KR20150126848A - Flame retardant polycarbonate - Google Patents

Abstract

A) 60 to 99 weight percent (pbw) of an aromatic poly (ester) carbonate having a weight average molecular weight of 25,000 or more; B) 1 to 20 parts per hundred (100 phr) ) Acrylate, and a composite rubber core containing an interpenetrating and non-separable polyorganosiloxane and a poly (meth) alkyl acrylate, wherein the polyorganosiloxane (C) 2 to 20 phr of a phosphorus-containing compound and a poly (meth) alkyl acrylate / grafted shell weight ratio of 70 to 90/5 to 15/5 to 15, and D ) 0.1 to 15 phr of a boron compound having an average particle diameter of 2 to 10 micrometers.

Description

Flame retardant polycarbonate {FLAME RETARDANT POLYCARBONATE}

<Cross reference of related application>

This application claims the benefit of U.S. Provisional Patent Application No. 61 / 775,806, entitled "Flame Retardant Polycarbonate, " filed March 11, 2013 under 35 USC § 119 (e) Incorporated herein by reference.

The present invention generally relates to polycarbonate compositions, and more particularly to polycarbonate compositions having improved flame retardancy.

U.S. Patent No. 4,888,388 issued to Hongo et al. Discloses a composition comprising a polycarbonate resin (A) or a mixture (A ') of a polycarbonate resin and a saturated polyester resin and / or a polyester elastomer, % Of a polyorganosiloxane rubber and 10 to 90% by weight of polyalkyl (meth) acrylate rubber on a compound rubber consisting of a total amount of 100% by weight of at least one vinyl monomer graft- (B) having a mean particle size of from 0.08 to 0.6 탆 and a mixture (B ') of such a compound rubber type graft copolymer (B) with a vinyl monomer, wherein the component B) or (B ') is in an amount such that the compound rubber is present in an amount of from 0.5 to 60% by weight, based on the total resin composition, Discloses a ribonate resin composition.

Wittmann et al., In U.S. Patent No. 5,030,675, discloses a process for the preparation of polycarbonates, polyalkylene terephthalates, grafts, polyesters, polyesters, Polymers, fluorinated polyolefins, and phosphorus compounds.

U.S. Patent No. 5,871,570 to Koyama et al. Includes the following components (A), (B), (C), (D), (E) (C), 2-10 parts by weight of (D), 0.05-2 parts by weight of (E), and 0.01-10 parts by weight of (F) per 100 parts by weight of a resin having a weight ratio of 75/25 to 90/10. Based flame retardant resin composition. (A) a polycarbonate resin having a viscosity-average molecular weight of 16,000 to 29,000, (B) a polyalkylene terephthalate resin, (C) a rubbery polymer, and an aromatic vinyl monomer, vinyl cyanide monomer, acrylic acid, (Meth) acrylic acid ester, and maleimide-type monomer, (D) an organic phosphorus-type flame retardant, (E) a fluorocarbon-type resin, and (F) A halogen-free epoxy compound. The flame retardant resin composition is halogen-free and is said to have well balanced properties of flame retardancy, impact strength, heat resistance, moldability, chemical resistance and heat-induced discoloration resistance, and improvement in silver streak formation have.

Matsumoto et al., In U.S. Patent No. 6,174,943, disclose a thermoplastic resin composition comprising (A) a polycarbonate resin and (B) an aromatic polyester resin in a weight ratio of (A) / (B) (R) thermoplastic resin composition comprising (C) 0.5 to 100 parts by weight of a silicate compound and (D) 0.5 to 30 parts by weight of an organic phosphorus-based flame retardant per 100 parts by weight of the flame retardant thermoplastic resin composition. The composition is said to have excellent salt resistance and drop-resistant properties without containing halogen atoms, and also to have excellent properties such as heat resistance, mechanical strength, solvent resistance, surface properties of moldings, and dimensional stability.

U.S. Patent No. 6,329,451 issued to Matsumoto et al. Discloses a flame retardant thermoplastic resin composition having a small amount of stabilized flame retardant incorporated therein, which achieves improvement in both heat resistance and flame retardancy without using chlorine or bromine, It has stability and almost no odor. The composition comprises (A) 50 to 95 parts by weight of a polycarbonate resin and (B) 5 to 50 parts by weight of a thermoplastic polyester resin, and (C) 0.1 to 5 parts by weight per 100 parts by weight of (A) (D) 0.1 to 100 parts by weight of the silicate compound per 100 parts by weight of the total amount of (D) (A) and (B).

