JP2002513837A - Flame-retardant polycarbonate / rubber-modified graft copolymer resin blend with low halogen content - Google Patents

Abstract

  (57) [Summary] An object of the present invention is to provide a thermoplastic resin composition exhibiting high performance and good flame retardancy and having a low fluorine content. The thermoplastic composition of the present invention comprises an aromatic polycarbonate resin, a discontinuous elastomeric phase dispersed in a continuous rigid thermoplastic phase, wherein at least a portion of the rigid thermoplastic phase is chemically grafted to the elastomeric phase. The modified rubber-modified graft copolymer, the phosphorus-containing flame retardant compound, and the fluoropolymer in an amount effective to improve the flame retardant performance of the composition. However, the fluorine content of this composition does not exceed 0.1% by weight.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

TECHNICAL FIELD OF THE INVENTION

The present invention relates to a flame-retardant resin composition mainly composed of a blend of a polycarbonate resin and a rubber-modified graft copolymer and having a low halogen content.

[0002]

[Prior art]

Flame retardant compositions containing an aromatic polycarbonate resin, a graft copolymer, a fluoropolymer and a phosphorus-containing flame retardant compound are known and have been found to exhibit good flame retardancy and good heat resistance. See, for example, U.S. Patent No. 5,204,394, assigned to the assignee of the present invention. The composition of U.S. Pat. No. 5,204,394 contains, for example, 0.2 to 0.5 pbw of polytetrafluoroethylene per 100 parts by weight (pbw) of the composition. In some applications, the amount of fluorine that may be included in the composition is, for example, 0.1% by weight of the acceptable fluorine content.
Restricted by government regulations such as DIN / VDE 0472, Part 815, Test B, which is restricted below.

[0003]

[Problems to be solved by the invention]

A thermoplastic resin composition that exhibits the high performance and good flame retardant properties of the composition disclosed in U.S. Pat. No. 5,204,394 and has a low fluorine content is desirable.

[0004]

[Means for Solving the Problems]

The thermoplastic resin composition of the present invention comprises: (a) an aromatic polycarbonate resin; and (b) a discontinuous elastomer phase dispersed in a continuous hard thermoplastic phase, wherein at least a portion of the hard thermoplastic phase is chemically converted to an elastomer phase. (C) a phosphorus-containing flame retardant compound, and (d) an effective amount of a fluoropolymer to improve the flame retardant performance of the composition, wherein: The fluorine content of the composition does not exceed 0.1% by weight.

The compositions of the present invention exhibit unexpectedly high performance and good flame retardant properties despite meeting the requirements of DIN / VDE 0472, 815 parts, low fluorine content of test B .

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION

In a preferred embodiment, the thermoplastic resin composition of the present invention comprises
60 to 95 pbw, more preferably 75 to 95 pbw, more preferably still 80 to 90 pbw, based on the bw, polycarbonate resin of 1 to 15 pbw
w, more preferably 4 to 10 pbw, still more preferably 5 to 7 pbw, a rubber-modified graft copolymer, 3 to 15 pbw, more preferably 5 to 12 pbw.
And more preferably from 8 to 10 pbw of a phosphorus-containing flame retardant compound, the amount of fluoropolymer being from 0.038 to 0.1 pbw, more preferably from 0.1 to 38 pbw.
It is effective to provide a fluorine content of from 0.5 to 0.1 pbw, and more preferably from 0.08 to 0.1 pbw.

Aromatic Polycarbonate Resin Aromatic polycarbonate resins suitable for use as the polycarbonate resin component of the thermoplastic resin composition of the present invention are known compounds, and their production and properties are described, for example, in US Pat. No. 3,169,121. No. 4487896 and No. 5
No. 411999, the disclosures of which are each incorporated herein by reference.

In a preferred embodiment, the aromatic polycarbonate resin component of the present invention comprises a dihydric phenol HO-A-OH (I) of the following structural formula (I) wherein A is a divalent aromatic group. A) and a carbonate precursor, and comprises a structural unit of the following formula (II):

[0009]

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Wherein A is as defined above.

The term “divalent aromatic group” as used herein refers to a divalent group containing a single aromatic ring, such as phenylene, for example, containing a fused aromatic ring system, such as naphthalene A divalent group is meant to include, for example, divalent groups containing two or more aromatic rings linked by non-aromatic bonds such as alkylene, alkylidene or sulfonyl groups, each of which is one of the aromatic rings. More than one site may be substituted, for example, by a halogen or (C ₁ -C ₆ ) alkyl group.

In a preferred embodiment, A is a divalent aromatic group of formula (III):

[0013]

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Suitable dihydric phenols include, for example, 2,2-bis (4-hydroxyphenyl) propane (“bisphenol A”), 2,2-bis (3,5-dimethyl-4-)
Hydroxyphenyl) propane, bis (4-hydroxyphenyl) methane, 4,
4-bis (4-hydroxyphenyl) heptane, 3,5,3 ', 5'-tetrachloro-4,4'-dihydroxyphenylpropane, 2,6-dihydroxynaphthalene, hydroquinone, 2,4'-dihydroxyphenylsulfone There is one or more of In a highly preferred embodiment, the dihydric phenol is bisphenol A.

