POLYCARBONATE BASED RESIN COMPOSITION AND MOLDED ARTICLES THEREOF

Abstract

The present invention relates to a polycarbonate based resin composition and molded articles thereof, and more particularly, to a polycarbonate based resin composition of which impact strength, flowability (fluidity), and the like, are improved, and molded articles thereof.

Claims

1. A polycarbonate based resin composition comprising: a copolycarbonate resin including a repeating unit represented by the following Chemical Formula 1, a repeating unit represented by the following Chemical Formula 3, and a repeating unit represented by the following Chemical Formula 4; and a first polycarbonate resin including a repeating unit represented by the following Chemical Formula 2: ##STR00020## in Chemical Formula 1, R.sub.1 to R.sub.4 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, Z.sub.1 is C.sub.1-10 alkylene unsubstituted or substituted with phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO, ##STR00021## in Chemical Formula 2, R.sub.5 to R.sub.12 are each independently hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, Z.sub.2 and Z.sub.3 are each independently C.sub.1-10 alkylene unsubstituted or substituted with phenyl, C.sub.3-15 cycloalkylene unsubstituted or substituted with C.sub.1-10 alkyl, O, S, SO, SO.sub.2, or CO, and A is C.sub.1-15 alkylene, ##STR00022## in Chemical Formula 3, each of X.sub.1 is independently C.sub.1-10 alkylene, each of R.sub.13 is independently hydrogen; C.sub.1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl-substituted C.sub.1-10 alkoxy, or C.sub.6-20 aryl; halogen; C.sub.1-10 alkoxy; allyl; C.sub.1-10 haloalkyl; or C.sub.6-20 aryl, and n is an integer of 10 to 200, ##STR00023## in Chemical Formula 4, each of X.sub.2 is independently C.sub.1-10 alkylene, each of Y.sub.1 is independently hydrogen, C.sub.1-6 alkyl, halogen, hydroxy, C.sub.1-6 alkoxy, or C.sub.6-20 aryl, each of R.sub.14 is independently hydrogen; C.sub.1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl-substituted C.sub.1-10 alkoxy, or C.sub.6-20 aryl; halogen; C.sub.1-10 alkoxy; allyl; C.sub.1-10 haloalkyl; or C.sub.6-20 aryl, and m is an integer of 10 to 200.

2. The polycarbonate based resin composition of claim 1, wherein: the first polycarbonate resin further includes a repeating unit represented by Chemical Formula 1.

3. The polycarbonate based resin composition of claim 1, further comprising a second polycarbonate resin including only a repeating unit represented by Chemical Formula 1.

4. (canceled)

5. The polycarbonate based resin composition of claim 1, wherein: the repeating unit represented by Chemical Formula 1 is derived from one or more aromatic diol compounds selected from the group consisting of bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)ether, bis(4-hydroxyphenyl)sulfone, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)ketone, 1,1-bis(4-hydroxyphenyl)ethane, bisphenol A, 2,2-bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(4-hydroxy-3,5-dibromophenyl)propane, 2,2-bis(4-hydroxy-3,5-dichlorophenyl)propane, 2,2-bis(4-hydroxy-3-bromophenyl)propane, 2,2-bis(4-hydroxy-3-chlorophenyl)propane, 2,2-bis(4-hydroxy-3-methylphenyl)propane, 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, 1,1-bis(4-hydroxyphenyl)-1-phenylethane, bis(4-hydroxyphenyl)diphenylmethane, and ,-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane.

6. The polycarbonate based resin composition of claim 1, wherein: the repeating unit represented by Chemical Formula 1 is represented by the following Chemical Formula 1-1: ##STR00024##

7. The polycarbonate based resin composition of claim 1, wherein: R.sub.5 to R.sub.12 are each independently hydrogen, methyl, chloro, or bromo.

8. The polycarbonate based resin composition of claim 1, wherein: Z.sub.1 and Z.sub.2 are each independently a linear or branched C.sub.1-10 alkylene unsubstituted or substituted with phenyl, cyclohexane-1,1-diyl, O, S, SO, SO.sub.2, or CO.

