (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters, unsaturated carboxylic acids and derivatives (such as anhydrides and Imides) of unsaturated carboxylic acids. (Co) polymers of are particularly suitable

• 1. C.1 50 to 99, preferably 60 to 80 parts by weight of vinyl aromatics and / or core-substituted vinyl aromatics such as styrene, α-methylstyrene, p-methylstyrene, p-chlorostyrene) and / or methacrylic acid (C ₁ -C ₈ ) -alkyl esters such as B. methyl methacrylate, ethyl methacrylate), and
• 2. C.2 1 to 50, preferably 20 to 40 parts by weight of vinyl cyanides (unsaturated nitriles) such as acrylonitrile and methacrylonitrile and / or (meth) acrylic acid (C ₁ -C ₈ ) alkyl esters (such as, for example, methyl methacrylate , n-butyl acrylate, t-butyl acrylate) and / or unsaturated carboxylic acids (such as maleic acid) and / or derivatives (such as anhydrides and imides) of unsaturated carboxylic acids (for example maleic anhydride and N-phenyl-maleimide).

The (co) polymers C are resinous, thermoplastic and rubber-free.

The copolymer of C.1 styrene and C.2 acrylonitrile is particularly preferred.

Preferred vinyl resins are copolymers of styrene and acrylonitrile in Ge weight ratio 90: 10 to 50: 50, styrene and / or acrylonitrile in whole or in part may be replaced by α-methylstyrene and / or methyl methacrylate.

The (co) polymers according to C are known and can be prepared by radical polymerization, in particular by emulsion, suspension, solution or bulk polymerization (see, for example, DE-AS 24 20 385, DE-A 27 24 360 ). The (co) polymers preferably have molecular weights M _w (weight average, determined by light scattering or sedimentation) between 15,000 and 200,000.

Component D

Flame retardants come as component D to be used according to the invention and optionally conventional additives such as lubricants, antistatic agents, mold release agents medium or mixtures in question.  

Examples of flame retardants are both halogen-containing and halogen-free ones Links.

Suitable halogen compounds are organic chlorine and / or bromine compounds gene.

Halogen-containing flame retardants are, for example

• 1. Chlorinated and brominated diphenyls, such as octachlorodiphenyl, decachlorodiphe nyl, octabromodiphenyl, decabromodiphenyl.
• 2. Chlorinated and brominated diphenyl ethers, such as octa- and decachlorodiphenyl ether and octa and decabromodiphenyl ether.
• 3. Chlorinated and brominated phthalic anhydride and its derivatives, such as Phthalimides and bisprithalimides, e.g. B. tetrachloric and tetrabromophthalic acid anhydride, tetrachloro- and tetrabromophthalimide, N, N'-ethylene-bis-tetrachloro- and N, N'-ethylene-bis-tetrabromophthalimide, N-methyltetrachloro- and N- Methyl tetrabromophthalimide.
• 4. Chlorinated and brominated bisphenols such as 2,2-bis (3,5-di-chloro-4-hydroxy phenyl) propane and 2,2-bis (3,5-di-bromo-4-hydroxyphenyl) propane.
• 5. 2,2-bis (3,5-di-chloro-4-hydroxyphenyl) propane oligocarbonate and 2,2-bis (3,5-di-bromo-4-hydroxyphenyl) propane oligocarbonate with a medium one Degree of polycondensation from 2 to 20.

Bromine compounds are preferred over chlorine compounds. Prefers are halogen-free flame retardants.  

All of them are usually suitable as flame retardants used phosphorus compounds, especially phosphine oxides and derivatives of Acids of phosphorus and salts of acids and acid derivatives of phosphorus.

Derivatives (e.g. esters) of acids of phosphorus and their salts are preferred, where acids of phosphorus, phosphoric acid, phosphonic acid, phosphinic acid, phos phorous acid, including in each case in dehydrated form, salts preferably Al Potassium, alkaline earth and ammonium salts of these acids and their derivatives (for example partially esterified acids) are included.