The carbonate precursor is one or more of a carbonyl halide, carbonate or haloformate. Suitable carbonyl halides include, for example, carbonyl bromide and carbonyl chloride. Suitable carbonates include, for example, diphenyl carbonate, dichlorophenyl carbonate, dinaphthyl carbonate, phenyltolyl carbonate, and ditolyl carbonate. Suitable haloformates include, for example, bishaloformates of dihydric phenols (such as hydroquinone) or glycols (such as ethylene glycol and neopentyl glycol). In a highly preferred embodiment, the carbonate precursor is carbonyl chloride.

Suitable aromatic polycarbonate resins include linear aromatic polycarbonate resins and branched aromatic polycarbonate resins. Suitable linear aromatic polycarbonate resins include, for example, bisphenol A polycarbonate resins. Suitable branched polycarbonates are known and are made by reacting a polyfunctional aromatic compound with a dihydric phenol and a carbonate precursor to form a branched polymer. See, for example, U.S. Patent Nos. 3,544,514, 3,635,895 and 4,001,184. The disclosures of each of these U.S. patents are hereby incorporated by reference. Polyfunctional compounds are generally aromatic and contain three or more functional groups, the functional groups being carboxyls, carboxylic anhydrides, phenols, haloformates or mixtures thereof, e.g.
1,1-tri (4-hydroxyphenyl) ethane, 1,3,5-trihydroxybenzene, trimellitic anhydride, trimellitic acid, trimellityl trichloride,
-Chloroformyl phthalic anhydride, pyromellitic acid, pyromellitic dianhydride, mellitic acid, mellitic anhydride, trimesic acid, benzophenone tetracarboxylic acid, benzophenone tetracarboxylic dianhydride and the like. Preferred polyfunctional aromatic compounds are 1,1,1-tri (4-hydroxyphenyl) ethane, trimellitic anhydride or trimellitic acid, or a haloformate derivative thereof.

In a preferred embodiment, the polycarbonate resin component of the present invention is a linear polycarbonate resin derived from bisphenol A and phosgene.

In a preferred embodiment, the weight average molecular weight of the polycarbonate resin is about 1000 as determined by gel permeation chromatography using polystyrene as a standard.
0 to about 200,000 grams / mole ("g / mole"). Such resins typically exhibit an intrinsic viscosity of about 0.3 to about 1.5 dl / g in methylene chloride at 25 ° C.

The polycarbonate resin is produced by a known method such as interfacial polymerization, transesterification, solution polymerization or melt polymerization.

[0020] Copolyester-carbonate resins are also suitable for use as the aromatic polycarbonate resin component of the present invention. Copolyester-carbonate resins suitable for use as the aromatic polycarbonate resin component of the thermoplastic resin composition of the present invention are known compounds whose manufacture and properties are described, for example, in US Pat.
No. 121, No. 4,430,484 and No. 4,487,896, the disclosures of which are each incorporated herein by reference.

The copolyester-carbonate resin is composed of a linear or randomly branched polymer and contains carbonate groups, carboxylate groups and aromatic carbocyclic groups as repeating units in the polymer chain. Is directly attached to a ring carbon atom of an aromatic carbocyclic group.

In a preferred embodiment, the copolyester-carbonate resin component of the present invention is derived from a carbonate precursor, one or more dihydric phenols and one or more dicarboxylic acids or dicarboxylic acid equivalents. In a preferred embodiment, the dicarboxylic acid is of the following formula (IV)

[0023]

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In the formula, A ′ is alkylene, alkylidene, cycloaliphatic or aromatic, preferably one or more sites on the unsubstituted phenylene group or the aromatic ring are each independently (C ₁ -C ₆ )
It is a substituted phenylene group substituted with alkyl. The copolyester-carbonate resin comprises a first structural unit of the above formula (II) and a second structural unit of the following formula (V).

[0025]

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Wherein A ′ is as defined above.

[0027] Suitable carbonate precursors and dihydric phenols are those set forth above.

Suitable dicarboxylic acids include, for example, phthalic acid, isophthalic acid, terephthalic acid,
Dimethyl terephthalic acid, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, sebacic acid, dimethylmalonic acid,
1,12-dodecanoic acid, cis-1,4-cyclohexanedicarboxylic acid, tra
There are ns-1,4-cyclohexanedicarboxylic acid, 4,4'-bisbenzoic acid, and naphthalene-2,6-dicarboxylic acid. Suitable dicarboxylic acid equivalents include, for example, the anhydride, ester or halide derivatives of the above-mentioned dicarboxylic acids, such as phthalic anhydride, dimethyl terephthalate, succinyl chloride, and the like.

In a preferred embodiment, the dicarboxylic acid is an aromatic dicarboxylic acid, more preferably one or more of terephthalic acid and isophthalic acid.

In a preferred embodiment, the ratio of ester bonds to carbonate bonds present in the copolyester-carbonate resin is from 0.25 to 0.9 ester bonds per carbonate bond.