9. The polycarbonate based resin composition of claim 1, wherein: A is a linear C.sub.1-10 alkylene.

10. The polycarbonate based resin composition of claim 1, wherein: the repeating unit represented by Chemical Formula 2 is represented by Chemical Formula 2-1: ##STR00025##

11. The polycarbonate based resin composition of claim 2, wherein: the first polycarbonate resin includes the repeating unit represented by Chemical Formula 1 and the repeating unit represented by Chemical Formula 2 at a weight ratio of 1:0.001 to 1:0.3.

12. The polycarbonate based resin composition of claim 1, wherein: the copolycarbonate resin includes the respective repeating units so that a weight ratio of the repeating unit represented by Chemical Formula 1 and a sum of weights of the repeating units represented by Chemical Formulae 3 and 4 is 1:0.001 to 1:0.5.

13. The polycarbonate based resin composition of claim 1, wherein: the repeating unit represented by Chemical Formula 3 is represented by Chemical Formula 3-2: ##STR00026##

14. The polycarbonate based resin composition of claim 12, wherein: R.sub.13 is methyl.

15. The polycarbonate based resin composition of claim 1, wherein: the repeating unit represented by Chemical Formula 4 is represented by Chemical Formula 4-2: ##STR00027##

16. The polycarbonate based resin composition of claim 14, wherein: R.sub.14 is methyl.

17.-18. (canceled)

Description

MODE FOR INVENTION

[0135] Hereinafter, preferable Examples of the present invention will be provided for better understanding of the present invention. However, the following Examples are provided only for illustration of the present invention, and should not be construed as limiting the present invention by the examples.

Preparation Example 1: Preparation of Polyorganosiloxane AP-30

[0136] ##STR00018##

[0137] After 42.5 g (142.8 mmol) of octamethylcyclotetrasiloxane and 2.26 g (16.8 mmol) of tetramethyldisiloxane were mixed with each other, the mixture was placed in a 3 L flask with 1 part by weight of acid clay (DC-A3) based on 100 parts by weight of octamethylcyclotetrasiloxane, and reacted at 60 C. for 4 hours. After the reaction was terminated, the reaction product was diluted with ethylacetate and quickly filtered using a celite. A repeating unit (n) of the unmodified polyorganosiloxane obtained as described above was 30 when confirmed through .sup.1H NMR.

[0138] 9.57 g (71.3 mmol) of 2-allylphenol and 0.01 g (50 ppm) of Karstedt's platinum catalyst were added to the obtained terminal-unmodified polyorganosiloxane and reacted at 90 C. for 3 hours. After the reaction was terminated, the unreacted polyorganosiloxane was removed by evaporation at 120 C. and 1 torr. The terminal-modified polyorganosiloxane obtained as described above was designated as AP-30. AP-30 was pale yellow oil, the repeating unit(n) was 30 when confirmed through .sup.1HNMR using Varian 500 MHz, and further purification was not required.

Preparation Example 2: Preparation of Polyorganosiloxane MB-60

[0139] ##STR00019##

[0140] After 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.5 g (11 mmol) of tetramethyldisiloxane were mixed with each other, the mixture was placed in a 3 L flask together with 1 part by weight of acid clay (DC-A3) based on 100 parts by weight of octamethylcyclotetrasiloxane, and reacted at 60 C. for 4 hours. After the reaction was terminated, the reaction product was diluted with ethylacetate and quickly filtered using a celite. A repeating unit (n) of the terminal-unmodified polyorganosiloxane obtained as described above was 60 when confirmed through .sup.1H NMR.

[0141] 6.13 g (29.7 mmol) of 3-methylbut-3-enyl 4-hydroxybenzoate and 0.01 g (50 ppm) of Karstedt's platinum catalyst were added to the obtained terminal-unmodified polyorganosiloxane and reacted at 90 C. for 3 hours. After the reaction was terminated, the unreacted polyorganosiloxane was removed by evaporation at 120 C. and 1 torr. The terminal-modified polyorganosiloxane obtained as described above was designated as MB-60. MB-60 was pale yellow oil, the repeating unit (m) was 60 when confirmed through .sup.1HNMR using Varian 500 MHz, and further purification was not required.