Particularly preferred phosphorus compounds are those of the formula (III)

in which
R ¹² , R ¹³ and R ¹⁴ independently of one another are an optionally halogenated C ₁ -C ₈ -alkyl or an optionally halogenated and / or alkylated C ₅ - or C ₆ -cycloalkyl or an optionally halogenated and / or alkylated and / or aralkylated C ₆ -C ₃₀ aryl
and
n and m are independently 0 or 1,

These phosphorus compounds are generally known (see for example Ullmann, Encyclopedia of Technical Chemistry, Volume 18, pages 301 ff, 1979). The aralkylier Ten phosphorus compounds are described, for example, in DE-OS 38 24 356 0 ben.  

Optionally halogenated C ₁ -C ₈ -alkyl radicals according to compounds of the formulas (III) and (IV) can be halogenated one or more times, be linear or branched. Examples of alkyl radicals are chloroethyl, 2-chloropropyl, 2,3-dibromopropyl, butyl, methyl or octyl.

Optionally halogenated and / or alkylated C ₅ - or C ₆ -cycloalkyls according to compounds of the formula (III) and / or (IV) are optionally mono- to poly-halogenated and / or alkylated C ₅ - or C ₆ -cycloalkyls, that is, for. B. cyclopentyl, cyclohexyl, 3,3,3-trimethylcyclohexyl and fully chlorinated cyclohexyl.

Optionally halogenated and / or alkylated and / or aralkylated C ₆ -C ₃₀ aryl radicals according to compounds of formula (III) are optionally mono- or polynuclear, halogenated once or more and / or alkylated and / or aralkylated, e.g. B. chlorophenyl, bromophenyl, pentachlorophenyl, pentabromophenyl, phenyl, cresyl, isopropylphenyl, benzyl-substituted phenyl and naphthyl.

Phosphorus compounds of the formula (III) which can be used according to the invention are, for. B. Tri butyl phosphate, tris (2-chloroethyl) phosphate, tris (2,3-dibromopropyl) phosphate, tri phenyl phosphate, tricresyl phosphate, diphenyl cresyl phosphate, diphenyl octyl phosphate, diphenyl 2-ethylcresyl phosphate, tri (isopropylphenyl) phosphate, Tris (p-benzylphenyl) phosphate, triphenylphosphine oxide, methanephosphonic acid di methyl ester, methanephosphonic acid diphenyl ester and phenylphosphonic acid diethyl ester.

Suitable flame retardants are also oligomeric phosphorus compounds of the formula (IV)

wherein
R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ independently of one another are C ₁ -C ₈ alkyl, preferably methyl, C ₅ -C ₆ cycloalkyl, C ₆ -C ₁₀ aryl, preferably phenyl, C ₇ -C ₁₂ aralkyl , preferably phenyl-C ₁ -C ₄ alkyl,
n independently of one another 0 or 1,
N 1 to 5 and
X is a mono- or polynuclear aromatic radical with 6 to 30 carbon atoms; preferably derived diphenols of formula (I), in particular bisphenol A, hydroquinone or resorcinol.

In the case of mixtures of several phosphates of the formula (IV), N represents an average between 1 and 5.

The molecular weight of the phosphorus compounds of the formula (IV) is in general nen less than 2000 g / mol, preferably less than 1000 g / mol. These are, for example described in EP-A 0 363 608.

Preferred flame retardants are also mixtures of phosphorus compounds of the formula (III) and phosphorus compounds of the formula (IV).  

The compositions according to the invention generally contain 0.5 to 25, preferably 2 to 20, in particular 3 to 15 parts by weight of phosphorus compounds (based on 100 parts by weight of total composition) as a flame retardant.

Examples of lubricants are hydrocarbons (e.g. paraffin oils, polyethylene waxes), alcohols (e.g. stearyl alcohol), carboxylic acids (e.g. lauric acid, palmitin acid, stearic acid), carboxamides (stearic acid amide, ethylenediamine bisstearyl amide), carboxylic acid esters (e.g. n-butyl stearate, stearyl stearate, glycerol monostearate, Glycerol tristearate, pentaerythritol tetrastearate); preferred lubricants are carbon acid amides and carboxylic acid esters.

