CA1279420C - Iron oxide pigmented, polycarbonate compositions - Google Patents
Iron oxide pigmented, polycarbonate compositionsInfo
- Publication number
- CA1279420C CA1279420C CA000515022A CA515022A CA1279420C CA 1279420 C CA1279420 C CA 1279420C CA 000515022 A CA000515022 A CA 000515022A CA 515022 A CA515022 A CA 515022A CA 1279420 C CA1279420 C CA 1279420C
- Authority
- CA
- Canada
- Prior art keywords
- iron oxide
- composition
- flame retarding
- bis
- polycarbonate resin
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
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Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/18—Oxygen-containing compounds, e.g. metal carbonyls
- C08K3/20—Oxides; Hydroxides
- C08K3/22—Oxides; Hydroxides of metals
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
- C08L69/00—Compositions of polycarbonates; Compositions of derivatives of polycarbonates
Abstract
IRON OXIDE PIGMENTED, POLYCARBONATE COMPOSITIONS
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a thermoplastic molding composition comprising a polycarbonate resin and a pigmenting amount of black iron oxide. The invention is predicated on the surprising findings that this composition yields stable, streaking-free molded articles. A preferred embodiment of the invention comprises a flame retarding agent and iron oxide based pigment selected from the group consisting of black iron oxide and red iron oxide, said flame retarding agent comprising polytetrafluoroethylene; the composition is charac-terized in that it is streaking-free and in that its flammability rating is at least 5V-1/8" in accordance with UL-94.
ABSTRACT OF THE DISCLOSURE
The present invention is directed to a thermoplastic molding composition comprising a polycarbonate resin and a pigmenting amount of black iron oxide. The invention is predicated on the surprising findings that this composition yields stable, streaking-free molded articles. A preferred embodiment of the invention comprises a flame retarding agent and iron oxide based pigment selected from the group consisting of black iron oxide and red iron oxide, said flame retarding agent comprising polytetrafluoroethylene; the composition is charac-terized in that it is streaking-free and in that its flammability rating is at least 5V-1/8" in accordance with UL-94.
Description
Mo-2727 IRON OXIDE PIGMENTED, POLYCARBONATE COMPOSITIONS
..
Field of the Invention The invention is directed to polycarbonate molding compositions and more particularly to pigmented, polycarbonate compositions.
Summary of the Invention The presen~ invention is directed to a thermoplastic molding composition comprising a polycarbonate resin and a pigmenting amount of iron oxide based pigment. The invention is predicated on the surprising finding that this composition yields stable, streaking-free molding articles. A preferred embodiment of the invention comprises a flame retarding agent and iron oxide based pigment selected from the group ` 15 consisting of black iron oxide and red iron o~ide, said flame retarding agent comprising polytetrafluoro-ethylene; the composition is typically characterized in that it is streaking-Eree and in that its flammability rating is at leas~ 5V~ " in accordance with UL-94.
BACKGROUND OF T~E INVENTION
.. .. _ .
Streaking is a term of art used to describe a ~articular surfacial, cosmetic defect in a molded part.
It is believed that this defect which appears as striations in molded pigmented articles results from poor dispersion of the pigment. Molding prepared from flame retardant, pigmented polycarbonates are sus-- ceptible to streaking particularly if the composition contains (polytetra:Eluoroethylene) PTFE.
Dispersion is defined as the breaking up of agglomerates of individual pigment particles which are held together by surface and/or electrostatic forces.
Mb-2727 '1 J~
After the breaking up of the agglomerations - by shearing action - the individual pigment particles must be wetted immediately if reagglomeration is to be pre-vented. A thorough dispersion of the pigment particles is essential in order to prevent pitting and streaking on the surfaces of extruded molded articles. Several solutions to the dispersion problem have been offered including adding dispersion aids - for instance, poly-ethylene glycol - and applying to the polycarbonate a low shear rate while applying a high shear rate to the pigment - U.S. Patent 3,507,951. It is noted that this patent at col. 4, lines 20 et seq. regards iron oxide pigment to be the equivalent of carbon black. Also, U.S. Patent 4,27~,244 is noted ~o regard carbon black to be the equivalent of iron oxide pigments in a poly-carbonate matrix - see col. ~.2, lines 24-25. Polymeric compounds containing olefinic unsaturation and epoxide groups were disclosed in U.S. Patent 3,761,440 to be useful in reducing the deleterious effects caused by moisture in pigmented polycarbonates. Silica has been disclosed in U.S. Patent 4,049,614 to aid in dispersing pigments in polycarbonate resins. U.S. Patent 3,875,123 disclosed polymeric UV absorbers for stabi-lizing polycarbonates including pigmented polycar-bonates. U.S. Patent 4,017,457 which discloses fer-rocene and ferrocene derivatives indicated that iron oxide can not be used as pigmentation agents in polycar-bonates because such iron compounds cause color in-stability and are detrimental to the mechanical proper-ties of the resin - see col. 3, lines 32 et seq. U.S.
Patent 4,289,745 disclosed acicular ferrite spinels said to be suitable as pigments in polycarbonates.
Lastly, ~he art is noted to disclose the use of red and Mo-2727 yellow lron oxide pigments in polycarbonate resins in Transparent Iron Oxide Pig_ents for Automotive Appll-cations, Wolfgang E. Adams, NATEC '83 Society of Plastics Engineers, Brookfield Center Conn. p. 19-20.
5 The suitability of iron oxide pigments in the context of the present invention is surprising in view of the art's teaching that black iron oxide starts to change color from black to brown (and finally red) at temperatures above 365F, which is considerably below 10 th~ processing tempera~ure of polycarbonate resins, i.e., 520F.