In a preferred embodiment, the copolyester-carbonate copolymer is about 1000
It has a weight average molecular weight of 0 to about 200,000 g / mol.

The copolyester-carbonate resin is manufactured by a known method such as, for example, interfacial polymerization, transesterification, solution polymerization or melt polymerization.

Rubber-Modified Thermoplastic Resin A rubber-modified thermoplastic resin suitable as the rubber-modified thermoplastic resin of the present invention comprises a continuous hard thermoplastic phase in which a discontinuous elastomer phase is dispersed and at least a part of the hard thermoplastic phase. Chemically grafted to the elastomer phase.

(A) Elastomer Phase Materials suitable for use as the elastomer phase are polymers having a glass transition temperature (Tg) of 25 ° C. or less, more preferably 0 ° C. or less, and even more preferably -30 ° C. or less. is there. The Tg of the polymer referred to in the present specification is a Tg value of the polymer measured by differential scanning calorimetry (heating rate: 20 ° C./min, Tg value is determined at an inflection point).

In a preferred embodiment, the elastomeric phase is one selected from conjugated diene monomers, non-conjugated diene monomers or (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers.
Consists of polymers having repeating units derived from more than one type of monoethylenically unsaturated monomer.

Suitable conjugated diene monomers include, for example, 1,3-butadiene, isoprene, 1,1,
3-heptadiene, methyl-1,3-pentadiene, 2,3-dimethylbutadiene, 2-ethyl-1,3-pentadiene, 1,3-hexadiene, 2,4-hexadiene, dichlorobutadiene, bromobutadiene, dibromobutadiene, and the like As well as conjugated diene monomer mixtures. In a preferred embodiment, the conjugated diene monomer is 1,3-butadiene.

Suitable non-conjugated diene monomers include, for example, ethylidene norbornene, dicyclopentadiene, hexadiene or phenylnorbornene.

The term “(C ₁ -C ₁₂ ) alkyl” as used herein refers to a straight-chain or branched alkyl substituent having 1 to 12 carbon atoms per group, for example, methyl , Ethyl, n-butyl, sec-butyl, t-butyl, n-propyl, isopropyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl and the like, and are referred to as "(meth) acrylate monomers". The term generically refers to acrylate and methacrylate monomers. Suitable (C ₁ -C ₁₂₎ alkyl (meth) acrylate monomer, ethyl acrylate, butyl acrylate, isopentyl acrylate, n- hexyl acrylate, 2-ethylhexyl acrylate of (C ₁ -C ₁₂₎ alkyl acrylates System monomers, and (C ₁ -C ₁₂ ) alkyl methacrylate analogs thereof, such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, butyl methacrylate, hexyl methacrylate, and decyl methacrylate.

The elastomer phase may include, as an optional component, at least one monomer selected from a (C ₂ -C ₈ ) olefin monomer, a vinyl aromatic monomer and a monoethylenically unsaturated nitrile monomer. Up to about 25% by weight ("wt%").

As used herein, the term “(C ₂ -C ₈ ) olefin monomer” refers to a group having 2 to 8 carbon atoms per molecule and one ethylenically unsaturated site per molecule. Having a compound. Suitable (C ₂ -C ₈₎ olefin monomers, such as ethylene, propene, 1-butene, 1-pentene, a heptene, and the like.

Suitable vinyl aromatic monomers include, for example, styrene and substituted styrenes having one or more alkyl, alkoxyl, hydroxyl or halo substituents attached to the aromatic ring, such as α-methylstyrene, p-methylstyrene, Vinyl toluene, vinyl xylene, trimethyl styrene, butyl styrene, chloro styrene, dichloro styrene, bromo styrene, p-hydroxy styrene, methoxy styrene and the like, and a vinyl-substituted condensed aromatic ring structure such as vinyl naphthalene and vinyl anthracene; There is a group monomer mixture.

The term “monoethylenically unsaturated nitrile monomer” as used herein is defined as
An acrylic compound having one nitrile group and one ethylenically unsaturated site per molecule, for example, acrylonitrile, methacrylonitrile, α-chloroacrylonitrile and the like.

The elastomeric phase comprises, as an optional component, a repeating unit derived from a polyethylenically unsaturated “crosslinkable” monomer such as butylene diacrylate, divinylbenzene, butenediol dimethacrylate, trimethylolpropane tri (meth) acrylate. May be contained in a small amount, for example, up to 5 wt%. As used herein, "
The term "polyethylenically unsaturated" means having two or more ethylenically unsaturated sites in one molecule.

[0044] The elastomeric phase may comprise a repeating unit derived from a polyethylenically unsaturated "grafting" monomer, particularly in embodiments where the elastomeric phase has repeating units derived from an alkyl (meth) acrylate monomer. Small units, eg 5
It may contain up to wt%. Suitable graft-linking monomers include a first ethylenically unsaturated moiety having a reactivity similar to that of the monoethylenically unsaturated monomer from which each backbone or branch is derived, and an elastomer. A second ethylenically unsaturated site having a relative reactivity substantially different from the reactivity of the monoethylenically unsaturated monomer from which the phase was derived, and during synthesis of the elastomeric phase, One site reacts,
There are monomers in which the second site is made available during subsequent reactions under different reaction conditions, such as the synthesis of a rigid thermoplastic phase. Suitable graft-linking monomers include, for example, allyl methacrylate, diallyl maleate, triallyl cyanurate.