Li et al., In U.S. Patent Application Publication No. 2008-0090961, provide a thermoplastic molding composition characterized by its flame retardancy and impact strength. Wherein the total weight of A) and B) is 100 parts of resin A) 70 to 99 parts of aromatic poly (ester) carbonate B) 1 to 30 parts of polyalkylene terephthalate, and C) 1 part of 100 parts of resin To 20 parts by weight of a composite rubber core containing a grafted shell containing a polymerized alkyl (meth) acrylate and a interpenetrating and non-separable polyorganosiloxane and a poly (meth) alkyl acrylate component, Graft (co) polymers having a core-shell morphology, D) 2 to 20 phr of a phosphorus-containing compound, and E) 0.1 to 2 parts by weight of a fluorinated polyolefin.

U.S. Patent No. 8,217,101 to Lee et al. Describes a thermoplastic molding composition characterized by its flame retardancy. The composition comprises A) an aromatic poly (ester) carbonate having a weight average molecular weight of at least 25,000, B) a (co) polyester, and C) a grafted shell containing a polymerized alkyl (meth) Wherein the weight ratio of the polyorganosiloxane / poly (meth) alkyl acrylate / grafted shell is in the range of from 70 to 100, wherein the polyorganosiloxane / poly (meth) acrylate / grafted shell has a core- D) phosphorus-containing compounds, E) fluorinated polyolefins and F) boron compounds having an average particle diameter of from 2 to 10 μm.

WO 94/11429 to Ogoe et al. Describes polycarbonate; Polyesters, acrylate polymers and / or styrenic thermoplastic resins; Poly (tetrafluoroethylene); Acid acceptors; And halogenated aryl phosphate; And optionally halogenated aromatic carbonate oligomers, which have a desirable balance of ignitability, impact resistance and solvent-resistant properties.

Urabe et al. Disclose in JP 04-345657 5 to 98% by weight of a halogenated aromatic polycarbonate resin, 0 to 93% by weight of a non-halogenated aromatic polycarbonate resin, 1 to 49% by weight of an aromatic poly Ester resin, and at least one vinyl monomer on rubber particles composed of a polyorganosiloxane rubber and a polyalkyl (meth) acrylate rubber intertwined so as not to be separated from each other with an average particle size of 0.08 to 0.6 탆 1 to 20% by weight of a grafted rubber polymer conjugate, or a mixture of 1 to 20% by weight of a grafted rubber polymer conjugate and a vinyl polymer, wherein the sum of the two polycarbonate resins is from 50 to &lt; RTI ID = 98% by weight, and the halogen content is 3 to 25% by weight, based on the total weight of the flame retardant polycarbonate compound.

JP 06-239965 of Urabe et al. Discloses a resin composition comprising (A) 50 to 90% by weight of an aromatic polycarbonate resin (preferably derived from bisphenol A), (B) 2 to 45% by weight of an aromatic polyester resin (For example, polyethylene terephthalate) and (C) 3-25% by weight of a halogenated bisphenol epoxy resin of the following formula.

Wherein X is Cl or Br; Y is alkylene, O, etc .; n is an average polymerization degree and 21 to 50; Component C is said to be produced by condensation of halogenated bisphenols, such as dibromobisphenol A, with epichlorohydrin.

Ono et al. Discloses in JP 2001-031860 a composition comprising 86.7 to 35% by weight of an aromatic polycarbonate resin (component a), 10 to 40% by weight of a polyalkylene terephthalate resin (component b), stabilized red phosphorus (component c) 0.1 to 1% by weight of polytetrafluoroethylene having a fibril forming ability (component e) and 0.1 to 1% by weight of an inorganic compound consisting essentially of silicate And 0.1 to 35% by weight of the component f) as a total of 100% by weight. The internal mechanism parts of the printing apparatus can be molded from such flame retardant thermoplastic resin composition.

(Ii) a polyalkylene terephthalate resin and a component (i) of 75/25 to 90/10, wherein (i) a PC resin having a viscosity-average molecular weight of from 16,000 to 29,000, (ii) 100 parts by weight of a resin prepared by mixing 100 parts by weight of a resin prepared by mixing 100 parts by weight of a resin obtained by mixing (i) And (C) 2-10 parts by weight of an organic phosphorus-based flame retardant consisting of a condensed phosphoric acid ester, preferably of the formula: and (D) 2-10 parts by weight of a copolymer containing at least one selected from the group consisting of maleic anhydride and maleimide- ) &Lt; / RTI &gt; fluoro-based resin with 0.05 to 2 parts by weight of a fluoro-based resin.

Wherein R ₁ and R ₂ are each a monofunctional aromatic or aliphatic group; R ₃ is a bifunctional aromatic group; n is 0-15.

