WO1999018284A1 - Compositions polymeres photostabilisantes et leurs procedes de production - Google Patents

Compositions polymeres photostabilisantes et leurs procedes de production Download PDF

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Publication number
WO1999018284A1
WO1999018284A1 PCT/US1997/017717 US9717717W WO9918284A1 WO 1999018284 A1 WO1999018284 A1 WO 1999018284A1 US 9717717 W US9717717 W US 9717717W WO 9918284 A1 WO9918284 A1 WO 9918284A1
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WIPO (PCT)
Prior art keywords
styrene
acrylonitrile
butadiene
polymer composition
polymer
Prior art date
Application number
PCT/US1997/017717
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English (en)
Inventor
Daniel Deschryver
Original Assignee
Albemarle Corporation
Priority date (The priority date 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 date listed.)
Filing date
Publication date
Application filed by Albemarle Corporation filed Critical Albemarle Corporation
Priority to PCT/US1997/017717 priority Critical patent/WO1999018284A1/fr
Priority to EP97909920A priority patent/EP1021610A4/fr
Publication of WO1999018284A1 publication Critical patent/WO1999018284A1/fr

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    • 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
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • the invention provides novel polymer compositions which are resistant to color changes induced by exposure to UV light .
  • the invention further provides a method of producing polymers which are resistant to color change upon exposure to UV light.
  • HIPS flame retardant high impact polystyrene
  • PC/ABS and ABS compositions wherein light induced color changes are offset or masked by the addition of one or more "fading dyes” or “fading pigments”.
  • the subject invention provides novel polymer compositions, such as high impact polystyrene (HIPS) compositions, wherein UV induced color changes, are effectively masked by the addition of one or more fading dyes or fading pigments, alone or in combination with conventional UV stabilizers and/or in combination with one or more thermal stabilizers.
  • HIPS high impact polystyrene
  • the present invention is suitable for any polymer which is subject to UV-induced color change.
  • the polymers will comprise those typically used in the manufacture of computers and other office equipment, such as high impact polystyrene, ABS, ASA, PC/ABS, PPO/PS blends, PVC and PVC blends.
  • the present invention was conceived after an observa- tion by the inventor that polymer compositions, even those containing conventional UV stabilizers, often discolor when subjected to accelerated weathering conditions. More specifically, it was observed that high impact polystyrene compositions, even those containing conventional UV stabi- lizers, were subject to UV-induced discoloration when subjected to accelerated weathering conditions.
  • accelerated weathering conditions comprise test environments which have been designed to aid in predicting the color fastness of polymer compositions when exposed to workplace or outdoor illumination conditions.
  • These test environments include illumina- tion from fluorescent, incandescent or window-filtered sunlight sources and thermal radiation.
  • a well-known example thereof comprises the Xenon arc exposure procedure of ASTM D4459-86 (which can be carried out in a eatherometer or Xenotest type equipment) , or in other Xenon arc type equipments (such as Suntest device) .
  • Other accelerated UV- exposure procedures exist and are used as well, for example, ASTM D4476-89.
  • the present inventor conceived that the color changes typically observed upon exposure of polymer compositions to UV light could be offset or potentially even totally masked by the addition of a "fading dye” or "fading pigment.” More specifically, it was conceived that an organic dye or pigment that is UV-light instable and subject to color change when exposed to UV light, if used as an additive in polymer compositions, could effectively "mask” or "off-set” the color changes attributable to UV degradation in the polymer. Thus, the present invention exploits the UV-instability of specific compounds, i.e., organic dyes or pigments which fade when exposed to
