Thermoplastic resin composition containing an organometallic colorant

Abstract: A thermoplastic resin composition having improved heat stability which comprises a thermoplastic resin which contains at least 5 % by weight of an α-alkyl-substituted aromatic copolymer comprising α-alkyl-substituted aromatic vinyl compound and at least one other comonomer copolymerizable therewith, wherein the composition contains an organometallic colorant containing free metal in an amount of not more than 2,000 ppm, from which a molded article having no or less silver streaks can be produced.

Description: The present invention relates to the use of an organic colorant in a thermoplastic resin composition. Particularly,the thermoplastio resin has improved heat stability and oan be molded even at high temperatures to give colored moldings having few or no silver streaks on the article. DE-A-24 01 088 describes a process for purification of Cu-phthalocyanine which, starting from a commercially available Cu-phthalocyanine having a free metal content of about 150 ppm, provides a phthalcyanine having not more than 50 ppm of free copper. JP-A-59 189 155 (Ca 102:133 000w) describes a resin composition comprising 100 part by weight of a [methylstyrene-based] resin and 0,1 parts of phthalocyanine blue (Cu-phthalocyanine). No content of the free metal is given. It is known that α-methylstyrene base copolymer with good heat resistance is produced by replacing a part or the whole of styrene in a styrene base resin such as a styrene-acrylonitrile copolymer with α-methylstyrene and that blend of the α-methylstyrene base copolymer with other resin such as an ABS graft polymer provides a resin composition which has improved heat resistance. The α-methylstyrene base copolymer and the blend of said copolymer with the ABS graft polymer are practically used. Such copolymer or blend may be colored by an inorganic or organic colorant. As an α-methylstyrene content in the copolymer or the blend increases, their heat resistance is improved but their processability is deteriorated. Therefore, the copolymer or the blend having the higher α-methylstyrene content should be processed at a higher temperature. But, at the higher processing temperature, silver streaks often appear on the surface of the molded article and do not disappear in subsequent fabrication steps such as coating. When the processing temperature is lowered to prevent the formation of silver streaks, processability is decreased and problems such as short molding are caused. It is known that, in general, the silver streaks appear more frequently when the resin contains a larger amount of volatile components. To remove the volatile components, the resin is intensively dried before molding. Since the presence of volatile components in the resin is not the sole cause for the silver streak and there may be some unknown causes, intensive drying of the resin does not necessarily prevent the formation of silver streaks. Addition of an antioxidant cannot prevent the formation of silver streaks either. In some cases, a colorant is added to the α-methylstyrene base copolymer and its resin composition before or during molding as in the case of other thermoplastic resin. Particularly, the addition of an organo-metallic colorant causes more frequently the silver streaks than other colorants. An object of the present invention is to provide a thermoplastic resin composition comprising an α-alkyl-substituted aromatic copolymer comprising repeating units of an alpha-alkyl-substituted aromatic vinyl compound which gives a molded article having few or no silver streak on its surface. The above object is met by the use of an organometallic colorant containing free metal content of not more than 2,000 ppm, in a thermoplastic resin composition which comprises a thermoplastic resin which contains at least 5 % by weight of an α-alkyl-substituted aromatic copolymer comprising repeating units of an α-alkyl-substituted aromatic vinyl compound and of at least one other comonomer