Yabuhara et al. Discloses a thermoplastic resin (preferably an aromatic polycarbonate / acrylonitrile-butadiene-styrene resin) other than the thermotropic liquid crystal polymer (A), (B) 0.01 -50 parts by weight of a thermotropic liquid crystal polymer (preferably a dicarboxylic compound such as a polyester-based polymer consisting of terephthalic acid and a dihydroxy compound such as ethylene glycol or hydroquinone), and (C) 1-30 parts by weight of a halogen- Lt; RTI ID = 0.0 &gt; phosphazene &lt; / RTI &gt; compounds.

Discloses a thermoplastic molding composition which is halogen-free and flame retardant. The composition comprises: A) from 60 to 99 parts by weight of an aromatic poly (ester) carbonate, and B) from 1 to 20 parts per hundred of resin (phr) of a grafted shell containing polymerized alkyl (meth) (Graphene) polymer having a core-shell morphology comprising a composite rubber core containing an interpenetrating and non-separable polyorganosiloxane and a poly (meth) alkyl acrylate component, C) from 2 to 20 phr of phosphorus- Containing compound, and D) 0.1 to 15 parts by weight of a boron compound having an average particle diameter of 2 to 10 mu m.

The present invention will now be described by way of illustration but without limitation. All numbers expressing quantities, percentages, etc. in the specification are to be understood as being modified in all instances by the term "about" Equivalents and molecular weights given herein as Daaltons (Da) are, unless otherwise stated, the number average equivalent weight and the number average molecular weight, respectively.

The composition of the present invention comprises A) from 60 to 99 weight percent (pbw), preferably from 70 to 95 pbw, most preferably from 70 to 85 pbw, having a weight average molecular weight of at least 25,000, preferably at least 26,000 g / mol Aromatic poly (ester) carbonate, B) from 1 to 20 parts, preferably from 2 to 15 parts, more preferably from 5 to 12 parts, and most preferably from 7 to 10 parts (phr in this context) per 100 parts of resin , A grafted shell containing a polymerized alkyl (meth) acrylate, and a composite-rubber core containing an interpenetrating and non-separable polyorganosiloxane and a poly (meth) alkyl acrylate component Wherein the weight ratio of polyorganosiloxane / poly (meth) alkyl acrylate / hard shell is 70 to 90/5 to 15/5 to 15, C) 2 to 20, preferably 5 to 15, particularly preferred Containing compound, preferably an organic phosphoric acid or phosphonic acid ester, and D) from 0.1 to 15, preferably from 1 to 10, most preferably from 2 to 10, most preferably from 2 to 10, 8 phr of a boron compound having an average particle diameter of 2 to 10 micrometers, preferably zinc borate. The composition of the present invention is halogen-free.

Component A

Suitable aromatic (co) polycarbonates and / or aromatic polyester carbonates are known. (Co) polycarbonates may be prepared by known methods (see, for example, Schnell ' " Chemistry and Physics of Polycarbonates ", Interscience Publishers, 1964), for example, Bayer Material Science Lt; RTI ID = 0.0 &gt; MAKROLON. &Lt; / RTI &gt; The aromatic polycarbonate can be produced by a known melting method or by a phase boundary method. Suitable aromatic dihydroxy compounds for the preparation of aromatic polycarbonates and / or aromatic polyester carbonates are according to the following formula (I).

(I)

In this formula,

A is a single bond, C ₁ - to C ₅ -alkylene, C ₂ - to C ₅ -alkylidene, C ₅ - to C ₆ -cycloalkylidene, -O-, -SO-, -CO-, -S -, -SO ₂ -; C ₆ - to C ₁₂ -arylene, in which another aromatic ring optionally containing a heteroatom may be condensed, or a radical according to the formula (II) or (III)

&Lt;

(III)

Substituent B independently of _one another represents C ₁ - to C ₁₂ -alkyl, preferably methyl,

x represents, independently of one another, 0, 1 or 2,

p represents 1 or 0,

R ⁵ and R ⁶ are selected individually for each X ^1, each independently from each other hydrogen or C ₁ - to C ₆ - alkyl, preferably represents hydrogen, methyl or ethyl,

X ¹ represents carbon and m represents an integer of 4 to 7, preferably 4 or 5, with the proviso that on at least one X ¹ atom, R ⁵ and R ⁶ are both alkyl groups.