In a preferred embodiment, the elastomeric phase comprises from 60 to 100 wt% of repeating units derived from one or more conjugated diene monomers, from a vinyl aromatic monomer and a monoethylenically unsaturated nitrile monomer. It contains 0 to 40% by weight of a repeating unit derived from one or more selected monomers, for example, from a styrene-butadiene copolymer, an acrylonitrile-butadiene copolymer or a styrene-butadiene-acrylonitrile copolymer. Become.

In another preferred embodiment, the elastomeric phase comprises one or more (C ₁ -C ₁₂ )
Contains repeating units derived from alkyl acrylate monomers. In a further preferred embodiment, the rubbery polymer backbone comprises one or more (C ₁ -C ₁₂ ) alkyl acrylate monomers, and more preferably one selected from ethyl acrylate, butyl acrylate and n-hexyl acrylate. It contains 40 to 95 wt% of repeating units derived from the above monomers.

In a preferred embodiment, the production of the elastomeric phase is optionally carried out in the presence of a radical initiator such as an azonitrile initiator, an organic peroxide initiator, a persulfate initiator or a redox initiator system. Aqueous emulsion polymerization in the presence of a chain transfer agent, such as an alkyl mercaptan, causes coagulation to form particles of the elastomer phase material. In a preferred embodiment, the emulsion polymerized particles of the elastomeric phase material have a weight average particle size as measured by light transmission of 50-800 nm, more preferably 100-500 nm. Optionally, the size of the emulsion polymerized elastomeric particles can be increased by mechanical or chemical agglomeration of the emulsion polymerized particles according to known techniques.

(B) Hard Thermoplastic Phase The hard thermoplastic resin phase is composed of one or more thermoplastic polymers and has a Tg of more than 25 ° C., preferably a Tg of 90 ° C. or more, more preferably a Tg of 100 ° C. or more. Have.

In a preferred embodiment, the rigid thermoplastic phase is selected from the group consisting of (C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers, vinyl aromatic monomers and monoethylenically unsaturated nitrile monomers. Or a mixture of two or more such polymers derived from one or more of the above-described monomers.
Suitable (C ₁ -C ₁₂₎ alkyl (meth) acrylate monomers, vinyl aromatic monomers and monoethylenically unsaturated nitrile monomers are those mentioned in the description of the elastomeric phase as described above.

In a highly preferred embodiment, the rigid thermoplastic phase comprises one or more vinyl aromatic polymers. Suitable vinyl aromatic polymers contain at least 50 wt% of repeating units derived from one or more vinyl aromatic monomers.

In a preferred embodiment, the rigid thermoplastic phase comprises a first repeat unit derived from one or more vinyl aromatic monomers and one or more monoethylenically unsaturated nitrile monomers. And a vinyl aromatic polymer having a second repeating unit.

The rigid thermoplastic phase is prepared by known methods, for example by bulk polymerization, emulsion polymerization, suspension polymerization or a combination thereof, wherein at least a part of the rigid thermoplastic phase is free of unsaturated sites present in the elastomer phase. Chemically bonds, or "grafts," to the elastomeric phase via a reaction with Unsaturation sites in the elastomer phase, for example,
It is provided by the unsaturated sites remaining in the repeating unit derived from the conjugated diene or the unsaturated sites remaining in the repeating unit derived from the graft-linking monomer.

In a preferred embodiment, at least a portion of the rigid thermoplastic phase is produced by an aqueous emulsion or aqueous suspension polymerization reaction in the presence of an elastomer phase and a polymerization initiator system, such as a heat or redox initiator system. .

In another preferred embodiment, at least a portion of the thermoplastic phase has particles of a material that will form an elastomeric phase dispersed in a monomer mixture that will form a rigid thermoplastic phase. Thereafter, the mixture is produced by a bulk polymerization method in which monomers of the mixture are polymerized to form a rubber-modified thermoplastic resin.

The amount of grafting that takes place between the hard thermoplastic phase and the elastomer phase will vary depending on the relative amount and composition of the elastomer phase. In a preferred embodiment, 10-90 wt% of the hard thermoplastic phase, preferably 30-80 wt%, more preferably 65-80 wt%.
80% by weight chemically grafts to the elastomeric phase, 10 to 9 of the hard thermoplastic phase
0 wt%, preferably 20-70 wt%, more preferably 20-35 wt% remains in a "free" state, i.e. without grafting.

The hard thermoplastic phase of the rubber-modified thermoplastic can be formed by (i) polymerization alone performed in the presence of the elastomer phase, or (ii) by polymerization in the presence of the elastomer phase. It can also be formed by adding one or more types of hard thermoplastic polymers separately polymerized to the hard thermoplastic polymer that has been used. In a preferred embodiment, less than 10 pbw, more preferably less than 5 pbw, of a separately polymerized rigid thermoplastic polymer is added to 100 pbw of the thermoplastic resin composition of the present invention. Most preferably, a separately polymerized hard thermoplastic polymer is not added to the thermoplastic resin composition of the present invention.