copolymerizable therewith for the purpose of providing colored moldings having few or no silver streaks on this surface. Generally, the α-alkyl-substituted aromatic vinyl compound contained in the α-alkyl-substituted aromatic copolymer used in the present invention is represented by the formula: wherein R 1 is C 1 -C 3 alkyl and R 2 is hydrogen, halogen or C 1 -C 3 alkyl. Specific example of the vinyl compound are α-methylstyrene, α-methyl-p-chlorostyrene, α-methyl-p-methylstyrene and the like. These vinyl compounds may be used individually or as a mixture of two or more of them. In view of heat resistance and a property balance of the copolymer, α-methylstyrene is preferred. As other comonomer copolymerizable with the α-alkyl-substituted aromatic vinyl compound, exemplified are aromatic vinyl compounds except the α-alkyl-substituted aromatic vinyl compound, vinyl cyanide, unsaturated carboxylic acids and their alkyl esters or anhydrides, maleimide and its N-alkyl or N-aryl substituted derivatives, rubbery polymers and the like. These comonomers may be used individually or as a mixture of two or more of them. Specific examples of the aromatic vinyl compound except the α-alkyl-substituted one are styrene, p-methylstyrene, nuclear halogen-substituted styrene and mixtures thereof. Among them, styrene is preferred. Specific examples of the vinyl cyanide are acrylonitrile, methacrylonitrile, maleonitrile, fumaronitrile and mixtures thereof. Among them, acrylonitrile is preferred. Specific examples of the unsaturated carboxylic acid and its alkyl ester or anhydride are acrylic acid, methacrylic acid, fumaric acid, itaconic acid, maleic acid, methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate and maleic anhydride. Among them, methyl methacrylate and maleic anhydride are preferred. Specific examples of maleimide and its N-alkyl or N-aryl substituted derivative are maleimide, methylmaleimide, ethylmaleimide, N-phenylmaleimide and O-chloro-N-phenylmaleimide. Among them, N-phenylmaleimide is preferred. Specific examples of the rubbery polymer are polybutadiene, butadiene-styrene copolymer, butadiene-acrylonitrile copolymer, ethylene-propylene copolymer, ethylene-propyrene-non-conjugated diene copolymer, polybutyl acrylate, ethylene-vinyl acetate copolymer and chlorinated polyethylene. The ratio of the α-alkyl-substituted aromatic vinyl compound and other comonomer in the α-alkyl-substituted aromatic copolymer is not limited. In view of the heat resistance and the property balance of the composition, a preferred content of the α-alkyl-substituted aromatic vinyl compound is from 5 to 90 % by weight and that of other comonomer is from 95 to 10 % by weight. Among other comonomers, styrene, acrylonitrile, methyl methacrylate, maleic anhydride, methacrylic acid, N-phenylmaleimide and polybutadiene are preferred. Specific examples of the α-alkyl-substituted aromatic copolymer are α-methylstyrene-acrylonitrile copolymer, α -methylstyrene-methyl methacrylate-(acrylonitrile or styrene) copolymer, α-methylstyrene-maleic anhydride-(acrylonitrile or styrene) copolymer, α-methylstyrene-N-phenylmaleimide-(acrylonitrile or styrene) copolymer, α-methylstyrene-polybutadiene-(acrylonitrile or styrene) copolymer and the like. There is no limitation on the structure of the α-alkyl-substituted aromatic copolymer. In view of the formation of silver streaks, heat resistance and processability of the composition, the copolymer preferably has an intrinsic viscosity of 0.3 to 1.0 (at 30°C in dimethylformamide). The α-alkyl-substituted aromatic copolymer may be prepared by any of conventional polymerization methods suitable for polymerisation of the α-alkyl-substituted aromatic vinyl compound, for example, emulsion polymerization, suspension polymerisation, solution polymerization, bulk polymerization and combinations thereof. Examples of other polymer which may be contained in the thermoplastic resin composition of the present invention are a polymer comprising at least one monomer of the above described monomers