  • UV-light by using these compounds as additives in order to produce polymer compositions which exhibit less color change when exposed to UV light .
  • a "fading dye” or “fading pigment” refers to an organic dye or organic pigment, or a combination thereof, the initial color of which changes (fades) upon exposure to UV light in such a way that it masks or offsets a color change the polymer normally undergoes when subjected to accelerated weathering conditions.
  • the fading dye or fading pigment will mask any color change of the polymer composition when subjected to accelerated weathering conditions.
  • such fading dyes or pigments will embrace any organic dye or pigment, or combination thereof, which exhibits a color change upon exposure to UV light that significantly offsets and ideally totally masks the color change that the polymer would normally undergo upon exposure to accelerated weathering conditions.
  • Exemplary fading dyes and pigments according to the invention include organic dyes and pigments such as anthra- quinones, quinophthalones, azo dyes/pigments, (phthalo) peri- nones, styryl compounds, cumulin, pyrazolon, naphthazin dyes, quinolines, as well as others. Further information on dyes can be found for example in Ullmann's Encyclopedia of Industrial Chemistry, 9:73-124 (1987); Kirk-Othmer' s Ency- clopedia of Chemical Technology, 8:159-212 (1979); and SRI International's Chemical Economic Handbook, "Dyes", 1996, pages 520.5000A-5005G. Similar chapters about (organic) pigments are found in these sources as well.
  • organic dyes and pigments such as anthra- quinones, quinophthalones, azo dyes/pigments, (phthalo) peri- nones, styryl compounds, cumulin, pyrazolon, naphthazin dyes
  • the fading dye must be stable (i.e., not degrade chemically) under the particular processing conditions used to convert the polymer formulation to its final form (e.g., injection molded article, blown film, etc) .
  • the amount of the fading dye may be varied over wide concentrations.
  • concentration will vary dependent upon factors including the particular polymer, the nature of the UV environment that the polymer will be exposed to (e.g., workplace or outdoor illumination conditions) , the susceptibility of the polymer to UV-induced color changes, whether other UV stabilizers or thermal stabilizers are present, among other factors.
  • polymers which are to be used in laboratory environments will require the addition of lesser amounts of the fading dye or pigment than polymers which are to be used in outdoor environments where UV exposure is substantially higher.
  • the concentration of fading dye or pigment in a polymer for indoor usage will vary from about 1 to 5,000 ppm, more preferably from about 5 to 1000 ppm and most preferably from 10 to 500 ppm.
  • the amount of fading dye or pigment in a polymer for outdoor usage will typically be significantly higher. Based on the results disclosed infra, it is anticipated that suitable amounts will range from about 1 to 10,000 parts per million, more preferably 5 to 2000 parts per million, and most preferably from about 10 to 1000 parts per million.
  • inorganic pigments as exemplified by titanium dioxide, carbon black, iron oxide (red) , Cr/Sb or Ni/Sb titanates (yellow) , ultramarine blue
  • the particular fading dye or fading pigment will depend largely on the nature of the base polymer.
  • the type and amount of dye or pigment is selected with a view toward compensating as much as possible the color change the formulation will undergo during a UV stability test such as the aforementioned ASTM D-4454-86 procedure.
  • the amount and types of fading dye or fading pigment contained in a specific polymer composition will be determined in general by (i) exposing a desired polymer composition lacking fading dye or fading pigments to accelerated weathering conditions; (ii) evaluating the color change (s) by standard methods known in the polymer art; and (iii) based on the degree and nature of the color change (s) selecting a fading dye or pigment, or combination thereof, and an appropriate concentration, which effectively offsets and potentially totally masks such color change (s) . Standardized methods for quantifying color changes are well known in the art.