In a preferred embodiment, the rubber-modified thermoplastic has repeating units derived from one or more conjugated diene monomers and optionally further comprises a vinyl aromatic monomer and a monoethylenically unsaturated monomer. A rigid thermoplastic phase comprising a vinyl aromatic monomer and a monoethylenic monomer, wherein the elastomeric phase comprises a polymer comprising repeating units derived from one or more monomers selected from saturated nitrile monomers. It is composed of a polymer having a repeating unit derived from one or more monomers selected from unsaturated nitrile monomers.

Individual Polymerization of Elastomer Phase and Rigid Thermoplastic Phase of Rubber-Modified Thermoplastic
The body is made up of the optional ingredients, provided that the Tg requirement for each phase is satisfied.
And 10 w of a third repeating unit derived from one or more other copolymerizable monomers.
t%, such copolymerizable monomers include, for example, acrylic
Monoethylenically unsaturated carboxylic acids, such as phosphoric acid, methacrylic acid or itaconic acid;
Hydroxy (C such as hydroxyethyl methacrylate₁-C₁₂) Alkyl (
(Meth) acrylate monomers, such as cyclohexyl methacrylate (C_Four-C_{1 Two} ) Cycloalkyl (meth) acrylate monomer, acrylamide and methacryl
(Meth) acrylamide monomers such as amides, N-alkylmaleimides and N-
Maleimide monomers such as arylmaleimide, maleic anhydride, vinyl acetate and
And vinyl esters such as vinyl propionate. As used herein, “(C _Four -C₁₂) Cycloalkyl "is a group having from 4 to 12 carbon atoms per group.
Means the cyclic alkyl substituent, and the term "(meth) acrylamide"
Mid and methacrylamide are generically referred to.

[0059]Fluoropolymer additive Suitable fluoropolymers and methods for making such fluoropolymers are known.
For example, U.S. Pat. Nos. 3,671,487, 3,723,373 and 3,703
See 383092. Suitable fluoropolymers include one or more fluoropolymers.
A homopolymer comprising a repeating unit derived from a fluorinated olefin monomer; and
There are copolymers. The term "fluorinated olefin monomer" refers to one or more fluorine atoms.
It means an olefin monomer having an atomic substitution. Suitable fluorinated olefin monomer
In the body, for example, CF_Two= CF_Two, CHF = CF_Two, CH_Two= CF_Two, CH_Two= CHF
, CCIF = CF_Two, CCl_Two= CF_Two, CCIF = CCIF, CHF = CCl_Two,
CH_Two= CCIF and CCl_Two= Fluoroethylenes such as CCIF, and CF_Three
CF = CF_Two, CF_ThreeCF = CHF, CF_ThreeCH = CF_Two, CF_ThreeCH = CH_Two, CF _Three CF = CHF, CHF_TwoCH = CHF and CF_ThreeCH = CH_TwoFluoroprop
There are rens. In a preferred embodiment, the fluorinated olefin monomer is tetraflu
Oroethylene (CF_Two= CF_Two), Chlorotrifluoroethylene (CCIF = CF _Two ), Vinylidene fluoride (CH_Two= CF_Two) And hexafluoropropylene (CF_Two = CFCF_Three).

[0060] Suitable fluorinated olefin homopolymers include, for example, poly (tetrafluoroethylene), poly (hexafluoropropylene).

Suitable fluorinated olefin copolymers include, for example, copolymers containing repeating units derived from two or more fluorinated olefin copolymers, such as poly (tetrafluoroethylene-hexafluoropropylene) And one or more fluorinated monomers such as poly (tetrafluoroethylene-ethylene-propylene) copolymers and one or more non-fluorinated monoethylenic copolymers copolymerizable with the fluorinated monomers. There are copolymers containing repeating units derived from saturated monomers. Suitable non-fluorinated monoethylenically unsaturated monomers include olefin monomers such as ethylene, propylene and butene, acrylate monomers such as methyl methacrylate and butyl acrylate, cyclohexyl vinyl ether, ethyl vinyl ether and n-butyl vinyl ether. And vinyl esters such as vinyl acetate and vinyl versatate.

[0062] In a highly preferred embodiment, the fluoropolymer is a poly (tetrafluoroethylene) homopolymer ("PTFE").

In a preferred embodiment, the fluoropolymer is added to the rubber-modified thermoplastic in the form of a fluoropolymer additive consisting of fluoropolymer particles encapsulated in a second polymer.

In a preferred embodiment, the fluoropolymer additive comprises 30-70 wt%, more preferably 40-60 wt%, of the fluoropolymer and 30-70 wt%, more preferably 40-60 wt% of the second polymer. Become.

To produce the fluoropolymer additive, a fluoropolymer in the form of an aqueous dispersion of fluoropolymer particles is combined with a second polymer, and the combined fluoropolymer particles and second polymer are combined with the second polymer. After precipitation, the precipitate is dried to form the fluoropolymer additive. In a preferred embodiment, the fluoropolymer particles range in size from 50 to 500 nanometers ("nm") as measured by electron microscopy.