Examples of antistatic agents are cationic compounds (e.g. quaternary ammonium, Phosphonium or sulfonium salts), anion-active compounds (e.g. alkyl sulfonates, alkyl sulfates, alkyl phosphates, carboxylates in the form of alkali or earth alkali metal salts), non-ionic compounds (e.g. polyethylene glycol esters, poly ethylene glycol ether, fatty acid esters, ethoxylated fatty amines); preferred antistatic are non-ionic compounds.

Examples of mold release agents are calcium stearate, zinc stearate, pentaerythritol tetra stearate; preferred mold release agent is pentaerithritol tetrastearate.

The polycarbonate / graft polymer molding compositions may contain fluorinated polyolefins for certain flame retardant requirements. These are of high molecular weight and have glass transition temperatures of above -30 ° C., generally above 100 ° C., fluorine contents, preferably from 65 to 76, in particular from 70 to 76% by weight, average particle diameter d ₅₀ from 0.05 to 1000, preferably 0.08 to 20 microns. In general, the fluorinated polyolefins have a density of 1.2 to 2.3 g / cm ³ . Preferred fluorinated polyolefins are polytetrafluoroethylene, polyvinylidene fluoride, tetrafluoroethylene / hexafluoropropylene and ethylene / tetrafluoroethylene copolymers. The fluorinated polyolefins are known (cf. "Vinyl and Related Polymer" from Schildknecht, John Wiley & Sons, Inc., New York, 1962, pages 484-494; "Fluoropolymers" from Wall, Wiley-Interscience, John Wiley & Sons, Inc., New York, Vol. 13, 1970, pages 623-654; "Modern Plastics Encyclopedia", 1970-1971, Vol. 47, No. 10A, October 1970, Mc Graw-Hill, Inc., New York, page 134, and 774; "Modern Plastics Encyclopedia", 1975-1976, October 1975, Vol. 52, No. 10A, Mc Graw-Hill, Inc., New York, pages 27, 28 and 472, and U.S. Patents 3,671,487, 3,723,373 and 3 838 092).

In general, the compositions contain 0.01 to 1, preferably 0.05 to 0.6 parts by weight of fluorinated polyolefin (based on 100 parts by weight of total) setting).

Contain particularly preferred compositions

• A) 60 to 98 parts by weight, preferably 70 to 95 parts by weight, especially before adds 75 to 90 parts by weight of at least one aromatic polycarbonate and / or polyester carbonate,
• B) 0.5 to 30 parts by weight, preferably 1 to 25 parts by weight, especially 2 to 20 parts by weight of at least one graft rubber according to component B,
• C) 0 to 40 parts by weight, preferably 0 to 30 parts by weight, in particular 0 to 20 parts by weight of vinyl (co) polymer,
• D) 0.5 to 25 parts by weight, preferably 2 to 20 parts by weight, in particular 3 to 15 parts by weight of at least one phosphorus compound selected from verbin extensions of the formula (III) or (IV) or mixtures thereof,
• E) 0.01 to 1.5 parts by weight, preferably 0.05 to 1 part by weight, in particular 0.1 to 0.8 parts by weight of fluorinated polyolefin

where the sum of the parts by weight is 100.  

In addition to the additives mentioned, the molding compositions according to the invention can further contain stabilizers, pigments, fillers and reinforcing materials. Before Drawn fillers are glass balls, mica, silicates, quartz, talc, titanium dioxide or wollastonite. Reinforcing materials are preferably glass or carbon fibers.

The molding compositions according to the invention, containing components A to D and ge optionally other known additives such as stabilizers, dyes, pigments, fillers and reinforcing agents and / or nucleating agents are made by using the each constituent mixed in a known manner and at temperatures of 200 ° C to 330 ° C in common units such as internal kneaders, extruders and double Shaft-screws melt-compounded or melt-extruded.