  • color changes may be quantified according to the Hunterlab system which expresses color change based on the delta E value, or according to the Cielab system which quantifies color changes based on the delta E* value.
  • color changes were, in general, determined according to the Cielab system which is conventionally used in Europe.
  • the particular manner that color change is expressed is not essen- tial to the invention. All that is essential is that the color change be offset and ideally totally masked as a result of the addition of the fading dye or fading pigment .
  • the Hunterlab or Cielab system is used to express color change, it is desirable that the ⁇ E or ⁇ E* value be as low as possible, ideally zero.
  • Cielab system expresses ⁇ E* according to the following equation:
  • ⁇ E* [( ⁇ L*) 2 + ( ⁇ a*) 2 + ( ⁇ b*) 2 ] 1/2
  • ⁇ L refers to the change in darkness or lightness (positive ⁇ L* means that the polymer has become darker (after the exposure) ; (negative) ⁇ L* means that the polymer has become lighter;
  • ⁇ a* refers to the change of color in the red-green axis (positive means color change towards red range, nega- tive towards green range) ;
  • ⁇ b* refers to color changes in the blue-yellow axis (positive color change means towards yellow range, negative toward blue range) .
  • a fading dye or fading pig- ment will preferably reduce the ⁇ E* or ⁇ E value which is observed in the absence of the fading dye or pigment by at least 10%, more preferably by at least 50% and ideally up to 100%.
  • the subject invention should be suitable for use in compensating for all types of color changes induced by UV- light, e.g. those on the yellow-blue axis (e.g. yellowing) and also shifts on the red-green axis.
  • a yellow fading dye for example, in the case of polymers which are subject to yellowing, it is advantageous to add a yellow fading dye to compensate for the color change.
  • a yellow fading dye examples thereof include Oracet Yellow GHS ® (Ciba) , (Color Number Solvent Yellow 163, CI 58890) which is an anthraquinone type fading dye and Makrolex Gelb G ® (Bayer) (Disperse Yellow 54, CI 47020), which is a quinophthalone dye.
  • the fading dye should aid in minimizing "delta E*", the total color difference, following performance of the UV-stability test for the application of interest.
  • this test is typically the ASTM D-4439-86 300 hours xenon-arc lamp weatherometer exposure test.
  • the particular test will depend upon the particular polymer and the UV-light conditions that it is to be ex- posed.
  • a fading dye should be selected so as to minimize or neutralize this effect. This can be done, e.g., by using a yellow dye which will fade away to a colorless species due, it is believed, to destruction of its conjugated bond system under the influence of the UV light.
  • the concept of using a fading dye to neutralize and/or minimize the UV-induced color change of a polymer formulation should have generic applicability.
  • it should be broadly applicable to both flame retardant and non-flame retardant compositions; to compositions based not only on styrene polymers such as HIPS, but any organic polymer; and not only for color shifts toward the yellow axis (i.e., the "b*" axis according to ASTM E
  • the grey colored formulations commonly used do not require the high coloring strength of organic dyes; however, in accordance with the present invention, organic dyes are used because of their poorer UV-light stability relative to inorganic pigments and this provides the desired "fading" effect.
  • the key is, of course, to judiciously select the particular type and concentration of fading dye to be used in the polymer formulation so as to maximize the reduction in ⁇ E or ⁇ E* .
  • polymer formulations according to the invention also may comprise conventional UV-stabilizers, e.g., UV-absorbers, in order to further compensate for the other adverse effects of UV-radiation, including color changes.