In a preferred embodiment, the fluoropolymer additive is prepared by emulsion polymerizing one or more monoethylenically unsaturated monomers in the presence of the aqueous fluoropolymer dispersion of the present invention. Form a second polymer below. Suitable monoethylenically unsaturated monomers are those disclosed above. Next, the emulsion is precipitated by addition of sulfuric acid or the like. This precipitate is dehydrated by centrifugation or the like,
It is then dried to obtain a fluoropolymer additive comprising a fluoropolymer and an associated second polymer. The dry emulsion polymerized fluoropolymer additive is in the form of a free flowing powder.

In a preferred embodiment, the monoethylenically unsaturated monomers that are emulsion polymerized to form a second polymer include vinyl aromatic monomers, monoethylenically unsaturated nitrile monomers, and ( It comprises one or more monomers selected from C ₁ -C ₁₂ ) alkyl (meth) acrylate monomers.

In a highly preferred embodiment, the second polymer comprises a repeating unit derived from styrene and acrylonitrile. More preferably, the second polymer consists of 60 to 90 wt% of repeating units derived from styrene and 10 to 40 wt% of repeating units derived from acrylonitrile.

The emulsion polymerization reaction mixture may contain, as an optional component, emulsified or dispersed particles of the third polymer (eg, an emulsified butadiene rubber latex or the like).

The emulsion polymerization reaction includes, for example, organic peroxide compounds such as benzoyl peroxide, persulfate compounds such as potassium persulfate, and 2,2′-azobis-2,3,3-trimethylbutyronitrile. It is started with a conventional radical initiator such as an azonitrile compound or a redox initiator system such as a combination of cumene hydroperoxide, ferrous sulfate, tetrasodium pyrosulfate and reducing sugars or sodium formaldehyde sulfoxylate.

[0071] To reduce the molecular weight of the second polymer, the reaction vessel during the polymerization reaction, such as an optional ingredients such as nonyl mercaptan and t- dodecyl mercaptan (C ₉ -
A chain transfer agent such as C ₁₃ ) alkyl mercaptan compound may be added. In a preferred embodiment, no chain transfer agent is used.

In a preferred embodiment, the stabilized fluoropolymer dispersion is charged to a reaction vessel and heated with stirring. The initiator system and one or more monoethylenically unsaturated monomers are then charged to the reaction vessel and heated to polymerize the monomers in the presence of the fluoropolymer particles of the dispersion to form a second polymer. To form

[0073] Suitable fluoropolymer additives and emulsion polymerization methods are described in EP-A-0739.
No. 914.

[0074] In a preferred embodiment, the weight average molecular weight of the second polymer ^{75 × 10 3 ~800 × 10 3} ( "Mw"), number average molecular weight of ^{30 × 10 3 ~200 × 10 3} ( "Mn"
) And a polydispersity (Mw / Mn) of 6 or less.

Phosphorus-Containing Flame Retardant Compounds Phosphorus-containing compounds suitable as the phosphorus-containing flame retardant compounds of the present invention are known compounds, such as triphenyl phosphate, tricresyl phosphate, tolyl phosphate, diphenyl tricresyl phosphate, phenyl There are monophosphate esters such as bisdodecyl phosphate, ethyl diphenyl phosphate, as well as diphosphate esters and oligomeric phosphates such as resorcinol diphosphate, diphenyl hydrogen phosphate, bisphenol A diphosphate, 2-ethylhexyl hydrogen phosphate. Suitable oligomeric phosphate compounds are described in commonly assigned "Aromatic Polycarbonate,
A polymer mixture comprising a styrene-containing copolymer and / or a graft copolymer and a flame retardant, and an article formed from the polymer mixture "by Johannes C.
Gossens) et al., U.S. Patent No. 5,672,645, the disclosure of which is incorporated herein by reference.

In a preferred embodiment, the phosphorus-containing compounds of the present invention are oligomeric compounds having the following structural formula (IV):

[0077]

Embedded image

Wherein R ₁ , R ₂ , R ₃ , R ₄ are each independently aryl, optionally substituted with halogen or alkyl, and X is arylene, optionally with halogen or alkyl. A, b, c and d may each independently be 0 or 1
And n is an integer of 1 to 5.

The term “aryl” as used herein refers to a monovalent group containing one or more aromatic rings per group, optionally wherein one or more aromatic rings is one or more alkyl groups (each preferably May be substituted with (C ₁ -C ₆ ) alkyl), and when the group contains two or more rings, it may be a condensed ring.

As used herein, the term “arylene” refers to a divalent group containing one or more aromatic rings per group, optionally with one or more aromatic rings having one or more alkyl groups (each preferably May be substituted with (C ₁ -C ₆ ) alkyl), and when the divalent group contains two or more rings, the ring may be a condensed ring, or an alkylene or alkylidene And any of them may be substituted with a halogen or a (C ₁ -C ₆ ) alkyl group at _one or more sites on the aromatic ring.

In a preferred embodiment, X is a group derived from resorcinol or hydroquinone.