DETAILED DESCRIPTION OF THE INVENTION
. . . _ _ The Polvcarbonate Resin .L
The polycarbonate resins useful in the 15 practice of the invention are homopolycarbonates, co-polycarbonates and terpolycarbonates or mixtures thereof. The polycarbonates generally have a molecular weight of 10,000-200,000 (weight average molecular weight), preferably 20,000-80,000 and their 20 melt flow rate, per ASTM D-1238 at 300C, is about 1 to about 24 gm/10 min, preferably about 2-21 gm/10 min. They may be prepared, for example, by the known diphasic interface process from a carbonic acid derivative such as phosgene and dihydroxy compounds by 25 polycondensation (see German Offenlegungsschriften 2,063,050; 2,063,052; 1,570,703; 2,211,956; 2,211,957;
French Patent 1,561,518; and the monograph H. Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York, 1964).
In the present context, dihydroxy compounds suitable for the preparation of the copolycarbonates of the invention conform to the structural formulae (1) or (23.
Mo-2727 .
J.
~7~
¦;A) OH (1) (Z)d 5 HO~
(Z) d Hp HO
(2) 0 (Z)f Z)~
wherein A denotes an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cyclo-alkylene group with 5 to 15 carbon atoms, a cyclo-alkylidene group with 5 to 15 carbon atoms, a carbonyl group, an oxygen atom, a sulfur atom, -SO~ or -S02-or a radical conforming to C~3 2 0 CH3 C~13 or CH~ CH3 e and g both denote the number O to l;
Z denot~s F, Cl, Br or Cl-C4-alkyl and if several Z
radicals are substituents in one aryl radical, they may be identical or different;
d denotes O or an integer of from 1 to 4; and f denotes O or an integer of from l to 3.
Among the useful bisphenols in the practice of the invention are hydroquinone 9 resorcinol, bis-(hydroxyphenyl)-alkanes, bis-(hydro~yphenyl)-ethers, bis-(hydroxyphenyl~-ketones, bis-(hydroxyphenyl)-sulfoxides, bis-(hydroxyphenyl)-sulfides, bis-~hydroxy-- Mo-2727 ~ PC-185 phenyl~-sulfones and ~,~'-bis-(hydroxyphenyl)-diiso-propyl-benzenes, as well as their nuclear-alkylated compounds. These and further suitable aromatic di-hydrox~ compo~mds are described, for example, in U.S.
S Pa-tents 3,028,356; 2,999,835; 3,148,172; 2,991,273;
..
Field of the Invention The invention is directed to polycarbonate molding compositions and more particularly to pigmented, polycarbonate compositions.
Summary of the Invention The presen~ invention is directed to a thermoplastic molding composition comprising a polycarbonate resin and a pigmenting amount of iron oxide based pigment. The invention is predicated on the surprising finding that this composition yields stable, streaking-free molding articles. A preferred embodiment of the invention comprises a flame retarding agent and iron oxide based pigment selected from the group ` 15 consisting of black iron oxide and red iron o~ide, said flame retarding agent comprising polytetrafluoro-ethylene; the composition is typically characterized in that it is streaking-Eree and in that its flammability rating is at leas~ 5V~ " in accordance with UL-94.
BACKGROUND OF T~E INVENTION
.. .. _ .
Streaking is a term of art used to describe a ~articular surfacial, cosmetic defect in a molded part.
It is believed that this defect which appears as striations in molded pigmented articles results from poor dispersion of the pigment. Molding prepared from flame retardant, pigmented polycarbonates are sus-- ceptible to streaking particularly if the composition contains (polytetra:Eluoroethylene) PTFE.
Dispersion is defined as the breaking up of agglomerates of individual pigment particles which are held together by surface and/or electrostatic forces.
Mb-2727 '1 J~
After the breaking up of the agglomerations - by shearing action - the individual pigment particles must be wetted immediately if reagglomeration is to be pre-vented. A thorough dispersion of the pigment particles is essential in order to prevent pitting and streaking on the surfaces of extruded molded articles. Several solutions to the dispersion problem have been offered including adding dispersion aids - for instance, poly-ethylene glycol - and applying to the polycarbonate a low shear rate while applying a high shear rate to the pigment - U.S. Patent 3,507,951. It is noted that this patent at col. 4, lines 20 et seq. regards iron oxide pigment to be the equivalent of carbon black. Also, U.S. Patent 4,27~,244 is noted ~o regard carbon black to be the equivalent of iron oxide pigments in a poly-carbonate matrix - see col. ~.2, lines 24-25. Polymeric compounds containing olefinic unsaturation and epoxide groups were disclosed in U.S. Patent 3,761,440 to be useful in reducing the deleterious effects caused by moisture in pigmented polycarbonates. Silica has been disclosed in U.S. Patent 4,049,614 to aid in dispersing pigments in polycarbonate resins. U.S. Patent 3,875,123 disclosed polymeric UV absorbers for stabi-lizing polycarbonates including pigmented polycar-bonates. U.S. Patent 4,017,457 which discloses fer-rocene and ferrocene derivatives indicated that iron oxide can not be used as pigmentation agents in polycar-bonates because such iron compounds cause color in-stability and are detrimental to the mechanical proper-ties of the resin - see col. 3, lines 32 et seq. U.S.
Patent 4,289,745 disclosed acicular ferrite spinels said to be suitable as pigments in polycarbonates.
Lastly, ~he art is noted to disclose the use of red and Mo-2727 yellow lron oxide pigments in polycarbonate resins in Transparent Iron Oxide Pig_ents for Automotive Appll-cations, Wolfgang E. Adams, NATEC '83 Society of Plastics Engineers, Brookfield Center Conn. p. 19-20.
5 The suitability of iron oxide pigments in the context of the present invention is surprising in view of the art's teaching that black iron oxide starts to change color from black to brown (and finally red) at temperatures above 365F, which is considerably below 10 th~ processing tempera~ure of polycarbonate resins, i.e., 520F.