Preparation Example 3: Preparation 1 of Copolycarbonate Resin

[0142] After placing 979.9 g of bisphenol A (BPA), 1,620 g of 32% aqueous NaOH solution, and 7,500 g of distilled water in a 20 L glass reactor and confirming that BPA was completely dissolved under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of p-tert-butylphenol (PTBP), 79.3179 g of previously prepared polyorganosiloxane (AP-30), and 8.8191 g of polyorganosiloxane (MB-60) of Preparation Example 2 were added thereto and mixed therewith (9 wt % of polyorganosiloxanes (AP-30+MB-60) were used based on BPA; repeating units represented by Chemical Formulae 1, 3, and 4 were formed so as to have contents corresponding thereto). 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added thereto dropwise for 1 hour. In this case, a PH of the aqueous NaOH solution was maintained at 12. After the dropwise addition was completed, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added thereto. After 10 minutes, a pH was adjusted to 3 with 1N aqueous hydrochloric acid solution, and then the resultant was washed with distilled water three times. Thereafter, a methylene chloride phase was separated, and precipitated in methanol, thereby obtaining a copolycarbonate resin (Mw: 34000) as powder.

Preparation Example 4: Preparation 2 of Copolycarbonate Resin

[0143] After placing 979.9 g of bisphenol A (BPA), 1,620 g of 32% aqueous NaOH solution, and 7,500 g of distilled water in a 20 L glass reactor and confirming that BPA was completely dissolved under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of p-tert-butylphenol (PTBP), 83.7814 g of previously prepared polyorganosiloxane (AP-30), and 4.4096 g of polyorganosiloxane (MB-60) of Preparation Example 2 were added thereto and mixed therewith (9 wt % of polyorganosiloxanes (AP-30+MB-60) were used based on BPA; repeating units represented by Chemical Formulae 1, 3, and 4 were formed so as to have contents corresponding thereto). 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added thereto dropwise for 1 hour. In this case, a PH of the aqueous NaOH solution was maintained at 12. After the dropwise addition was completed, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added thereto. After 10 minutes, a pH was adjusted to 3 with 1N aqueous hydrochloric acid solution, and then the resultant was washed with distilled water three times. Thereafter, a methylene chloride phase was separated, and precipitated in methanol, thereby obtaining a copolycarbonate resin (Mw: 34000) as powder.

Preparation Example 5: Preparation 3 of Copolycarbonate Resin

[0144] After placing 979.9 g of bisphenol A (BPA), 1,620 g of 32% aqueous NaOH solution, and 7,500 g of distilled water in a 20 L glass reactor and confirming that BPA was completely dissolved under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of p-tert-butylphenol (PTBP), 52.914 g of previously prepared polyorganosiloxane (AP-30), and 5.88 g of polyorganosiloxane (MB-60) of Preparation Example 2 were added thereto and mixed therewith (6 wt % of polyorganosiloxanes (AP-30+MB-60) were used based on BPA; repeating units represented by Chemical Formulae 1, 3, and 4 were formed so as to have contents corresponding thereto). 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added thereto dropwise for 1 hour. In this case, a PH of the aqueous NaOH solution was maintained at 12. After the dropwise addition was completed, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added thereto. After 10 minutes, a pH was adjusted to 3 with 1N aqueous hydrochloric acid solution, and then the resultant was washed with distilled water three times. Thereafter, a methylene chloride phase was separated, and precipitated in methanol, thereby obtaining a copolycarbonate resin (Mw: 34000) as powder.

Preparation Example 6: Preparation 4 of Copolycarbonate Resin

[0145] After placing 979.9 g of bisphenol A (BPA), 1,620 g of 32% aqueous NaOH solution, and 7,500 g of distilled water in a 20 L glass reactor and confirming that BPA was completely dissolved under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of p-tert-butylphenol (PTBP), and 88.191 g of previously prepared polyorganosiloxane (AP-30) were added thereto and mixed therewith (9 wt % of polyorganosiloxane (AP-30) was used based on BPA; repeating units represented by Chemical Formulae 1 and 3 were formed so as to have contents corresponding thereto). 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added thereto dropwise for 1 hour. In this case, a PH of the aqueous NaOH solution was maintained at 12. After the dropwise addition was completed, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added thereto. After 10 minutes, a pH was adjusted to 3 with 1N aqueous hydrochloric acid solution, and then the resultant was washed with distilled water three times. Thereafter, a methylene chloride phase was separated, and precipitated in methanol, thereby obtaining a copolycarbonate resin (Mw: 34000) as powder.