In a preferred embodiment, R ₁ , R ₂ , R ₃ , R ₄ are each phenyl, and a, b,
c and d are each 1; X is phenylene; n is 2; or the phosphate-containing compound is a phosphorus compound having an average value of n of 1-2, more preferably 1.2-1.7. It is a blend of contained oligomers.

Other Additives The thermoplastic resin composition of the present invention may contain, as optional components, various conventional additives, for example, as described below.

(1) Antioxidants, for example, organic phosphites such as tris (nonyl-phenyl) phosphite, (2,4,6-tri-tert-butylphenyl) (2
-Butyl-2-ethyl-1,3-propanediol) phosphite, bis (2
4-di-t-butylphenyl) pentaerythritol diphosphite or distearylpentaerythritol diphosphite and the like, and alkylated monophenols, polyphenols, alkylation reaction products of polyphenols and dienes, such as p-cresol and diene Alkylated hydroquinones, hydroxylated thiodiphenyl ethers, alkylidene-
Bisphenols, benzyl compounds, acylaminophenols, β- (3,5
Ester of di-tert-butyl-4-hydroxyphenol) propionic acid with a monohydric or polyhydric alcohol, β- (5-tert-butyl-4-hydroxy-
Ester of 3-methylphenyl) propionic acid with a monohydric or polyhydric alcohol, β
Esters of-(5-tert-butyl-4-hydroxy-3-methylphenyl) propionic acid with monohydric or polyhydric alcohols, esters of thioalkyl or thioaryl compounds such as distearyl thiopropionate, dilauryl thiopropion , Ditridecylthiodipropionate and the like, β- (3,5-di-tert)
-Butyl-4-hydroxyphenol) amides of propionic acid and the like.

(2) UV absorbers and light stabilizers, such as (i) 2- (2′-hydroxyphenyl) benzotriazoles, 2-hydroxy-benzophenones, (ii) esters of substituted and unsubstituted benzoic acids , (Iii) acrylates, (iv) nickel compounds and the like.

(3) Metal deactivators, for example, N, N′-diphenyloxalic acid diamide, 3
-Salicyloylamino-1,2,4-triazole and the like.

(4) Peroxide scavengers, for example, (C ₁₀ -C ₂₀ ) alkyl esters of β-thiodipropionic acid, mercaptobenzimidazole and the like.

(5) Polyamide stabilizer.

(6) Basic co-stabilizers, for example, melamine, polyvinylpyrrolidone, triallyl cyanurate, urea derivatives, hydrazine derivatives, amines, polyamides, polyurethanes and the like.

(7) Sterically hindered amines such as triisopropanolamine or 2,4
-Dichloro-6- (4-morpholinyl) -1,3,5-triazine and 1,6-diamine, N, N'-bis (2,2,4,6-tetramethyl-4-piperidenyl)
Reaction products of hexane with polymers.

(8) Neutralizing agents, for example, magnesium stearate, magnesium oxide, zinc oxide, zinc stearate, hydrotalcite and the like.

(9) Fillers and reinforcing materials, for example, silicate, TiO ₂ , glass fiber, carbon black, graphite, calcium carbonate, talc, mica and the like.

(10) Other additives, for example, a lubricant such as pentaerythritol tetrastearate, an EBS wax, a silicone fluid, a plasticizer, an optical brightener, a pigment, a dye, a colorant, a flame retardant, and an antistatic agent , Foaming agent and the like.

(11) Flame retardant additives other than the above-mentioned phosphorus-containing flame retardant additives, for example, borate-based flame retardant compounds.

The thermoplastic resin composition of the present invention can be prepared by melt mixing using, for example, a two-roll mill, a Banbury mixer, or a single-screw or twin-screw extruder under the conditions suitable for producing a blend of components. Prepared by mixing and mixing the components of the composition of the present invention, and in some cases the composition thus obtained may be brought into a granular form, for example by pelletizing or grinding.

The thermoplastic resin composition of the present invention can be usefully molded by various means such as injection molding, extrusion, rotation molding, blow molding, and thermoforming, for example, housings for computers and office equipment, household electric appliances, and the like. Can be molded into

[0097]

【Example】

Examples 1-2 and Comparative Examples C1-C3 The components used in the thermoplastic resin compositions of Examples 1-2 and Comparative Examples C1-C3 of the present invention were as follows.

PC-1: a branched polycarbonate resin having a weight average molecular weight of about 32,000 g / mol derived from bisphenol A and phosgene.

PC-2: a linear polycarbonate resin derived from bisphenol A, phosgene and trimellitic acid trichloride and having a weight average molecular weight of about 31,000 g / mol.

ABS: Emulsion-polymerized acrylonitrile-butadiene-styrene (“ABS
") A graft copolymer comprising 50 pbw of a discontinuous elastomer phase (butadiene) and 50 pbw of a hard thermoplastic phase (75 pbw of styrene and acrylonitrile 2).
Acrylonitrile-butadiene-styrene graft copolymer consisting of 5 pbw copolymer).

TSAN: an additive (50 wt% PTFE, 50 wt% styrene-acrylonitrile copolymer) produced by copolymerizing styrene and acrylonitrile in the presence of an aqueous PTFE dispersion.