DETAILED DESCRIPTION OF THE INVENTION
. . . _ _ The Polvcarbonate Resin .L
The polycarbonate resins useful in the 15 practice of the invention are homopolycarbonates, co-polycarbonates and terpolycarbonates or mixtures thereof. The polycarbonates generally have a molecular weight of 10,000-200,000 (weight average molecular weight), preferably 20,000-80,000 and their 20 melt flow rate, per ASTM D-1238 at 300C, is about 1 to about 24 gm/10 min, preferably about 2-21 gm/10 min. They may be prepared, for example, by the known diphasic interface process from a carbonic acid derivative such as phosgene and dihydroxy compounds by 25 polycondensation (see German Offenlegungsschriften 2,063,050; 2,063,052; 1,570,703; 2,211,956; 2,211,957;
French Patent 1,561,518; and the monograph H. Schnell, "Chemistry and Physics of Polycarbonates", Interscience Publishers, New York, 1964).
In the present context, dihydroxy compounds suitable for the preparation of the copolycarbonates of the invention conform to the structural formulae (1) or (23.
Mo-2727 .
J.
~7~
¦;A) OH (1) (Z)d 5 HO~
(Z) d Hp HO
(2) 0 (Z)f Z)~
wherein A denotes an alkylene group with 1 to 8 carbon atoms, an alkylidene group with 2 to 8 carbon atoms, a cyclo-alkylene group with 5 to 15 carbon atoms, a cyclo-alkylidene group with 5 to 15 carbon atoms, a carbonyl group, an oxygen atom, a sulfur atom, -SO~ or -S02-or a radical conforming to C~3 2 0 CH3 C~13 or CH~ CH3 e and g both denote the number O to l;
Z denot~s F, Cl, Br or Cl-C4-alkyl and if several Z
radicals are substituents in one aryl radical, they may be identical or different;
d denotes O or an integer of from 1 to 4; and f denotes O or an integer of from l to 3.
Among the useful bisphenols in the practice of the invention are hydroquinone 9 resorcinol, bis-(hydroxyphenyl)-alkanes, bis-(hydro~yphenyl)-ethers, bis-(hydroxyphenyl~-ketones, bis-(hydroxyphenyl)-sulfoxides, bis-(hydroxyphenyl)-sulfides, bis-~hydroxy-- Mo-2727 ~ PC-185 phenyl~-sulfones and ~,~'-bis-(hydroxyphenyl)-diiso-propyl-benzenes, as well as their nuclear-alkylated compounds. These and further suitable aromatic di-hydrox~ compo~mds are described, for example, in U.S.
S Pa-tents 3,028,356; 2,999,835; 3,148,172; 2,991,273;
3,271,367; and 2,999,846. Further examples of suitable bisphenols are 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol-A), 2,4-bis~(hydroxyphenyl)-2-methyl-butane, l,l-bis-(4-hydroxyphenyl)-cyclohexane, 10 ~ bis-(4-hydroxyphenyl)-p-diisopropyl-benzene, 2,2-bis-(3-methyl-4-hydroxyphenyl)-propane, 2,2-bis-(3-chloro-~-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxyphenyl)-methane, 2,2-bis-(3,5-dime~hyl-4-hydroxyphenyl)-propane, bis-(3,5-dimethyl-4-hydroxy-15 phenyl)-sulfide, bis-(3,5-dimethyl-4-hydroxyphenyl)-sulfoxide, bis-(3,5 dimethyl-4-hydroxyphenyl)-sulfone, hydroxybenzophenone, 2,4-bis-(3,5-dimethyl-4-hydroxy-phenyl)-2-methylbutane, 1,1-bis-(3,5-dimethyl-4-hydroxyphenyl)-cyclohexane, ~,~'-bis-(3,5-dimethyl-20 4-hydroxyphenyl)-p-diisopropyl benzene, and 4,4'-sulfonyldiphenyl.
Examples of particularly preferred aromatic bisphenols are 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane and 25 1,1-bis-(4-hydroxyphenyl)-cyclohexane.
The most preferred bisphenol is 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol-A).
The polycarbonates of the invention may entail in their structure units derived from one or 30 more of the suitable bisphenols.
Among the resins suitable in the practice of the invention are included phenolphthalein-based polycarbonate, copolycarbonates and terpolycarbonates Mo-2727 ,.
such as are described in U.S. Patents 3,036,036 and 4,210,741. ~lso suitable are the resins described in U.S. Patent 4,515,921.
The polycarbonates o~ ~he invention may also 5 be branched by condensing therein small quan~ities, e.g., 0.05-2.0 mol ~ (based on the quantity of bis-phenols used) of polyhydroxyl compounds. Polycar-bonates of this type have been described, for example~
in German Offenlegungsschriften 1,570,553; 2,116,974 10 and 2,113,374; British Patents 885,442 and 1,079,821 and U.S. Patents 3,544,514 and 4,185,009. The follow-ing are some examples of polyhydro~yl compounds which may be used for this purpose: phloroglucinol;
4,6-dimethyl-2,4,6-tri-(4-hydro~yphenyl)-heptane;
15 1,3,5-tri-(4-hydroxyphenyl)-ethane; tri-(4-hydroxy-phenyl)-phenylmethane; 2,2-bis~[4,4-(4,4'-dihydroY~y-diphenyl)-cyclohexyl]-propane; 2,4-bis-(4-hydroxy-1-isopropylidine)-phenol; 2,6-bis-(2'-dihydroxy-5'-methylbenzyl)-4-methylphenol; 2,4-dihydroxy-benzoic 20 acid; 2--(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane and 1,4-bis-(4',4"-dihydroxytriphenylmethyl)-benzene. Some of the other polyf~mctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(4-hydroxyphenyl)-2-oxo-2,3-25 dihydroindole.
In addition to the polycondensation processmentioned above, other processes for the preparation of the polycarbonates of the invention are polyconden-sation in a homogeneous phase and transesterification.