Preferred aromatic dihydroxy compounds are selected from the group consisting of hydroquinone, resorcinol, dihydroxydiphenol, bis- (hydroxyphenyl) -C ₁ -C ₅ -alkane, bis- (hydroxyphenyl) -C ₅ -C ₆ -cyclo (Hydroxyphenyl) ether, bis- (hydroxyphenyl) sulfoxide, bis- (hydroxyphenyl) ketone, bis- (hydroxyphenyl) -sulfone and?,? - bis ) -Diisopropylbenzene. &Lt; / RTI &gt; Particularly preferred aromatic dihydroxy compounds are 4,4'-dihydroxydiphenyl, bisphenol A, 2,4-bis- (4-hydroxyphenyl) -2-methylbutane, 1,1- Hydroxyphenyl) -cyclohexane, 1,1-bis- (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 4,4'-dihydroxydiphenyl sulfide, 4,4'- Dihydroxydiphenyl-sulfone. Especially preferred is 2,2-bis- (4-hydroxyphenyl) -propane (bisphenol A). These compounds may be used individually or in any desired mixture form.

Chain terminations suitable for the preparation of thermoplastic aromatic polycarbonates include phenol, p-chlorophenol, p-tert-butylphenol, also long chain alkylphenols such as 4- (1,3-tetramethylbutyl) -phenol, Or a monoalkylphenol or dialkylphenol having a total of 8 to 20 carbon atoms in the alkyl substituent, such as 3,5-di-tert-butylphenol, p-isooctylphenol, p- Phenol and 2- (3,5-dimethylheptyl) -phenol and 4- (3,5-dimethylheptyl) -phenol. The amount of the chain terminator to be used is generally 0.5 to 10% based on the total molar amount of the aromatic dihydroxy compound used.

The polycarbonate may be prepared in a known manner, preferably by reacting a compound having three or more functional groups, for example, a compound having three or more phenolic groups, in an amount of from 0.05 to 5 parts by weight, based on the total molar amount of the aromatic dihydroxy compound used, 2.0% &lt; / RTI &gt;

Aromatic polyester carbonates are known. Such suitable resins are disclosed in U.S. Patent Nos. 4,334,053, 6,566,428 and CA 1173998, which are incorporated herein by reference.

An aromatic dicarboxylic acid dihalide for the production of aromatic polyester carbonates is prepared by reacting isophthalic acid, terephthalic acid, diphenyl ether 4,4'-dicarboxylic acid and dianhydrides of naphthalene-2,6-dicarboxylic acid . Particularly preferred is a mixture of diatomic dihalides of isophthalic acid and terephthalic acid in a ratio of from 1:20 to 20: 1. Branching agents may also be used in the preparation of suitable polyester carbonates, for example, carboxylic acid chlorides having three or more functional groups such as trimesic acid trichloride, cyanuric acid trichloride, 3,3'-, 4,4'-benzophenone-tetracarboxylic acid tetrachloride, 1,4,5,8-naphthalenetetracarboxylic acid tetrachloride or pyromellitic acid tetrachloride (based on the dicarboxylic acid dichloride used ), Or a phenol having 3 or more functional groups such as, for example, fluoroglucinol, 4,6-dimethyl-2,4,6-tri- (4-hydroxyphenyl) Dimethyl-2,4,6-tri- (4-hydroxyphenyl) -heptane, 1,3,5-tri- (4-hydroxyphenyl) Bis (4-hydroxyphenyl) -cyclohexyl] -phosphorane, tri- (4-hydroxyphenyl) (4-hydroxyphenyl-isopropyl) -phenol, tetra- (4-hydroxyphenyl) -methane, 2,6- 4-methylphenol, 2- (4-hydroxyphenyl) -2- (2,4-dihydroxyphenyl) -propane, tetra- (4- [4-hydroxyphenyl-isopropyl] Methane, 1,4-bis [4,4'-dihydroxy-triphenyl) -methyl] -benzene can be used in an amount of 0.01 to 1.0 mol% based on the diphenol used. The phenolic branching agent may be introduced into the reaction vessel with diphenol, and the acid chloride branching agent may be introduced with the acid dichloride.

The content of the carbonate structural unit in the thermoplastic aromatic polyester carbonate is preferably 100 mol% or less, especially 80 mol% or less, particularly preferably 50 mol% or less, based on the total amount of the ester group and the carbonate group to be. Both the esters and the carbonates contained in the aromatic polyester carbonates can be present in the polycondensation product in block form or in a randomly distributed manner.

The thermoplastic aromatic poly (ester) carbonate has a weight average molecular weight (measured by gel permeation chromatography) of at least 25,000, more preferably at least 26,000. Preferably, they have a maximum weight average molecular weight of 35,000 g / mol, more preferably 32,000 g / mol or less, particularly preferably 30,000 g / mol or less. The thermoplastic aromatic poly (ester) carbonates may be used alone or in any desired mixture.