RDP: Resorcinol diphosphate (Rheofos RDP, manufactured by FMC Corporation, Ltd.).

TiO ₂ : Titanium dioxide (RFC5, Tioxide Europe
)).

Each composition was prepared by mixing the above components in the relative amounts (pbw) shown in Table I using a twin screw extruder. These compositions were then treated at 255 ° C. for 6 hours.
Samples for testing were formed by injection molding in a mold at 0 ° C.

The samples were tested according to the following method. That is, the melt volume rate (m
The elt volume rate is measured according to ISO 1133 at 260 ° C. with a 5 kilogram weight, the notched Izod impact performance is measured according to ISO 180, the Vicat B temperature is measured according to ISO 306, and the tensile properties are ISO 527.
The flame retardant properties were measured according to UL94 and CSTBNFP92505. The compliance of the composition is such that D requires less than 0.1 wt% fluorine content.
Evaluated according to IN / VDE 0472, 815 parts, test B.

As a result of the test, the melt viscosity (“MVR”) of each composition of Examples 1 and 2 and Comparative Examples C1 to C3 was defined as milliliter / 10 minutes (“ml / 10 min”) and room temperature (“RT "), as 10 ° C. and 0 kilometers notched Izod impact strength at ° C. joules / square meter (" KJ / m ² "), tensile strength and tensile modulus as Newtons / square millimeter (" N / mm ² ") Elongation at break as percent (%) of initial length, Vicat B temperature as ° C., UL94 grade as V-
0, V-1, or V-2, total extinction time in seconds ("s"), flame drip as number per 5 samples, and DIN / VDE 0472, 815 parts, Compliance by Test B and CSTBNFP 92505, respectively. It is shown in Table I as "Pass" or "Fail".

[0107]

[Table 1]

[0108]

【The invention's effect】

Despite satisfying the low fluorine content requirement of DIN / VDE 0472, 815 parts, test B, the compositions of the present invention exhibit unexpectedly high performance and good flame retardant properties.

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Claims (14)

[Claims] 1. A thermoplastic resin composition, comprising: (a) an aromatic polycarbonate resin; and (b) a discontinuous elastomer phase dispersed in a continuous hard thermoplastic phase, wherein at least a portion of the hard thermoplastic phase is A rubber-modified graft copolymer chemically grafted to the elastomeric phase, (c) a phosphorus-containing flame retardant compound, and (d) an amount of a fluoropolymer effective to improve the flame retardant performance of the composition. Wherein the fluorine content of the composition does not exceed 0.1% by weight. 2. A composition comprising 60 to 95 parts by weight of a polycarbonate resin, 1 to 15 parts by weight of a rubber-modified graft copolymer, and 3 to 15 parts by weight of a phosphorus-containing flame retardant compound, based on 100 parts by weight of the composition. Composition 1 wherein the amount of fluoropolymer is
The composition of claim 1, which is effective to provide a fluorine content of the fluoropolymer of 0.038 to 0.1 parts by weight based on 00 parts by weight. 3. The composition according to claim 1, wherein the aromatic polycarbonate resin comprises a linear aromatic polycarbonate resin. 4. The composition of claim 1, wherein the aromatic polycarbonate resin comprises a branched aromatic polycarbonate resin. 5. The method according to claim 1, wherein the elastomer phase is polybutadiene rubber or poly (styrene-styrene).
(Butadiene) rubber, wherein the rigid thermoplastic phase comprises structural units derived from one or more monomers selected from vinyl aromatic monomers and monoethylenically unsaturated nitrile monomers. Item 10. The composition according to Item 1. 6. The hard phase according to claim 5, wherein the hard phase comprises a copolymer derived from a monomer selected from the group consisting of styrene, α-methylstyrene and acrylonitrile.
A composition as described. 7. The phosphorous-containing compound has the structural formula: Wherein R ₁ , R ₂ , R ₃ and R ₄ are each independently aryl and optionally substituted with halogen or alkyl, and X is arylene and optionally substituted with halogen or alkyl. A, b, c and d each independently represent 0
Or 1 and n is an integer of 1 to 5]. 8. The composition according to claim 7, wherein R ₁ , R ₂ , R ₃ and R ₄ are each phenyl, a, b, c and d are each 1 and X is phenylene. 9. The composition according to claim 7, wherein n is 2. 10. The composition of claim 7, wherein the phosphate is a blend of phosphorus-containing oligomers wherein n has an average value of 1-2. 11. The composition according to claim 1, wherein the fluoropolymer is a tetrafluoroethylene polymer. 12. The fluoropolymer emulsion polymerizes one or more monoethylenically unsaturated monomers in the presence of an aqueous dispersion of the fluoropolymer to form a second polymer in the presence of the fluoropolymer. The composition according to claim 1, which is added to the composition in the form of an additive produced thereby. 13. The composition of claim 12, wherein the additive is prepared by emulsion polymerization of styrene and acrylonitrile in the presence of an aqueous dispersion of a fluoropolymer. 14. An article formed from the composition of claim 1.