such as the aromatic vinyl compounds except the a-alkyl-substituted aromatic vinyl compound, vinyl cyanide, the unsaturated carboxylic acids and their alkyl esters or anhydrides and maleimide and its N-alkyl or N-aryl substituted derivatives; and conventional resins such as polycarbonate, polyphenyleneoxide, polysulfone, polyester, polyamide, polyacetal and the like. These other polymers may be used individually or as a mixture of two or more polymers. In view of the property balance of the resin composition, preferred other polymers are a copolymer of the aromatic vinyl compound with vinyl cyanide and/or the alkyl ester of unsaturated carboxylic acid, a graft polymer of the rubbery polymer with the aromatic vinyl compound, vinyl cyanide and/or the alkyl ester of unsaturated carboxylic acid, and a mixture of the former copolymer and the latter graft polymer. The amount of α-alkyl-substituted aromatic copolymer is at least 5 % by weight, more preferably from 5 to 95 % by weight based on the whole weight of the thermoplastic resin. According to the present invention, an organometallic colorant containing free metal content of not more than 2,000 ppm is used as a colorant not to increase the amount of the free metal in the composition so large as the conventional colorant. Specific examples of such organometallic colorant are (i) Phthalocyanine containing Co, (ii) Lothol® Red containing Ba, Ca, Na, Sr, Mn or Fe, (iii) Lake Red containing Ba or Al, (iv) Brilliant Carmine (Pigment Scarlet) containing Ba, Ni, Cu, Pb or Ca, (v) Alizarln Lake containing Ca, Ba, Al, Sr, Pb, Mg or Fe, (vi) Watchung® Red (Permanent Red) containing Ca or Mn, (vii) Naphtol Green containing Ba or Fe, (viii) Acid Green Lake containing Ba, and mixtures thereof. Significant improvement of suppression effect on silver streak is achieved when Phthalocyanine type pigment containing copper which is thermally unstable and induces silver streaks is used according to the present invention. When the amount of free metal in the colorant exceeds 2,000 ppm, the silver streaks appears on the molded article of the thermoplastic resin composition. Preferably, the colorant contains a free metal content of not more than 1,000 ppm. When the colorant contains more than 2,000 ppm of free metal, it is thermally treated in sulfuric acid to reduce the content of free metal to 2,000 ppm or less. The content of free metal is determined by extracting the free metal elements from the colorant with an inorganic acid such as sulfuric acid and measuring the amount of free metal contained in the acid by atomic-absorption spectroscopy or colorimetry. A ratio of the thermoplastic resin and the organometallic colorant is not limited, and the resin composition can be colored in any color with adequate chroma, hue and color value by a suitable organometallic colorant. Usually, the organometallic colorant is added in an amount of 0.01 to 20 parts by weight per 100 parts by weight of the thermoplastic resin. When the color concentrate is prepared, the colorant is added in an amount of 5 to 100 parts by weight per 100 parts by weight of the thermoplastic resin. The amount of free metal introduced in the resin composition from the colorant is preferably not more than 100 ppm based on the total weight of the thermoplastic resin and the organometallic colorant. Preferably, the thermoplastic resin composition of the present invention comprises the thermoplastic resin and the organometallic colorant containing not more than 1,000 ppm of free metal, and the free metal content in the composition is not more than 50 ppm based on the total weight of the thermoplastic resin and the organometallic colorant. The thermoplastic resin composition of the present invention may be prepared by any of conventional mixing or kneading methods, for example, by using a Banbury mixer, a single or twin screw extruder, and the like. In addition to the above essential components, the thermoplastic resin composition of the present invention may contain any conventional additive