  • UV-stabilizers are well known in the art, and include hindered amine light stabilizers (HALS) and UV- absorbers like 2- (2 ' -hydroxypheny1) benzotriazoles, 2- hydroxybenzophenones, esters of substituted benzoic acids (like, for example, 3 , 5-di (t-butyl) , 4-hydroxybenzoic acid, n-hexyl ester), 2- (2 -hydroxypheny1) -1, 3 , 5-triazines, acryl- ates, nickel phenolates, oxalic acid diamides and benzoxazi- nones .
  • HALS hindered amine light stabilizers
  • UV- absorbers like 2- (2 ' -hydroxypheny1) benzotriazoles, 2- hydroxybenzophenones, esters of substituted benzoic acids (like, for example, 3 , 5-di (t-butyl) , 4-hydroxybenzoic acid, n-hexyl ester), 2- (2 -hydroxyphen
  • Tinuvin ® 770 bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate) (HALS)
  • Tinuvin P bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate
  • Tinuvin P bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate
  • Tinuvin P bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate
  • Tinuvin P bis (2, 2, 6, 6-tetramethyl-4-piperidyl) sebacate
  • Tinuvin P benzotriazole light stabilizer (2- (2H-benzotria- zol-2-yl) -p-cresol
  • Tinuvin ® 328 benzotriazole light stabilizer (2-2H-benzotriazol-2-yl) -4, 6-ditertpentylphenol)
  • Chimassorb ® 119 FL hinderedered amine light stabilizer (HALS)
  • the present invention is not limited to the usage of any specific
  • the subject polymer compositions comprise a thermal stabilizer as this has been discovered to result in a further reduction in UV- induced color changes of polymer subjected to accelerated weathering conditions.
  • the selected thermal stabilizer should, of course, be stable under the particular polymer processing conditions and not adversely affect the properties of the particular polymer.
  • Thermal stabilizers suitable for use in the invention include by way of example zeolite A, TSPP (tetrasodium pyrophosphate) , hydrotalcite type stabilizers (e.g., basic magnesium aluminum hydroxy carbonate) , epoxidized fatty acids such as epoxidized soybean oil (ESBO) , as well as other typical thermal stabilizers having known usage in other areas such as are used for the stabilization of PVC or thermally sensitive (cyclo) aliphatic brominated flame retardants (e.g., hexabromocyclodo- decane (HBCD) ) , etc.
  • zeolite A tetrasodium pyrophosphate
  • hydrotalcite type stabilizers e.g., basic magnesium aluminum hydroxy carbonate
  • epoxidized fatty acids such as epoxidized soybean oil (ESBO)
  • ESBO epoxidized soybean oil
  • antioxidants have a beneficial effect; examples are primary antioxidants (hindered phenols) and secondary antioxidants (phosphites, phosphonites and thioesters) ; other types are known from the literature.
  • the subject polymeric compositions will comprise other additives conventionally used therein such as impact modifiers, lubricants, processing aids, other colorants, primary and secondary antioxidants, metal deactivators, nucleating agents, fillers and reinforcing agents (like glass fibers), plasticizers, antistatic additives, etc.
  • additives conventionally used therein such as impact modifiers, lubricants, processing aids, other colorants, primary and secondary antioxidants, metal deactivators, nucleating agents, fillers and reinforcing agents (like glass fibers), plasticizers, antistatic additives, etc.
  • thermoplastic or thermoset polymers such as styrenics (homopolymers and copolymers) , like HIPS, ABS and ASA; styrenic blends and alloys, such as PC/ABS; polyolefins, including by way of example PE and PP; PVC and PVC blends; engineering thermoplastics, including by way of example polyamides, polycarbonates, and polyesters; polyphenyleneoxide and polyphenyleneoxide blends, such as PPO/PS; syndiotactic polystyrene and polyketone .
  • styrenics homopolymers and copolymers
  • styrenic blends and alloys such as PC/ABS
  • polyolefins including by way of example PE and PP
  • PVC and PVC blends engineering thermoplastics, including by way of example polyamides, polycarbonates, and polyesters
  • polyphenyleneoxide and polyphenyleneoxide blends such as PPO/PS
  • styrenic homopolymers examples include polysty- rene, poly (alphamethylstyrene) and poly (p-methylstyrene) .