30 The suitable processes are disclosed in U.S. Patents 3,028,365; 2,999,846; 3,153,008; and 2,991,273.
Mo-2727 The preferred process for the preparation of polycarbonates ls the inter~acial polycondensation process.
Other methods of synthesis in forming the 5 polycarbonates of the invention such as disclosed in U.S. Patent 3,912,688, may be used.
Suitable polycarbonate resins are available in commerce, ~or instance, under the tradenames Merlon-FCR, Merlon M-39, Merlon M-40 and Merlon M-50, 10 all of which are bisphenol-A based on homopoly-carbonate resins differing in terms of their respective molecular weights and characterized in that their melt indices per ASTM D-1238 are 17-24, 12-24, 6-11.9 and 3.0-5.9 gm/10 min, respectively, all 15 available from Mobay Corporation of Pittsburgh, Pennsylvania.
The art has long recognized that red iron oxide (G -Fe203 ) iS relatively heat-stable up to 1000C, while both yellow (~ FeOOH) and black (FE304) 20 iron oxides have a limited thermal stability. The yellow iron oxide starts to dellydrate at about 356F
and its color changes to red. The black iron oxide changes at about the same temperature to ~-FE2O3 (brown) and then to red oxide.
In the context of the present invention black iron oxide pigment was found to be a suitable replacement for prior art carbon black in preparing pigmented polycarbonate articles. In a more preferred embodiment black iron oxide pigment and red iron oxide 30 pigments were found to he most suitable in preparing streaking-free, flame resistant ? PTFE containing polycarbonate moldings.
Mo-2727 PC-1~5 . .
Synthe-tic iron oxide pigments are known.
They may be manufac~ured for instance by the reduction oÇ mononitro~enzene with metallic iron and are readily available in commerce. Among the suitable iron oxide 5 pigments are the black and red iron oxide pigments marketed under tlle tradename Bayferrox*, from ~ayer AG
and from ~lobay Corporation.
The pigments which are suitable in the present context, regardless of their origin, are 10 preferably spheroidal in their particle shape and have a predominant particle si~e beLween 0.01 and 2 micron, more preferably 0.1 ~o 0.6 micron. Most preferably the pigment particles are "microniæed". The micronized pigments - prepared by Jet milling - are 15 characterized in that their particle size is identical to that of the unmicronized version except that the later feature relatively larger agglomerations whereas the micronized versions are of mostly agglomerations consisting of fewer particles.
Polytetrafluoroethylene (PTFE) is well known in the art and its utility as a drip suppressant in flame retarding formulations of polycarbonate resins has long been recognized. In the context of the present invention, PTFE is used at a level of 0.05% to 25 about 1.0~, preferably 0.10-0.6~ relative to the weight of the polycarbonate resin. The preferred PTFE
in the present context is of the type that forms fibrils upon the application of shear, known in the art as ASTM-Type 3.
Flame retardant agents for polycarbonate resins are known in the art. These agents have been widely reported in the paten~ literature and include halogenated compounds, especially brominated compounds *Trademark Mo-2727 _ 9 and most particularly aromatic brominated compounds.
Also included are sulfonate salts of alkali metals or alkaline earth metals. Also included are the complex ion metal salts, such as sodium aluminum fluoride, and s phosphorus compounds. The relevant literature includes U.S. Patent 3,146,254, which discloses tri-bisphenol-A
ester of phosphoric acid, U.S. Patent 3,823,175 relating to halogenated neopentyl chloroformates, U.S.
Patent 4,195,155 entailing disulfonic acid salts and U.S. Patent 4,269,762 relating to tetrahydro-carbylborate salts. Also relevant are U.S. P~tents 3,027,349 (phosphate polymers), 3,475,372 (metal salts of mercap~obenzotriazoles), 3,509,090 (halogenated organosilicones), 3,535,300 (organo metal salts), 3,557,053 (tris-halophenyl phosphates), 3,597,390 (tris-halophenyl phosphites), 3,775,367 (perfluoro sulfonate salts), 3,836,490 (alkali metal salts), 3,875,107 (alkali metal salts), 4,017,457 (ferrocene), 4,098,754 (alkali metal organic salts), 4,100,130 (sul:Eur), 4,174,359 (oligomeric tetrabromo polycar-bonate and sulfonate salts), 4,223,100 (alkali metal salts, PTFE and an aromatically bound bromine) as well as U.S. Patents 3,382,207 (decabromodiphenyl car-bonate), 3,647,747 (barium carbonate), 3,651,174 (BaCO3, organosiloxane and PTFE)9 3,796,772 (titanates), 3,867,336 (an aryloxy substituted poly-halogenated aromatic compound~; U.S. Patents 3,9319100, 3,940,36~, 3,951,910, 3,953,396, 3,978,024, 4,001,175, 4,007,175, 4,032,5069 4,033,930, 4,039,509, 490649101, 4,067,846, 49073,768, 49075,164, 49093,590, 4,093,5~9, 4,1049245, 4,104,246, 491159354, 4,153,595, 4,2~1,832, 49263,201, 4,268,429, 3,9099490, 3,917,5599 3,~19,167 (sulfonic acid salts), 3,9339734 (sulfvnates), Mo-2727 :
~ ~7~
3,948,851~ 4,092,291 (sulfone~sulfonic salts), 3,953,399 (carboxylic acid esters), 3,971,756 (alkali metal salts and siloxanes), 4,028,297 (salts of inorganic sulfur oxyacids), 4,066,618 (metal salts of 5 halogenated nonaromatic carboxylic acid), 4,069,201, 4,111,977 ~unsubstituted or halogenated oxocarbon acids), 4,104,253, 4,113,695 (halogenated organic metal salts), 4,209,427 ~formaldehydes), 4,220,583 (partially florinated olefins), 4,235,978 10 (organopolysiloxanes), 4,241,434 (alkali or alkaline earth metal salts), 4,254,252 (cyclic polyformates) and 4,366,283 (perhalometalates). Preferably the flame retarding agents are complex ion metal salts, sulfonate salts and halogenated aromatic compounds;
15 cryolite is most preferred.