The present invention thus also relates to a method for the production of thermoplastic molding compositions containing components A to D and optionally stabilizers, dyes, pigments, fillers and reinforcing materials and / or nucleating agent, which is characterized in that the components A to D and optionally stabilizers, dyes, pigments, flow agents, fillers and reinforcing materials and / or nucleating agents after mixing Temperatures of 200 to 330 ° C in common aggregates dated or melt extruded.

The mixing of the individual components can both successively in a known manner cessive and simultaneous, both at about 20 ° C (room temperature temperature) as well as at higher temperatures.

The molding compositions of the present invention can be used for the production of farm products pern of any kind can be used. In particular, molded articles can be injection molded getting produced. Examples of moldings that can be produced are: housing parts each Kind, e.g. B. for household appliances, such as juicers, coffee machines, blenders, for the office machines, or cover plates for the construction sector and parts for the motor vehicle sector. you will be  also used in the field of electrical engineering because they have very good elec have tric properties.

The molding compositions are particularly suitable for producing thin-walled molds share (e.g. data technology housing parts), where particularly high demands on notch impact strength, elongation at break and stress crack resistance of the used Plastics are provided.

Another form of processing is the production of molded articles by blowing shape or by deep drawing from previously made sheets or foils.  

Examples Components used

• 1. A1: polycarbonate based on bisphenol A with a relative solution viscosity of 1.28 measured in methylene chloride at 25 ° C and a concentration of 0.5 g / 100 ml
• 2. A2: polycarbonate based on bisphenol A with a relative solution viscosity of 1.20 measured in methylene chloride at 25 ° C and a concentration of 0.5 g / 100 ml
• 3. B0: Graft polymer obtained by emulsion polymerization of 40 parts by weight of a monomer mixture of styrene and acrylonitrile (weight ratio 73: 27) in the presence of 60 parts by weight (calculated as a solid) of a polybutadiene latex having an average particle size ( d ₅₀ ) of approx. 280 nm, addition of approx. 1.0 part by weight of a phenolic antioxidant, coagulation with a magnesium sulfate / acetic acid mixture and drying of the polymer powder,
• 4. B1: 8 parts by weight (calculated as solid) of an anionically emulsified polybutadiene latex (latex A) produced by radical polymerization with ad ₅₀ value of 277 nm, ad ₉₀ -d ₁₀ value of 44 nm and a gel content of 58% by weight and 50 parts by weight (calculated as a solid) of an anionically emulsified polybutadiene latex (latex B) produced by radical polymerization with ad ₅₀ value of 415 nm, ad ₉₀ d ₁₀ value of 144 nm and a gel content of 83 wt .-% are brought to a solids content of about 20 wt .-% with water, then heated to 63 ° C and mixed with 0.5 parts by weight of potassium peroxodisulfate (dissolved in water). Thereafter, 42 parts by weight of a mixture of 73% by weight of styrene and 27% by weight of acrylonitrile and 0.1 part by weight of tert-dodecyhnercaptan are metered in uniformly over the course of 4 hours; parallel to this, 1 part by weight (calculated as the solid substance) of the sodium salt of a resin acid mixture (Dresinate 731, dissolved in alkaline water) is metered in over 4 hours. After a 4-hour reaction time, the graft latex is co-regulated with the addition of approx. 1.0 part by weight of a phenolic antioxidant with a magnesium sulfate / acetic acid mixture and, after washing with water, the resulting powder is dried at 70 ° C. in vacuo .
• 5. C: styrene / acrylonitrile copoly mixture with a styrene / acrylonitrile ratio of 72: 28 mol of a weight viscosity of 0.55 dl / g (measurement in dimethyl fomamid at 20 ° C)
• 6. D1: Flame retardant: Resorcinol oligophosphate, Fyrolflex® RDP from AKZO No bel Chemicals GmbH, Düren, Germany
• 7. D2: Flame retardant: triphenyl phosphate, Disflamoll® TP from Bayer AG, Le Verkusen, Germany
• 8. E: Fluorinated polyolefin: The tetrafluoroethylene polymer is coagulated Mixture of a graft polymer emulsion according to B1 in water and egg ner tetrafluoroethylene polymer emulsion used in water. The Ge weight ratio of graft polymer B1 to tetrafluoroethylene polymer in the mixture is 90% by weight to 10% by weight. The tetrafluoethylene poly Merisat emulsion has a solids content of 60% by weight, the particles The size is between 50 and 500 nm. The graft polymer emulsion has a solids content of 34% by weight.