which is added to the thermoplastic resin. Examples of such additive are an inorganic colorant, an organic colorant, an inorganic filler, an antioxidant, a plasticizer, an antistatic agent, an ultraviolet light absorber, a flame retardant, a blowing agent, a lubricant and the like. The present invention will be illustrated by following Examples, which do not limit the present invention. In Examples, "parts" and "%" are by weight unless otherwise indicated. Example 1 and Comparative Example 1 Preparation of α-alkyl-substituted aromatic copolymer In a reactor an interior space of which had been replaced with nitrogen, 30 % of a monomer mixture (I) shown in Table 1 was added and reacted at 70°C for 1 hour and then the rest of the monomer mixture (I) was continuously added over 3 hours to continue polymerization. After exothermic heat due to polymerization was not generated any more, a monomer mixture (II) was continuously added over 1 hour at 70°C. After the completion of polymerization, the reaction mixture was salted out, and the product was dried to obtain an α-alkyl-substituted aromatic copolymer (a-1 to a-3). Copolymer a-1 a-2 a-3 Monomer mixture (I) α-Methylstyrene 70 80 30 Acrylonitrile 5 8 3 t-Dodecylmercaptan 0.05 0.05 0.05 Sodium laryl sulfate 2 2 2 Potassium persulfate 0.5 0.5 0.5 Deionized water 120 120 120 Monomer mixture (II) α-Methylstyrene 0 0 10 Styrene 0 0 10 Acrylonitrile 25 12 27 Methyl methacrylate 0 0 10 N-phenylmaleimide 0 0 10 Intrinsic viscosity 0.60 0.48 0.55 Preparation of ABS graft polymer In a reactor an interior space of which had been replaced with nitrogen, a composition shown in Table 2 was polymerized at 65°C for 6 hours. The resulting polymer latex was salted out with potassium chloride and dried. Component Parts Polybutadiene latex 40 (solid components) Styrene 40 Acrylonitrile 20 t-Dodecylmercaptan 0.3 Potassium persulfate 0.3 Disproportionated potassium rosinate 2.0 Water Up to 150 AS copolymer Styrene-acrylonitrile copolymer "Sebian® N-JD" manufactured by Daicel Chemical Industries, Ltd. (acrylonitrile content, 27 %; intrinsic viscosity, 0.62 in dimethylformaide at 30°C). Polycarbonate Polycarbonate "Panlite® l-1250" Teijin Chemical Co., Ltd. (poly-4,4'-dioxydiphenyl-2,2-propane carbonate). Colorant Phthalocyanine Blue "Sumitone® Cyanine Blue GH" manufactured by Sumitomo Chemical Company, Ltd, which contains 2,850 ppm of free metal. Antioxidant (a) n-Octadecyl-3-(4'-hydroxy-3',5'-di-tert-butylphenyl) propionate "Irganox® 1076" manufactured by Ciba-Geigy, (Japan) Limited. (b) 1,3,5-Trimethyl-2,4,6-tris-(3.5-d-tert-butyl-4-hydroxybenzyl)benzene "Irganox® 1330" manufactured by Ciba-Geigy (Japan) Limited. (c) Phenyl-β-naphthylamine Examples 2-5 and Comparative Examples 2-3 Preparation of organometallic colorant A commercially available copper Phthalocyanine Blue containing 2,850 ppm of free copper elements (Comparative Example 2) was heated in sulfuric acid under such conditions that the treated Phthalocyanine contained 53 ppm (Example 2), 470 ppm (Example 3), 930 ppm (Example 4), 1,850 ppm (Example 5) or 2,150 ppm (Comparative Example 3) to obtain respective colorant. Examples 6-8 and Comparative Examples 4-5 A commercially available copper Phthalocyanine Green containing 3,130 ppm of free copper elements (Comparative Example 4) was heated in sulfuric acid under such conditions that the treated Phthalocyanine contained 170 ppm (Example 6), 850 ppm (Example 7), 1,730 ppm (Example 8) or 2,230 ppm (Comparative Example 5) to obtain respective colorant. Example 9 In this Example, the α-alkylsubstituted aromatic copolymer (a-1 to a-3) was prepared in the same manner as in Example 1, and the ABS graft polymer was prepared in the same manner as in Example 1 but adding 0.5 part of 4,4'-butylidene-bis-(6-tert.