The compositions of the invention may contain about 0.04 to about 4.0 gms of black iron oxide per 1 po~md of polycarbonate resin. In the preferred flame resistant embodiment, the compositions contain 20 about 0.06 to about 3.0% of a paclcage of a flame retarding agent and PTFE. Preferably the amount of the flame retarding agent and PTFE is that which is sufficient to render the composition a flammability rating of IJL,-94-5V (1/8" specimens). More preferably 25 the amo~mt of flame retarding agent is about 0.01 to about 2.0~, most preferably 0.05-1.0~. The amount of iron oxide pigment in the composition is typically about 0.04 to about 4.0 gms per 1 pound of polycarbonate resin.
The invention is further illustrated, but is not intended to be limited by the following examples in which all parts and percentages are by weight unless oth~rwise specified.
~o-2727 ~, L2~3 EXAMPLES
Experimental 1. Flame resistant, pigmented polycarbonate compositions were prepared in accordance with the invention and their surface properties in terms of streaking were compared to prior art compositions.
Essentially it was found that the PTFE-containing, iron oxide pigmented compositions were streak-free whereas the comparable prior art compositions which were similar ~hereto in all respects~ e~cept for the substltution of carbon black for iron oxide, exhibited an objectionable degree o~ streaking. In carrying out the comparison, the compositions contain d about 96%
polycarbonate resin (a 1:1 mixture of linear and branched BPA-derived homopolymers) 0.4~ cryolite and 0.31~ of PTFE (ASTM Type 3). To this basic composition there were added in the first instance about 3.7% of a color premix package containing carbon black and in the second instance about 3.8Z of a similar premix package containing iron oxide based black pigment. The premix package contained about 4% of the iron oxide (black) or about 0.5% of carbon black and about 19% of TiO2 as a co-pigment as well as auxiliary additives such as a thermal stabilizer and a mold release a~ent neither of which are critical to the invention. The preparation of the compositions and the molding operation followed conventional procedures known in the polycarbonate - art. The particular pigment used in the compositions of these examples were Bayferrox 318M, a micronized black iron oxide (Fe3O4) having a predominant particle size of about 0.2 microns. Visual inspection of parts molded from the compositions (molded on a 6" x 6" pl~que mold with a melt temperature of 530F and a Mo-2727 mold temperature of 150F) indicated a clear advantage in terms of freedom from streaking to be associated with the parts where iron oxide served as a pigment.
The melt indices of the compositions were in the range of about 5-6 gm/10 min; all exhibited a flammability rating of V-0 in accordance with UL-94 (l/16"
specimens) and all passed UL-94 5V rating (1/8"
specimens). The mechanical properties of the compositions of the invention were virtually identical to those o the prior art compositions where carbon black was used as a pigment even though substantially more iron oxide derived pigment was used to obtain pigmentation equivalent to the carbon black.
2. The data reported below summarized the findings respecting the properties o iron o~ide black, pigmented polyearbonate compositions as a function of the loading o pigment (318M3 with and without TiO2 as a co-pigment. The data points to the surprising degree of stability of the iron oxide pigments in polycarbonate moldings, at molding temperatures of up to 650F.
Mo-2727 A(~ B(a) C
Polycarbonate resin1 lb. 1 lb. 1 lb. 1 lb.
Black Iron Oxide(l)0.06 0.9 0.06 0.9 TiO2 6.8 6.8 Color Light Dark Trans- Opaque Grey Grey parent Black Black Melt flow, gm/10 min.
550F molding, 3S sec. cycle time 10.97 10.90 10.60 11.0 700F molding, 60 sec. cycle time 14~15 16.30 13.00 12.90 Color stability Color difference (AE) 550-600F 0.75 0.99 1.91 0.37 550-650F 0.09 0.51 3.11 0.59 550-700F 1.53 1.76 3.65 0.60 Impact strength, Izod-Notched, (ft. lbs/in.) 550F molding, 35 sec. 15.8 15.7 15.6 15.4 ` 700F molding, 60 sec. 15.8 15.8 15.7 15.5 Relative viscosity, extruded pellets 1.264 1.272 1.265 1.272 material molded ~t 550F 1.264 1.267 1.267 1.272 650F 1.268 1.259 1.267 1.265 700F 1.252 1.247 1.259 1.247 (1) gms/l lb. of polycarbonate.
(a) Compositions A and B contain a melt-stabilizer having no criticality to the invention.
~o-2727 Although the invention has been described in detail in the foregoing for the purpose of illustr~tion, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo-2727 PC-1~5
Examples of particularly preferred aromatic bisphenols are 2,2-bis-(4-hydroxyphenyl)-propane, 2,2-bis-(3,5-dimethyl-4-hydroxyphenyl)-propane and 25 1,1-bis-(4-hydroxyphenyl)-cyclohexane.
The most preferred bisphenol is 2,2-bis-(4-hydroxyphenyl)-propane (bisphenol-A).
The polycarbonates of the invention may entail in their structure units derived from one or 30 more of the suitable bisphenols.
Among the resins suitable in the practice of the invention are included phenolphthalein-based polycarbonate, copolycarbonates and terpolycarbonates Mo-2727 ,.
such as are described in U.S. Patents 3,036,036 and 4,210,741. ~lso suitable are the resins described in U.S. Patent 4,515,921.