Mold release agent: pentaerythritol tetrastearate  The components described above are given in Table 1 Amounts homogeneously mixed and mixed in an internal mixer at approx. 200 ° C to 220 ° C finally converted into granules.

Table 1

Composition and properties of the molding compounds

The heat resistance according to Vicat B is determined in accordance with DIN 53 460 (ISO 306) on rods measuring 80 × 10 × 4 mm ³ .

The elongation at break is determined in accordance with ISO 527.

The MVR (melt volume flow rate) is determined according to ISO 1133. The determinations The impact strength is measured according to IO 180/1 A.

The fire behavior is according to UL Subj. 94 V on bars of dimension Measured 127 × 12.7 × 1.6 mm, produced on an injection molding machine at 260 ° C.  

Table 2

Composition and properties of the molding compounds

Both in Table 1 and in Table 2 (flame-retardant PC / ABS molding compounds) show the molding compositions according to the invention, which have a special graft polymer included, significant property improvements in terms of impact strength and Elongation at break.

Claims (2)

1. Containing polycarbonate compositions

• A) 5 to 95 parts by weight of aromatic polycarbonate,
• B) 1 to 50 parts by weight of at least one graft rubber, which it is available by emulsion polymerization of styrene and acrylonitrile in a weight ratio of 90:10 to 50:50, wherein styrene and / or acrylonitrile can be replaced in whole or in part by α-methylstyrene , Methyl methacrylate or N-phenylmaleimide, in the presence of at least two rubber latices of types (A) and (B), each containing 0 to 50% by weight of another vinyl monomer copolymerized ent, and the mass ratio of monomers used to rubber latices used 25: 75 to 70: 30, characterized in that the rubber latex (B1) has a particle diameter d ₅₀ ≦ 350 nm, a width of the particle size distribution (measured as d ₉₀ -d ₁₀ from the integral particle size distribution) of 30 to 100 nm, and a gel content ≦ 70% by weight, and the rubber latex (B2) has a particle diameter d ₅₀ ≧ 350 nm, a width of the particle size distribution (measured as d ₉₀ d ₁₀ from the integral particle size distribution) of 50 to 500 nm and a gel content ≧ 70% by weight, and the difference in the mean particle diameter of B1 and B2 is ≧ 50 nm,
• C) 0 to 50 parts by weight of at least one thermoplastic homopolymer, copolymer or terpolymer comprising styrene, α-methylstyrene, acrylonitrile, methyl methacrylate, N-substituted maleimide or mixtures thereof,

and if necessary

• A) 0.5 to 25 parts by weight (each per 100 parts by weight of A + B + C + D) at least one flame retardant and, if appropriate, customary additives.

2. Compositions according to claim 1 containing flame retardants selected from at least one phosphate or mixtures thereof of the formula (III)
in which
R ¹² , R ¹³ and R ¹⁴ independently of one another are an optionally halogenated C ₁ -C ₈ alkyl or an optionally halogenated and / or alkylated C ₅ or C ₆ cycloalkyl or an optionally halogenated and / or alkylated and / or aralkylated C ₆ -C ₃₀ aryl
and
n and m are independently 0 or 1, or
oligomeric phosphorus compounds of the formula (IV)
wherein
R ¹⁵ , R ¹⁶ , R ¹⁷ , R ¹⁸ independently of one another are C ₁ -C ₈ alkyl, C ₅ -C ₆ cycloalkyl, C ₆ -C ₁₀ aryl, C ₇ -C ₁₂ aralkyl,
n independently of one another 0 or 1,
N 1 to 5 and
X is a mono- or polynuclear aromatic radical with 6 to 30 carbon atoms.