Component B

Suitable graft (co) polymers in the context of the present invention have a core / shell structure. It has been found that it is possible to obtain a composite rubber core comprising a polyorganosiloxane and an alkyl (meth) acrylate, preferably a polysiloxane and a butyl acrylate, on a composite rubber core comprising interpenetrating and inseparable interpenetrating network (IPN) And optionally graft polymerizing the copolymerizable vinyl monomers. The shell is a polymeric hard phase containing alkyl methacrylate, preferably methyl methacrylate. The weight ratio of polysiloxane / alkyl (meth) acrylate / light phase is 70 to 90/5 to 15/5 to 15, preferably 75 to 85/7 to 12/7 to 12, most preferably 80/10/10 .

The glass transition temperature of the rubber core is preferably less than 0 占 폚, more preferably less than -20 占 폚, particularly less than -40 占 폚. The amount of component B present in the composition of the present invention is from 1 to 20, advantageously from 2 to 15, preferably from 5 to 12, most preferably from 7 to 10 phr.

A preferred rubber core has a median particle size (d ₅₀ value) of 0.05 to 5 micrometers, more preferably 0.1 to 2 micrometers, especially 0.1 to 1 micrometer. The median value can be determined by ultracentrifugation measurement (W. Scholtan, H. Lange, Kolloid, Z. and Z. Polymere 250 (1972), 782-1796).

The polyorganosiloxane component in the graft (co) polymer can be prepared by reacting an organosiloxane with a multifunctional crosslinking agent by an emulsion polymerization method. In addition, suitable unsaturated organosiloxanes can be added to insert the graft-active sites in the rubber.

The organosiloxane is generally cyclic and the ring structure preferably contains from 3 to 6 Si atoms. Examples thereof include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like. , Which may be used alone or as a mixture of two or more such compounds. The organosiloxane component is present in the silicone acrylate rubber in an amount of at least 70%, preferably at least 75%, based on the weight of the graft (co) polymer.

Suitable crosslinking agents are trifunctional or silane silane compounds. Preferred examples include trimethoxymethylsilane, triethoxyphenylsilane, tetramethoxysilane, tetraethoxysilane, tetra-n-propoxysilane and tetrabutoxysilane.

The graft-active moiety can be incorporated into the polyorganosiloxane component of the silicone acrylate rubber by incorporating a compound according to any of the following structures.

In this formula,

R ⁵ represents methyl, ethyl, propyl or phenyl,

R &lt; ⁶ &gt; represents hydrogen or methyl,

n represents 0, 1 or 2,

p represents 1 to 6;

(Meth) acryloyloxysilane is a preferred compound for forming structure (GI-1). Preferred (meth) acryloyloxysilanes are selected from the group consisting of? -Methacryloyloxyethyl-dimethoxy-methyl-silane,? -Methacryloyloxypropyl-methoxy-dimethylsilane,? -Methacryloyloxypropyl -Dimethoxy-methyl-silane, -methacryloyloxypropyl-trimethoxy-silane, -methacryloyloxypropylethoxy-diethyl-silane, -methacryloyloxypropyl-di Methyl-silane and? -Methacryloyloxybutyl-diethoxy-methyl-silane.

Vinyl siloxanes, especially tetramethyl-tetravinyl-cyclotetrasiloxanes, are suitable for forming structure (GI-2).

p-vinylphenyl-dimethoxy-methylsilane is suitable, for example, to form structure (GI-3). ? -mercaptopropyldimethoxy-methylsilane,? -mercaptopropylmethoxy-dimethylsilane,? -mercaptopropyl-diethoxymethylsilane and the like are suitable for forming the structure (GI-4).

The amount of these compounds is 10% or less (based on the weight of the polyorganosiloxane), preferably 0.5 to 5.0%.

The acrylate component of the silicone acrylate composite rubber may be prepared from alkyl (meth) acrylates, crosslinkers and graft-active monomer units.

Examples of preferred alkyl (meth) acrylates are alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, n-butyl acrylate, 2-ethylhexyl acrylate; And alkyl methacrylates such as hexyl methacrylate, 2-ethylhexyl methacrylate and n-lauryl methacrylate, with n-butyl acrylate being particularly preferred.

A polyfunctional compound can be used as a crosslinking agent. Examples thereof include ethylene glycol dimethacrylate, propylene glycol dimethacrylate, 1,3-butylene glycol dimethacrylate and 1,4-butylene glycol dimethacrylate.