The polycarbonates o~ ~he invention may also 5 be branched by condensing therein small quan~ities, e.g., 0.05-2.0 mol ~ (based on the quantity of bis-phenols used) of polyhydroxyl compounds. Polycar-bonates of this type have been described, for example~
in German Offenlegungsschriften 1,570,553; 2,116,974 10 and 2,113,374; British Patents 885,442 and 1,079,821 and U.S. Patents 3,544,514 and 4,185,009. The follow-ing are some examples of polyhydro~yl compounds which may be used for this purpose: phloroglucinol;
4,6-dimethyl-2,4,6-tri-(4-hydro~yphenyl)-heptane;
15 1,3,5-tri-(4-hydroxyphenyl)-ethane; tri-(4-hydroxy-phenyl)-phenylmethane; 2,2-bis~[4,4-(4,4'-dihydroY~y-diphenyl)-cyclohexyl]-propane; 2,4-bis-(4-hydroxy-1-isopropylidine)-phenol; 2,6-bis-(2'-dihydroxy-5'-methylbenzyl)-4-methylphenol; 2,4-dihydroxy-benzoic 20 acid; 2--(4-hydroxyphenyl)-2-(2,4-dihydroxyphenyl)-propane and 1,4-bis-(4',4"-dihydroxytriphenylmethyl)-benzene. Some of the other polyf~mctional compounds are 2,4-dihydroxybenzoic acid, trimesic acid, cyanuric chloride and 3,3-bis-(4-hydroxyphenyl)-2-oxo-2,3-25 dihydroindole.
In addition to the polycondensation processmentioned above, other processes for the preparation of the polycarbonates of the invention are polyconden-sation in a homogeneous phase and transesterification.
30 The suitable processes are disclosed in U.S. Patents 3,028,365; 2,999,846; 3,153,008; and 2,991,273.
Mo-2727 The preferred process for the preparation of polycarbonates ls the inter~acial polycondensation process.
Other methods of synthesis in forming the 5 polycarbonates of the invention such as disclosed in U.S. Patent 3,912,688, may be used.
Suitable polycarbonate resins are available in commerce, ~or instance, under the tradenames Merlon-FCR, Merlon M-39, Merlon M-40 and Merlon M-50, 10 all of which are bisphenol-A based on homopoly-carbonate resins differing in terms of their respective molecular weights and characterized in that their melt indices per ASTM D-1238 are 17-24, 12-24, 6-11.9 and 3.0-5.9 gm/10 min, respectively, all 15 available from Mobay Corporation of Pittsburgh, Pennsylvania.
The art has long recognized that red iron oxide (G -Fe203 ) iS relatively heat-stable up to 1000C, while both yellow (~ FeOOH) and black (FE304) 20 iron oxides have a limited thermal stability. The yellow iron oxide starts to dellydrate at about 356F
and its color changes to red. The black iron oxide changes at about the same temperature to ~-FE2O3 (brown) and then to red oxide.
In the context of the present invention black iron oxide pigment was found to be a suitable replacement for prior art carbon black in preparing pigmented polycarbonate articles. In a more preferred embodiment black iron oxide pigment and red iron oxide 30 pigments were found to he most suitable in preparing streaking-free, flame resistant ? PTFE containing polycarbonate moldings.
Mo-2727 PC-1~5 . .
Synthe-tic iron oxide pigments are known.
They may be manufac~ured for instance by the reduction oÇ mononitro~enzene with metallic iron and are readily available in commerce. Among the suitable iron oxide 5 pigments are the black and red iron oxide pigments marketed under tlle tradename Bayferrox*, from ~ayer AG
and from ~lobay Corporation.
The pigments which are suitable in the present context, regardless of their origin, are 10 preferably spheroidal in their particle shape and have a predominant particle si~e beLween 0.01 and 2 micron, more preferably 0.1 ~o 0.6 micron. Most preferably the pigment particles are "microniæed". The micronized pigments - prepared by Jet milling - are 15 characterized in that their particle size is identical to that of the unmicronized version except that the later feature relatively larger agglomerations whereas the micronized versions are of mostly agglomerations consisting of fewer particles.
Polytetrafluoroethylene (PTFE) is well known in the art and its utility as a drip suppressant in flame retarding formulations of polycarbonate resins has long been recognized. In the context of the present invention, PTFE is used at a level of 0.05% to 25 about 1.0~, preferably 0.10-0.6~ relative to the weight of the polycarbonate resin. The preferred PTFE
in the present context is of the type that forms fibrils upon the application of shear, known in the art as ASTM-Type 3.
Flame retardant agents for polycarbonate resins are known in the art. These agents have been widely reported in the paten~ literature and include halogenated compounds, especially brominated compounds *Trademark Mo-2727 _ 9 and most particularly aromatic brominated compounds.
Also included are sulfonate salts of alkali metals or alkaline earth metals. Also included are the complex ion metal salts, such as sodium aluminum fluoride, and s phosphorus compounds. The relevant literature includes U.S. Patent 3,146,254, which discloses tri-bisphenol-A
ester of phosphoric acid, U.S. Patent 3,823,175 relating to halogenated neopentyl chloroformates, U.S.