  • copolymers include copolymers of styrene or alpha-methylstyrene with dienes or acryl derivatives, such as styrene-butadiene, styrene-acrylonitrile, styrene-maleic anhydride, styrene-butadiene-alkylacrylate and -methacryl- ate, styrene-alkylmethacrylate, and styrene-acrylonitrile- methacrylate .
  • Impact modified versions are typically used in applications like business electronics housings.
  • Copolymers are often used.
  • examples of mixtures of higher impact resistance are, for example, above-mentioned styrenic homo- or copolymers with other polymers like, for example, a diene-polymer, an ethylene-propylene-diene terpolymer or a polyacrylate, or block copolymers like styrene- butadiene-styrene, styrene-isoprene-styrene, styrene-ethyl- ene/butylene-styrene or styrene-ethylene/propylene-styrene .
  • graft copolymers are copolymers of styrene or alpha-methylstyrene like, for example, styrene on polybutadiene, styrene on polybutadiene-styrene or polybutadiene- acrylonitrile-copolymers, styrene and acrylonitrile or methylacrylonitrile on polybutadiene; styrene, acrylonitrile and methylmethacrylate on polybutadiene; styrene and maleic anhydride on polybutadiene; styrene, acrylonitrile and maleic anhydride or maleic imide on polybutadiene; styrene and maleic imide on polybutadiene, styrene and alkylacryl- ates or alkylmethacrylates on polybutadiene; styrene and acrylonitrile on ethylene-propylene-diene
  • the polymer will comprise a high impact polystyrene (HIPS) polymer composition.
  • HIPS high impact polystyrene
  • flame retardants used in flame retarded polymer formulations that can benefit from the present invention can be found for example in Gachter/Muller "Polymer Additives" Handbook, publisher Carl Hanser, 1990, pages 717-721. However this is of course an incomplete list of flame retardants, as many new flame retardants have appeared on the market since the time of publication.
  • brominated flame retardants include: ethylene-bis (pentabromophenyl) and alkylene-bis (pentabromophenyl) ethylene-bis (tetrabromophthalimide) , bis (tetrabromo- phthalimide) , and alkylene-bis (tetrabromo phthalimide) deca-, octa- and pentabromodiphenyloxide bis (tribromophenoxy) ethane octabromotrimethylphenylindane hexabromocyclododecane - tetrabromobisphenol-A and derivatives of tetrabromobis- phenol-A, like for example tetrabromobisphenol-A-bis (2- hydroxyethyl ether) and tetrabromobisphenol-A- bis (2,3- dibromopropyl ether) tetrabromobisphenol-A carbonate oligomers
  • chlorinated flame retardants examples include:
  • These flame retardants can be used in the typical concentrations, for example from 0.5 to 30 weight %, more typically from 5 to 20 weight %.
  • metal oxides like Sb oxides or Na antimonate, or Sb-free synergists can be used in subject polymer formulations.
  • Examples include phosphorus-based FR's, such as triphenylphosphate, resorcinoldiphenylphosphate and other phosphates; red phosphorus; P/halogen systems; P/N systems; intumescent systems; inorganic systems, such as Mg hydroxide, aluminum trihydrate, boron-containing compounds and melamine-containing compounds; etc.
  • the FR PC/ABS used in this example contains ethylenebis (tetrabromophthalimide and antimony trioxide as the flame retardant system.
  • Some key properties of this FR PC/ABS are as follows : Vicat 5 kg : 108 °C; Izod impact strength : 49 kJ/m2; MFI (260°C/5 kg) : 17 g/10 min.; UL-94 flammability rating at 1.6 mm specimen thickness : V-0.
  • UV-stabilitv of FR PC/ABS Delta E color change after 100 hours Suntest exposure
  • UV-stabilit of FR HIPS Color change after 300 hours Weatherometer exposure (ASTM D4459-86)
  • Irganox 168 ® Irganophosphite Phenol, 2 , 4 -bis (1 , 1-dimethyl ethyl) - , phosphite .
  • Irgaplastol CM50 1/1 Mix of Carbon Black (Pigment Black 7 Colour Index 77266) and Calcium Carbonate.
  • Kronos 2220 Titanium Dioxide white pigment.
  • Bayferrox 13OM Fe203 , containing some Si02 + A1203 ; Pigment Red 101; Color Index 77491.
  • Light yellow 6R (Lichtgelb 6R) : Chromrutilgelb; (Ti, Cr, Sb)02; Pigment Brown 24; Color Index 77310.
  • Monarch 800 carbon black; Pigment Black 7; Color Index