Preparation Example 7: Preparation 1 of First Polycarbonate Resin

[0146] After placing 976.9 g of bisphenol A (BPA), 1,620 g of 32% aqueous NaOH solution, and 7,500 g of distilled water in a 20 L glass reactor and confirming that BPA was completely dissolved under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of p-tert-butylphenol (PTBP), and 7.81 g of previously prepared bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl) decanedioate (BPDA) were added thereto and mixed therewith (0.8 wt % of BPDA was used based on BPA; repeating units represented by Chemical Formulae 1 and 2 were formed so as to have contents corresponding thereto). 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added thereto dropwise for 1 hour. In this case, a PH of the aqueous NaOH solution was maintained at 12. After the dropwise addition was completed, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added thereto. After 10 minutes, a pH was adjusted to 3 with 1N aqueous hydrochloric acid solution, and then the resultant was washed with distilled water three times. Thereafter, a methylene chloride phase was separated, and precipitated in methanol, thereby obtaining a polycarbonate resin (Mw: 34000) as powder.

Preparation Example 8: Preparation 2 of First Polycarbonate Resin

[0147] After placing 968.9 g of bisphenol A (BPA), 1,620 g of 32% aqueous NaOH solution, and 7,500 g of distilled water in a 20 L glass reactor and confirming that BPA was completely dissolved under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of p-tert-butylphenol (PTBP), and 29.32 g of previously prepared bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl) decanedioate (BPDA) were added thereto and mixed therewith (3.0 wt % of BPDA was used based on BPA; repeating units represented by Chemical Formulae 1 and 2 were formed so as to have contents corresponding thereto). 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added thereto dropwise for 1 hour. In this case, a PH of the aqueous NaOH solution was maintained at 12. After the dropwise addition was completed, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added thereto. After 10 minutes, a pH was adjusted to 3 with 1N aqueous hydrochloric acid solution, and then the resultant was washed with distilled water three times. Thereafter, a methylene chloride phase was separated, and precipitated in methanol, thereby obtaining a polycarbonate resin (Mw: 34000) as powder.

Preparation Example 9: Preparation 3 of First Polycarbonate Resin

[0148] After placing 943.7 g of bisphenol A (BPA), 1,620 g of 32% aqueous NaOH solution, and 7,500 g of distilled water in a 20 L glass reactor and confirming that BPA was completely dissolved under nitrogen atmosphere, 3,670 g of methylene chloride, 17.9 g of p-tert-butylphenol (PTBP), and 96.34 g of previously prepared bis(4-(2-(4-hydroxyphenyl)propan-2-yl)phenyl) decanedioate (BPDA) were added thereto and mixed therewith (10.0 wt % of BPDA was used based on BPA; repeating units represented by Chemical Formulae 1 and 2 were formed so as to have contents corresponding thereto). 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added thereto dropwise for 1 hour. In this case, a PH of the aqueous NaOH solution was maintained at 12. After the dropwise addition was completed, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added thereto. After 10 minutes, a pH was adjusted to 3 with 1N aqueous hydrochloric acid solution, and then the resultant was washed with distilled water three times. Thereafter, a methylene chloride phase was separated, and precipitated in methanol, thereby obtaining a polycarbonate resin (Mw: 34000) as powder.