The following compounds can be used individually or in combination to insert graft-active sites: allyl methacrylate, triallyl cyanurate, triallyl isocyanurate, allyl methacrylate. Allyl methacrylate can also act as a crosslinking agent. These compounds may be used in an amount of 0.1 to 20% based on the weight of the acrylate rubber component.

Methods of preparing silicone acrylate composite rubbers preferably used in compositions according to the present invention and grafting them with monomers are described, for example, in U.S. Patent Nos. 4,888,388 and 4,963,619, both of which are incorporated herein by reference.

Grafting of the graft base (here B.1) can be carried out in suspension, dispersion or emulsion. Continuous or discontinuous emulsion polymerization is preferred. The graft polymerisation can be carried out using free radical initiators (e. G., Peroxides, azo compounds, hydroperoxides, persulfates, perphosphates) and optionally anionic emulsifiers such as carboxonium salts, sulfonates or organic sulphates .

The graft shell (B.2)

B.2.1 (For example, styrene, alpha-olefins) of from 0 to 80%, preferably from 0 to 50%, especially from 0 to 25% (based on the weight of the grafted shell) -Methylstyrene, p-methylstyrene), vinyl cyanide (e.g., acrylonitrile and methacrylonitrile), and

B.2.2 (meth) acrylic acid (C ₁ -C ₈ ) -alkyl esters (based on the weight of the grafted shell) of from 100 to 20%, preferably from 100 to 50%, in particular from 100 to 75% (E.g., methyl methacrylate, n-butyl acrylate, tert-butyl acrylate) and derivatives of unsaturated carboxylic acids such as anhydrides and imides (e.g., maleic anhydride and N- Amide) and at least one monomer selected from the group consisting of

&Lt; / RTI &gt;

Preferred grafted shells comprise at least one (meth) acrylic acid (C ₁ -C ₈ ) -alkyl ester, especially methyl methacrylate.

Component C

Suitable phosphorus-containing compounds in the context of the present invention include oligomeric organic phosphoric or phosphonic acid esters structurally according to formula IV:

(IV)

In this formula,

R ¹ , R ² , R ³ and R ⁴ independently of one another denote C ₁ -C ₈ -alkyl, C _5-6 -cycloalkyl, C _6-20 -aryl or C _{7-12 -aralkyl} , Each is optionally substituted by alkyl, preferably C _1-4 -alkyl,

n independently represents 0 or 1, preferably 1,

q represents from 0.5 to 30, preferably from 0.8 to 15, particularly preferably from 1 to 5, in particular from 1 to 2,

X is a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms, an aliphatic radical having 2 to 30 carbon atoms, which may be OH-substituted and contain up to 8 ether linkages. Aliphatic radicals can be linear or branched.

Preferably, R ¹ , R ² , R ³ and R ⁴ each independently of one another represent C _1-4 -alkyl, phenyl, naphthyl or phenyl-C _1-4 -alkyl. In embodiments where any of R ¹ , R ² , R ³ and R ⁴ is aromatic, the aromatic group may be substituted by an alkyl group, preferably C _1-4 -alkyl. Particularly preferred aryl radicals are cresyl, phenyl, xylyenyl, propylphenyl or butylphenyl.

In a preferred embodiment, X represents a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms. It is preferably derived from any of the aromatic dihydroxy compounds of formula (I).

X particularly preferably represents at least one member selected from the group consisting of

In particular, X may be derived from resorcinol, hydroquinone, bisphenol A or diphenyl phenol, particularly preferably bisphenol A.

Another suitable phosphorous-containing compound is a compound of formula IVa:

&Lt; Formula IVa >

In this formula,

R ¹ , R ² , R ³ , R ⁴ , n and q are as defined above for formula (IV)

m independently represents 0, 1, 2, 3 or 4,

R ⁵ and R ⁶ independently of one another represent C _1-4 -alkyl, preferably methyl or ethyl,

Y is C ₁ - to C ₇ -alkylidene, C _1-7 -alkylene, C _5-12 -cycloalkylene, C _5-12 -cycloalkylidene, -O-, -S-, -SO ₂ - Or -CO-, preferably isopropylidene or methylene.

Especially preferred are the following formulas.

In the above formula, q is 1 to 2.

Such phosphorus compounds are known (see, for example, U.S. Patent Nos. 5,204,394 and 5,672,645, both of which are incorporated herein by reference), or by known methods (see, for example, Ullmanns Enzyklopädie der technischen Chemie, p. 301 et seq., 1979; Houben-Weyl, Methoden der organischen Chemie, Vol 12/1, p. 43; Beilstein Vol.