-butyl-3-methylphenol) and 0.3 part of dilauryl 3,3'-thiodipropionate to 100 parts of the polymer latex. The AS copolymer, polycarbonate and the antioxidant were the same as used in Example 1. As the colorant, the colorant prepared in Examples 2-8 or Comparative Examples 2-5 was used and no metal-deactivating agent was used. Composition Nos. 1-17 100 Parts of the thermoplastic resin mixture (70 % of α-alkyl-substituted aromatic copolymer and 30 % of the ABS graft polymer) and 2.5 or 6 parts of the organometallic colorant and 1 part of the antioxidant (a, b or c) (in Composition Nos. 13, 15, 16 and 17, the antioxidant was used.) were mixed by the Banbury mixer and kneaded and extruded by an extruder to produce colored pellets. After drying the pellets at 110°C for 4 hours, they were molded under the same conditions as in Example 1 to prepare four sample plates (from second to fifth shots) (each 90 mm x 40 mm x 3 mm). The formation of silver streaks was visually observed and evaluated according to the following criteria: O: No silver streak ▵: Silver streaks formed slightly X: Silver streaks formed XX: A large number of silver streaks formed The composition of the colored resin composition and the evaluation results are show in Table 3. Molding conditions A (3.5 ounce) 103,5 ml injection molding machine FS-75 manufactured by Nissei Jushi. Resin temperature: 280°C (preset temp.: 270°C) 290°C (preset temp.: 280°C) Detention time: 3 or 10 minutes Back pressure: (5 kg/cm 2 ) 490 kPa Injection rate: 8/10 Screw rotation rate: 100 rpm Mold temperature: 75°C Molding cycle: 8 sec. (injection)/15 sec. (cooling)/5 sec. (removing) A sample plate made from each of two colored thermoplastic resin compositions one of which contained the commercially available organometallic colorant containing more than 2,000 ppm of free metal and the other of which contained the organometallic colorant according to the present invention containing 2,000 ppm or less of free metal was examined on heat deflection temperature (¼") 6,35 mm, (264 psi) 1,8x10 7 Pa, no annealing), processability (230°C), (60 kg/cm 2 ) 59kPa and notched Izod impact strength (¼") 6,35 mm, (23°C). It was confirmed that there was no material difference between two compositions. Composition Nos. 18-23 100 Parts of the thermoplastic resin mixture (40 % of α-alkyl-substituted aromatic copolymer (a-1), 35 % of the ABS graft polymer and 25 %arts of the AS copolymer) and 5 parts of the organometallic colorant and 1 part of the antioxidant were mixed by the Banbury mixer and kneaded and extruded by an extruder to produce colored pellets. The sample plates were produced in the same manner as above and evaluated with respect to the formation of silver streaks in the same way as above. The composition and the evaluation results are shown in Table 5. A sample plate made from each of two colored thermoplastic resin compositions one of which contained the commercially available organometallic colorant containing more than 2,000 ppm of free metal and the other of which contained the organometallic colorant according to the present invention containing 2,000 ppm or less of free metal was examined on heat deflection temperature (¼") 6,35 mm, (264 psi) 1,8x10 7 Pa, no annealing), processability (230°C), (60 kg/cm 2 ) 59kPa and notched Izod impact strength (¼") 6,35 mm, (23°C). It was confirmed that there was no material difference between two compositions. Composition No. Organometallic colorant Free metal Silver streaks Kind Parts Free metal (ppm) (Resin+Colorant) (ppm) 280°C x 3 min 290°C x 3 min 290°C x 10 min 18 C. Ex. 2 5 2,850 135.7 XX XX XX 19 Ex. 2 5 53 2.5 O O O 20 Ex. 3 5 470 22. 4 O O O 21 Ex. 4 5 930 44.3 O O O 22 Ex. 5 5 1,850 88.1 O O ▵ 23 C. Ex. 3 5 2,150 102.4 XX XX XX Composition Nos. 24-33 100 Parts of the thermoplastic resin mixture (20 % of α-alkyl-substituted aromatic copolymer (a-3), 30 % of the ABS graft polymer and 50 % of polycarbonate) and 1.5 or 6 parts of the organometallic colorant and 1 part of the antioxidant were mixed by the Banbury mixer and kneaded and extruded by an extruder to produce colored pellets. The sample plates were produced in the same manner as above and evaluated with respect to the formation of silver streaks in the same way as above. The composition and the