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Compositions Of Macromolecular Compounds (AREA)

Abstract

L'invention concerne des compositions polymères qui résistent aux changements de couleur induits par UV et leurs procédés de production. Ces compositions renferment une teinture ou un pigment organique qui se décolore à l'exposition à la lumière ultraviolette ce qui a pour effet de corriger ('masquer') les changements de couleur induits par UV.
PCT/US1997/017717 1997-10-03 1997-10-03 Compositions polymeres photostabilisantes et leurs procedes de production WO1999018284A1 (fr)

Priority Applications (2)

Application Number Priority Date Filing Date Title
PCT/US1997/017717 WO1999018284A1 (fr) 1997-10-03 1997-10-03 Compositions polymeres photostabilisantes et leurs procedes de production
EP97909920A EP1021610A4 (fr) 1997-10-03 1997-10-03 Compositions polymeres photostabilisantes et leurs procedes de production

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PCT/US1997/017717 WO1999018284A1 (fr) 1997-10-03 1997-10-03 Compositions polymeres photostabilisantes et leurs procedes de production

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WO1999018284A1 true WO1999018284A1 (fr) 1999-04-15

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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6894102B2 (en) 2002-05-20 2005-05-17 General Electric Syndiotactic polystyrene blends
WO2023209007A1 (fr) * 2022-04-29 2023-11-02 Ineos Styrolution Group Gmbh Composition de copolymère acrylonitrile styrène acrylate (asa) présentant une bonne résistance aux uv et une teneur réduite en agents absorbant les uv

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US4581396A (en) * 1968-09-18 1986-04-08 Raychem Corporation Flame retardants and compositions containing them
US5028792A (en) * 1987-03-19 1991-07-02 Xytronyx, Inc. System for the visualization of exposure to ultraviolet radiation
US5049600A (en) * 1990-01-23 1991-09-17 The B. F. Goodrich Company Multi-component stabilizer system for polyolefins pigmented with phthalocyanine pigments

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EP0009299A1 (fr) * 1978-07-03 1980-04-02 Imperial Chemical Industries Plc Matière organique à couleur stabilisée
US4743642A (en) * 1986-09-08 1988-05-10 The Dow Chemical Company Color balanced rubber-reinforced plastic
US5240977A (en) * 1990-01-23 1993-08-31 The B. F. Goodrich Company Multi-component stabilizer system for polyolefins pigmented with azo and disazo pigments
US5190710A (en) * 1991-02-22 1993-03-02 The B. F. Goodrich Company Method for imparting improved discoloration resistance to articles

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US4581396A (en) * 1968-09-18 1986-04-08 Raychem Corporation Flame retardants and compositions containing them
US5028792A (en) * 1987-03-19 1991-07-02 Xytronyx, Inc. System for the visualization of exposure to ultraviolet radiation
US5049600A (en) * 1990-01-23 1991-09-17 The B. F. Goodrich Company Multi-component stabilizer system for polyolefins pigmented with phthalocyanine pigments

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Title
H. LIND, "Light Stabilizing for Plastics", GERMAN PLASTICS, (Translated from KUNSTSTOFFE 69, Vol. 7, pages 397-402), pages 12-16. *
IMPERIAL CHEMICAL INDUSTRIES LIMITED, THE CPÖPRING OF PLASTICS, PROVIDENCE, RHODE ISLAND: ARNOLD, HOFFMAN & CO. INCORPORATED, 1960, pages 9-13 and 55-59. *

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US6894102B2 (en) 2002-05-20 2005-05-17 General Electric Syndiotactic polystyrene blends
WO2023209007A1 (fr) * 2022-04-29 2023-11-02 Ineos Styrolution Group Gmbh Composition de copolymère acrylonitrile styrène acrylate (asa) présentant une bonne résistance aux uv et une teneur réduite en agents absorbant les uv

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EP1021610A1 (fr) 2000-07-26

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