Component C is present in the composition of the present invention in an amount of from 2 to 20, preferably from 5 to 15, particularly preferably from 7 to 15, most preferably from 10 to 15 phr.

Component D

Suitable boron compounds in the context of the present invention are not particularly limited as long as they are compounds having a boron atom. Examples thereof include boric acid, boron oxide and borate salts. The borates include zinc borate, such as zinc tetraborate, zinc metaborate and basic zinc borate; Barium borate such as barium orthoborate, barium metaborate, barium diborate and barium tetraborate; Lead borate, cadmium borate and magnesium borate. These boric acid compounds may be used alone or in combination as a mixture of two or more.

A preferred boron compound is zinc borate. The preferred formula of the zinc borate is mZnO and nB ₂ O ₃ and xH ₂ O, wherein the ratio of x / m / n is about 0 to 7/1 to 5/2 to 6. Such borates are well known and commercially available. The average particle diameter is from 2 to 10 [mu] m, advantageously from 4 to 6 [mu] m, or from 8 to 10 [mu] m. The particle size and particle diameter always indicate the average particle diameter.

Other ingredients

The composition of the present invention may further comprise additives known to function in relation to the thermoplastic molding composition containing the poly (ester) carbonate. They may contain further additives such as lubricants, release agents such as, for example, pentaerythritol tetrastearate, nucleating agents, antistatic agents, heat stabilizers, light stabilizers, hydrolytic stabilizers, fillers and reinforcing agents, colorants or pigments, ) Flame retardant or a flame retardant synergist. The composition of the present invention is halogen-free.

The compositions of the present invention can be prepared conventionally using conventional equipment and the following conventional procedures. The composition of the present invention can be used for producing any kind of molding by thermoplastic methods such as injection molding, extrusion and blow molding methods.

<Examples>

The present invention is further illustrated by the following examples, but it is not limited thereto. All amounts given as "parts" and "percent" are to be construed as being by weight unless otherwise indicated.

In the preparation of the exemplified compositions, the components and additives were melt compounded in a twin screw extruder ZSK 30 at a temperature profile of 120-280 占 폚. The obtained pellets were dried in a forced air convection oven at 110 DEG C for 4 to 6 hours. The components were injection molded (melt temperature 265-285 占 폚, mold temperature about 75 占 폚).

In the preparation of the compositions described below, the following ingredients were used:

Bisphenol-A based homopolycarbonate having a melt flow rate of about 4 g / 10 min (at 300 DEG C, 1.2 Kg) according to PC ASTM D 1238;

(MMA) -grafted siloxane (Si) -butylacrylate (BA) composite rubber containing Si-BA in the elastomeric MMA shell and core and Si / BA / MMA weight ratio of 80/10/10, methyl methacrylate ;

P-compound according to the formula:

Zinc borate An average particle diameter of 5 micrometers and is commercially available from Chemtura as ZB-467.

The non-optical density of the flame treated smoke was determined on a 1.5 mm plaque using a heat flux of 35 kW / m &lt; ² &gt; according to ASTM E662 flame treatment.

The cone peak heat release rate was determined on a 1.5 mm plaque using a heat flux of 35 kW / m &lt; ² &gt; according to ASTM E662.

The melt flow rate (MVR) of the composition was determined according to ASTM D-1238 at 300 DEG C under a load of 1.2 kg.

The Vicat temperature (VICAT) was determined according to ASTM D 1525 using a load of 50 Newton and a heating rate of 120 ° C / h.

The heat distortion temperature (HDT) was determined at 0.455 MPa, 120 占 폚 / h (HDT1) and 1.82 MPa, 120 占 폚 / h (HDT2) according to ASTM D 648.

Notched Izod impact energy was determined on a 1/8 "sample at 23 ° C in accordance with ASTM D 256.

The results of these tests are reported in Table I below.

<Table I>

The above embodiments of the present invention are provided for illustration, but are not limited thereto. It will be apparent to those of ordinary skill in the art that the embodiments described herein may be altered or modified in various ways without departing from the spirit and scope of the invention. The scope of the invention should be determined by the appended claims.

Various aspects of the subject matter described herein are set forth in the following numbered items:

1. A) 60 to 99 weight percent (pbw) of an aromatic poly (ester) carbonate having a weight average molecular weight of at least 25,000, B) 1 to 20 parts per hundred (100 phr) Acrylate, and a composite rubber core containing a polyorganosiloxane and an interpenetrating and non-separable poly (meth) alkyl acrylate, wherein the polyorganosiloxane / C) 2 to 20 phr of a phosphorus-containing compound, and D) a poly (meth) alkyl acrylate / grafted shell in a weight ratio of 70 to 90/5 to 15/5 to 15, 0.1 to 15 phr of a boron compound having an average particle diameter of 2 to 10 micrometers.