evaluation results are shown in Table 5. A sample plate from each of two colored thermoplastic resin compositions one of which contained the commercially available organometallic colorant containing more than 2,000 ppm of free metal and the other of which contained the organometallic colorant according to the present invention containing 2,000 ppm or less of free metal was examined on heat deflection temperature (¼") 6,35 mm, (264 psi) 1,8x10 7 Pa, no annealing), processability (230°C), (60 kg/cm 2 ) 59kPa and notched Izod impact strength (¼") 6,35 mm, (23°C). It was confirmed that there was no material difference between two compositions. Composition No. Organometallic colorant Free metal Silver streaks Kind Parts Free metal (ppm) (Resin+Colorant) (ppm) 280°C x 3 min 290°C x 3 min 290°C x 10 min 24 C. Ex. 4 1.5 3,130 46.3 X X XX 25 Ex. 6 1.5 170 2.5 O O O 26 Ex. 7 1.5 850 12.6 O O O 27 Ex. 8 1.5 1,930 28.5 O O ▵ 28 C. Ex. 5 1.5 2,230 33.0 X X XX 29 C. Ex. 4 6 3,130 177.2 X X XX 30 Ex. 6 6 170 9.6 O O O 31 Ex. 7 6 850 48.1 O O O 32 Ex. 8 6 1,930 109.2 O ▵ ▵ 33 C. Ex. 5 6 2,230 126.2 X X XX Composition Nos. 34-36 100 Parts of the thermoplastic resin mixture (70 % of α-alkyl-substituted aromatic copolymer (a-3) and 30 % of the ABS graft polymer, 0.3 part of titanium oxide, 0.2 part of carbon black, 0.3 part of iron oxide red, 0.2 part of perylene red, 2.0 parts of the organometallic colorant (Comparative Example 2 or Example 2 or 3), 0.5 part of ethylene-bisstearamide as a processing aid and 0.5 part of calcium stearate were mixed by the Banbury mixer and kneaded and extruded by an extruder to produce colored pellets. The sample plates were produced in the same manner as above and evaluated with respect to the formation of silver streaks in the same way as above. The composition and the evaluation results are shown in Table 6. A sample plate made from each of two colored thermoplastic resin compositions one of which contained the commercially available organometallic colorant containing more than 2,000 ppm of free metal and the other of which contained the organometallic colorant according to the present invention containing 2,000 ppm or less of free metal was examined on heat deflection temperature (¼") 6,35 mm, (264 psi) 1,8x10 7 Pa, no annealing), processability (230°C), (60 kg/cm 2 ) 59kPa and notched Izod impact strength (¼") 6,35 mm, (23°C). It was confirmed that there was no material difference between two compositions. Composition No. Organometallic colorant Free metal Silver streaks Kind Parts Free metal (ppm) (Resin+Colorant) (ppm) 280°C x 3 min 290°C x 3 min 290°C x 10 min 18 C. Ex. 2 2 2,850 55.3 X X XX 19 Ex. 2 2 53 1.0 O O O 20 Ex. 3 2 470 9.1 O O O

Claims: Use of an organometallic colorant containing free metal content of not more than 2,000 ppm, in a thermoplastic resin composition which comprises a thermoplastic resin which contains at least 5 % by weight of an α alkyl-substituted aromatic copolymer comprising repeating units of an α-alkyl-substituted aromatic vinyl compound and of at least one other comonomer copolymerizable therewith for the purpose of providing colored moldings having few or no silver streaks in its surface. Use according to claim 1, wherein the thermoplastic resin comprises the α-alkyl-substituted aromatic copolymer and at least one other thermoplastic polymer selected from the group consisting of a copolymer of an aromatic vinyl compound with vinyl cyanide and/or an alkyl ester of unsaturated carboxylic acid and a graft polymer of a rubbery polymer with and aromatic vinyl compound, vinyl cyanide and/or the alkyl ester of unsaturated carboxylic acid. Use according to claim 2 comprising 5 to 95 % by weight of α-alkyl-substituted aromatic copolymer and 95 to 5 % by weight of said other thermoplastic polymer.

Inventors: HASHIMOTO KENJI, MINEMATSU HIROYUKI, TAKAHASHI SYUZI, HASHIMOTO,KENJI, MINEMATSU,HIROYUKI, TAKAHASHI,SYUZI
Applicants: SUMITOMO DOW LTD, SUMITOMO DOW LIMITED
Application year: 1987
Main classification: C08K5
IPC codes: C08K5, C09B67