Patent 4,195,155 entailing disulfonic acid salts and U.S. Patent 4,269,762 relating to tetrahydro-carbylborate salts. Also relevant are U.S. P~tents 3,027,349 (phosphate polymers), 3,475,372 (metal salts of mercap~obenzotriazoles), 3,509,090 (halogenated organosilicones), 3,535,300 (organo metal salts), 3,557,053 (tris-halophenyl phosphates), 3,597,390 (tris-halophenyl phosphites), 3,775,367 (perfluoro sulfonate salts), 3,836,490 (alkali metal salts), 3,875,107 (alkali metal salts), 4,017,457 (ferrocene), 4,098,754 (alkali metal organic salts), 4,100,130 (sul:Eur), 4,174,359 (oligomeric tetrabromo polycar-bonate and sulfonate salts), 4,223,100 (alkali metal salts, PTFE and an aromatically bound bromine) as well as U.S. Patents 3,382,207 (decabromodiphenyl car-bonate), 3,647,747 (barium carbonate), 3,651,174 (BaCO3, organosiloxane and PTFE)9 3,796,772 (titanates), 3,867,336 (an aryloxy substituted poly-halogenated aromatic compound~; U.S. Patents 3,9319100, 3,940,36~, 3,951,910, 3,953,396, 3,978,024, 4,001,175, 4,007,175, 4,032,5069 4,033,930, 4,039,509, 490649101, 4,067,846, 49073,768, 49075,164, 49093,590, 4,093,5~9, 4,1049245, 4,104,246, 491159354, 4,153,595, 4,2~1,832, 49263,201, 4,268,429, 3,9099490, 3,917,5599 3,~19,167 (sulfonic acid salts), 3,9339734 (sulfvnates), Mo-2727 :
~ ~7~
3,948,851~ 4,092,291 (sulfone~sulfonic salts), 3,953,399 (carboxylic acid esters), 3,971,756 (alkali metal salts and siloxanes), 4,028,297 (salts of inorganic sulfur oxyacids), 4,066,618 (metal salts of 5 halogenated nonaromatic carboxylic acid), 4,069,201, 4,111,977 ~unsubstituted or halogenated oxocarbon acids), 4,104,253, 4,113,695 (halogenated organic metal salts), 4,209,427 ~formaldehydes), 4,220,583 (partially florinated olefins), 4,235,978 10 (organopolysiloxanes), 4,241,434 (alkali or alkaline earth metal salts), 4,254,252 (cyclic polyformates) and 4,366,283 (perhalometalates). Preferably the flame retarding agents are complex ion metal salts, sulfonate salts and halogenated aromatic compounds;
15 cryolite is most preferred.
The compositions of the invention may contain about 0.04 to about 4.0 gms of black iron oxide per 1 po~md of polycarbonate resin. In the preferred flame resistant embodiment, the compositions contain 20 about 0.06 to about 3.0% of a paclcage of a flame retarding agent and PTFE. Preferably the amount of the flame retarding agent and PTFE is that which is sufficient to render the composition a flammability rating of IJL,-94-5V (1/8" specimens). More preferably 25 the amo~mt of flame retarding agent is about 0.01 to about 2.0~, most preferably 0.05-1.0~. The amount of iron oxide pigment in the composition is typically about 0.04 to about 4.0 gms per 1 pound of polycarbonate resin.
The invention is further illustrated, but is not intended to be limited by the following examples in which all parts and percentages are by weight unless oth~rwise specified.
~o-2727 ~, L2~3 EXAMPLES
Experimental 1. Flame resistant, pigmented polycarbonate compositions were prepared in accordance with the invention and their surface properties in terms of streaking were compared to prior art compositions.
Essentially it was found that the PTFE-containing, iron oxide pigmented compositions were streak-free whereas the comparable prior art compositions which were similar ~hereto in all respects~ e~cept for the substltution of carbon black for iron oxide, exhibited an objectionable degree o~ streaking. In carrying out the comparison, the compositions contain d about 96%
polycarbonate resin (a 1:1 mixture of linear and branched BPA-derived homopolymers) 0.4~ cryolite and 0.31~ of PTFE (ASTM Type 3). To this basic composition there were added in the first instance about 3.7% of a color premix package containing carbon black and in the second instance about 3.8Z of a similar premix package containing iron oxide based black pigment. The premix package contained about 4% of the iron oxide (black) or about 0.5% of carbon black and about 19% of TiO2 as a co-pigment as well as auxiliary additives such as a thermal stabilizer and a mold release a~ent neither of which are critical to the invention. The preparation of the compositions and the molding operation followed conventional procedures known in the polycarbonate - art. The particular pigment used in the compositions of these examples were Bayferrox 318M, a micronized black iron oxide (Fe3O4) having a predominant particle size of about 0.2 microns. Visual inspection of parts molded from the compositions (molded on a 6" x 6" pl~que mold with a melt temperature of 530F and a Mo-2727 mold temperature of 150F) indicated a clear advantage in terms of freedom from streaking to be associated with the parts where iron oxide served as a pigment.
The melt indices of the compositions were in the range of about 5-6 gm/10 min; all exhibited a flammability rating of V-0 in accordance with UL-94 (l/16"
specimens) and all passed UL-94 5V rating (1/8"
specimens). The mechanical properties of the compositions of the invention were virtually identical to those o the prior art compositions where carbon black was used as a pigment even though substantially more iron oxide derived pigment was used to obtain pigmentation equivalent to the carbon black.
2. The data reported below summarized the findings respecting the properties o iron o~ide black, pigmented polyearbonate compositions as a function of the loading o pigment (318M3 with and without TiO2 as a co-pigment. The data points to the surprising degree of stability of the iron oxide pigments in polycarbonate moldings, at molding temperatures of up to 650F.
Mo-2727 A(~ B(a) C
Polycarbonate resin1 lb. 1 lb. 1 lb. 1 lb.
Black Iron Oxide(l)0.06 0.9 0.06 0.9 TiO2 6.8 6.8 Color Light Dark Trans- Opaque Grey Grey parent Black Black Melt flow, gm/10 min.
550F molding, 3S sec. cycle time 10.97 10.90 10.60 11.0 700F molding, 60 sec. cycle time 14~15 16.30 13.00 12.90 Color stability Color difference (AE) 550-600F 0.75 0.99 1.91 0.37 550-650F 0.09 0.51 3.11 0.59 550-700F 1.53 1.76 3.65 0.60 Impact strength, Izod-Notched, (ft. lbs/in.) 550F molding, 35 sec. 15.8 15.7 15.6 15.4 ` 700F molding, 60 sec. 15.8 15.8 15.7 15.5 Relative viscosity, extruded pellets 1.264 1.272 1.265 1.272 material molded ~t 550F 1.264 1.267 1.267 1.272 650F 1.268 1.259 1.267 1.265 700F 1.252 1.247 1.259 1.247 (1) gms/l lb. of polycarbonate.