2. A composition according to item 1, wherein the aromatic poly (ester) carbonate is a homopolycarbonate based on bisphenol A.

3. The composition of item 1, wherein the graft (co) polymer is present in an amount of 2 to 15 phr.

4. The composition of item 1, wherein the phosphorus compound is a member selected from the group consisting of phosphoric acid esters and phosphonic acid esters.

5. The composition of item 4, wherein said member is structurally according to formula IV:

(IV)

Wherein R ¹ , R ² , R ³ and R ⁴ are each independently of the other C ₁ - to C ₈ -alkyl, C _5-6 -cycloalkyl, C _6-20 -aryl or C _{7-12 -aralkyl} , N is independently 0 or 1, q is 0.5 to 30, X is a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms, or an aliphatic radical having 2 to 30 carbon atoms .

6. The composition of item 4 wherein said compound is structurally according to the formula:

7. The composition of item 1, wherein the boron compound is zinc borate.

8. The composition of item 1, wherein the boron compound is present in an amount of 1 to 10 phr.

nB₂O₃

xH₂O에 따른 것이며, 여기서 x/m/n의 비는 0 내지 7/1 내지 5/2 내지 6인 조성물.9. The method according to item 1, wherein the boron compound has the formula mZnO

nB ₂ O ₃

xH ₂ O, wherein the ratio of x / m / n is from 0 to 7/1 to 5/2 to 6.

10. The composition according to item 1, wherein the average particle diameter is from 4 to 6 占 퐉.

11. The composition according to item 1, wherein the average particle diameter is 8 to 10 micrometers.

12. A composition according to item 1, characterized in that it comprises a lubricant, a releasing agent, a nucleating agent, an antistatic agent, a heat stabilizer, a hydrolytic stabilizer, a light stabilizer, a colorant, a pigment, a filler, Lt; RTI ID = 0.0 &gt; 1, &lt; / RTI &gt;

Claims (12)

A) 60 to 99 weight percent (pbw) of an aromatic poly (ester) carbonate having a weight average molecular weight of at least 25,000;
B) from 1 to 20 parts per hundred 100 parts of the resin (phr) of a grafted shell containing a polymerized alkyl (meth) acrylate, and an interpenetrating and non-separable polyorganosiloxane and poly (meth) Wherein the weight ratio of polyorganosiloxane / poly (meth) alkyl acrylate / grafted shell is from 70 to 90/5 to 15/5 to 15, wherein the weight ratio of polyorganosiloxane / poly (Co) polymers;
C) from 2 to 20 phr of a phosphorus-containing compound; And
D) 0.1 to 15 phr of a boron compound having an average particle diameter of 2 to 10 micrometers
&Lt; / RTI &gt; The composition of claim 1, wherein the aromatic poly (ester) carbonate is a homopolycarbonate based on bisphenol A. The composition of claim 1, wherein the graft (co) polymer is present in an amount of from 2 to 15 phr. The composition of claim 1, wherein the phosphorus compound is a member selected from the group consisting of phosphoric acid esters and phosphonic acid esters. 5. The composition of claim 4, wherein the member is structurally according to formula IV:
(IV)

In this formula,
R ¹ , R ² , R ³ and R ⁴ independently of one another denote C ₁ - to C ₈ -alkyl, C _5-6 -cycloalkyl, C _6-20 -aryl or C _{7-12 -aralkyl} ,
n independently represents 0 or 1,
q represents 0.5 to 30,
X is a mononuclear or polynuclear aromatic radical having 6 to 30 carbon atoms, or an aliphatic radical having 2 to 30 carbon atoms. 5. The composition of claim 4, wherein the member is structurally according to the formula:

In the above formula, q is 1 to 2. The composition of claim 1, wherein the boron compound is zinc borate. The composition of claim 1, wherein the boron compound is present in an amount of from 1 to 10 phr. The method according to claim 1, wherein the boron compound has the formula mZnO

nB ₂ O ₃

xH ₂ O, wherein the ratio of x / m / n is from 0 to 7/1 to 5/2 to 6. The composition of claim 1, wherein the average particle diameter is from 4 to 6 占 퐉. The composition of claim 1, wherein the average particle diameter is from 8 to 10 micrometers. The composition according to claim 1, comprising a lubricant, a releasing agent, a nucleating agent, an antistatic agent, a heat stabilizer, a hydrolytic stabilizer, a light stabilizer, a colorant, a pigment, a filler, &Lt; / RTI &gt;