(a) Compositions A and B contain a melt-stabilizer having no criticality to the invention.
~o-2727 Although the invention has been described in detail in the foregoing for the purpose of illustr~tion, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo-2727 PC-1~5
Claims (8)
1. A thermoplastic molding composition comprising (i) polycarbonate resin (ii) a flame retarding package and (iii) a pigmenting amount of iron oxide based pigment selected from the group consisting of black iron oxide and red iron oxide wherein said flame retarding package comprises a flame retarding agent and polytetrafluoroethylene and is present at a level of 0.06 to 3.0% relative to the weight of the polycarbonate resin.
2. The composition of Claim 1 wherein said polytetrafluoroethylene is of ASTM Type 3.
3. The composition of Claim 1 wherein said iron oxide has a predominant particle size between 0.01 and 2 micron.
4. The composition of Claim 3 wherein said iron oxide is micronized.
5. The composition of Claim 1 wherein said polytetrafluoroethylene is present at a level of about 0.05 to about 1.0% relative to the weight of said composition.
6. The composition of Claim 1 wherein said polycarbonate resin is a homopolymer based on bisphenol-A.
7. The thermoplastic molding composition of Claim 1 wherein said iron oxide based pigment is present at a level of about 0.04 to 4.0 gms per pound of polycarbonate resin.
Mo-2727
Mo-2727
8. A thermoplastic molding composition comprising (i) polycarbonate resin (ii) a flame retarding package and (iii) iron oxide based pigment selected from the group consisting of black iron oxide and red iron oxide wherein said flame retarding package comprises a flame retarding agent and a polytetrafluoroethylene and wherein said (ii) is present in a sufficient amount to render said composition at least a 5 V-1/8" rating in accordance with UL-94 flammability test.
Mo-2727
Mo-2727
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US766,746 | 1985-08-16 | ||
| US06/766,746 US4650823A (en) | 1985-08-16 | 1985-08-16 | Iron oxide pigmented, polycarbonate compositions |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1279420C true CA1279420C (en) | 1991-01-22 |
Family
ID=25077401
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA000515022A Expired - Fee Related CA1279420C (en) | 1985-08-16 | 1986-07-30 | Iron oxide pigmented, polycarbonate compositions |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US4650823A (en) |
| EP (1) | EP0212411B1 (en) |
| CA (1) | CA1279420C (en) |
| DE (1) | DE3679471D1 (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5041479A (en) * | 1988-12-20 | 1991-08-20 | The Dow Chemical Company | Dispersing ignition resistant additives into carbonate polymers |
| US5276077A (en) * | 1992-06-03 | 1994-01-04 | The Dow Chemical Company | Ignition resistant carbonate polymer blends |
| DE19907831A1 (en) * | 1999-02-24 | 2000-08-31 | Bayer Ag | Flame-retardant thermoplastic molding compound |
| US6944115B2 (en) * | 2000-09-29 | 2005-09-13 | General Electric Company | Colored data storage media |
| US6475588B1 (en) | 2001-08-07 | 2002-11-05 | General Electric Company | Colored digital versatile disks |
| US6475589B1 (en) | 2001-12-17 | 2002-11-05 | General Electric Company | Colored optical discs and methods for making the same |
| CN116444973B (en) * | 2023-04-26 | 2024-02-13 | 金发科技股份有限公司 | Flame-retardant polycarbonate material and preparation method and application thereof |
Family Cites Families (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3507951A (en) * | 1966-07-19 | 1970-04-21 | Mobay Chemical Corp | Colored polycarbonates and process for preparing the same |
| NL160310C (en) * | 1970-04-22 | 1979-10-15 | Bayer Ag | PROCESS FOR PREPARING PIGMENTED THERMOPLASTIC AROMATIC POLYCARBONATE RESINS. |
| US3875123A (en) * | 1972-06-28 | 1975-04-01 | Bayer Ag | Polymers and copolymers based on alkenoyl-oxybenzylidene-malonic esters as uv-absorbers and plastics stabilized therewith |
| US4017457A (en) * | 1975-10-06 | 1977-04-12 | Mobay Chemical Corporation | Flame retardant polycarbonate compositions |
| US4049614A (en) * | 1975-10-20 | 1977-09-20 | Mobay Chemical Corporation | Pigmented polycarbonates |
| US4279244A (en) * | 1977-12-15 | 1981-07-21 | Mcalister Roy E | Radiant energy heat exchanger system |
| US4223100A (en) * | 1979-04-18 | 1980-09-16 | Mobay Chemical Corporation | Flame retardant aromatic polycarbonate with good mechanical properties and melt stability |
| US4292294A (en) * | 1979-05-09 | 1981-09-29 | Basf Wyandotte Corporation | Yellow pigments stable at high temperatures |
| HU187403B (en) * | 1982-08-11 | 1986-01-28 | Mta Koezponti Kemiai Kutato Intezet,Hu | Composition containing poli/vinil-chlorid/ or poliolefin |
| IL72879A (en) * | 1984-09-06 | 1988-12-30 | Ginegar Kibbutz | Plastic sheeting |
-
1985
- 1985-08-16 US US06/766,746 patent/US4650823A/en not_active Expired - Fee Related
-
1986
- 1986-07-30 CA CA000515022A patent/CA1279420C/en not_active Expired - Fee Related
- 1986-08-04 DE DE8686110739T patent/DE3679471D1/en not_active Expired - Fee Related
- 1986-08-04 EP EP86110739A patent/EP0212411B1/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| EP0212411A3 (en) | 1989-01-18 |
| EP0212411B1 (en) | 1991-05-29 |
| EP0212411A2 (en) | 1987-03-04 |
| DE3679471D1 (en) | 1991-07-04 |
| US4650823A (en) | 1987-03-17 |
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