Preparation Example 10: Preparation 4 of Polycarbonate Resin

[0149] After placing 979.9 g of bisphenol A (BPA), 1,620 g of 32% aqueous NaOH solution, and 7,500 g of distilled water in a 20 L glass reactor and confirming that BPA was completely dissolved under nitrogen atmosphere, 3,670 g of methylene chloride and 17.9 g of p-tert-butylphenol (PTBP) were added thereto and mixed therewith. 3,850 g of methylene chloride in which 542.5 g of triphosgene was dissolved was added thereto dropwise for 1 hour. In this case, a PH of the aqueous NaOH solution was maintained at 12. After the dropwise addition was completed, the mixture was aged for 15 minutes, and 195.7 g of triethylamine was dissolved in methylene chloride and added thereto. After 10 minutes, a pH was adjusted to 3 with 1N aqueous hydrochloric acid solution, and then the resultant was washed with distilled water three times. Thereafter, a methylene chloride phase was separated, and precipitated in methanol, thereby obtaining a polycarbonate resin (Mw: 34000) as powder.

Examples 1 to 5 and Comparative Examples 1 to 5: Preparation of Polycarbonate Based Resin Composition and Molded Articles Thereof

[0150] The copolycarbonate resin and the polycarbonate resin were mixed according to the composition illustrated in the following Table 1. Additionally, based on 1 part by weight of the resin mixture, 0.050 parts by weight of tris(2,4-di-tert-butylphenyl)phosphite, 0.010 parts by weight of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, and 0.030 parts by weight of pentaerythritoltetrastearate were added thereto, and the resulting mixture was pelletized using a 30 mm twin-screw extruder provided with a vent, and was injection-molded at a cylinder temperature of 300 C. and a mold temperature of 80 C. using a N-20C injection-molding machine (JSW Co.), thereby preparing a desired specimen.

TABLE-US-00001 TABLE 1 Comparative Comparative Comparative Comparative Comparative Example 1 Example 2 Example 3 Example 4 Example 5 Example 1 Example 2 Example 3 Example 4 Example 5 Co-PC Prepara- Preparation Preparation Preparation Preparation X Preparation X Preparation Preparation Resin* tion Example 3 Example 3 Example 4 Example 5 (0) Example 3 (0) Example 6 Example 6 (wt %) Example 3 (50) (50) (50) (50) (100) (100) (50) (50) First PC Prepara- Preparation Preparation Preparation Preparation Preparation X Preparation X Preparation resin* tion Example 8 Example 9 Example 8 Example 8 Example (0) Example 9 (0) Example 9 (wt %) Example 7 (50) (50) (50) (50) 10* (100) (50) (50) (100) *Co-PC Resin: Copolycarbonate resin *First PC resin: first polycarbonate resin *Preparation Example 10: Since the specimen was prepared without using BPDA, the specimen did not correspond to the first polycarbonate resin, but corresponded to a general polycarbonate resin (corresponding to the second polycarbonate resin).

Experimental Example: Confirm of Characteristics of Polycarbonate Based Resin Composition and Injected Specimen

[0151] Weight average molecular weights of the copolycarbonate resins and the polycarbonate resins prepared in Examples and Comparative Examples were measured by GPC using PC standard and Agilent 1200 series.

[0152] In addition, physical properties of the compositions and injection specimens obtained in Examples and Comparative Examples were measured by the following methods, and the results were illustrated in the following Table 2.

[0153] 1) Room-Temperature Impact Strength: measured at 23 C. in accordance with ASTM D256 ( inch, Notched Izod).

[0154] 2) Low-Temperature Impact Strength: measured at 30 C. in accordance with ASTM D256 ( inch, Notched Izod).

[0155] 3) YI (Yellow Index): Specimen (width/length/thickness=60 mm/40 mm/3 mm) was injection-molded at 300 C., and then YI (Yellow Index) was measured under the following conditions by using Color-Eye 7000A (X-rite Inc.) in accordance with ASTM D1925. [0156] Measurement temperature: room temperature (23 C.) [0157] Aperture size: Large area of view

[0158] Measurement method: transmittance was measured in a spectral range (360 nm to 750 nm) [0159] 4) Flowability (MI): measured in accordance with ASTM D1238 (300 C., 1.2 kg condition).

TABLE-US-00002 TABLE 2 Room-Temperature Low-temperature Impact Strength Impact Strength MI (J/m) (J/m) YI (g/10 min) Example 1 980 900 1.98 6.8 Example 2 900 830 1.98 7.1 Example 3 830 810 1.95 12.2 Example 4 845 780 1.96 6.8 Example 5 800 680 1.94 8.1 Comparative 950 190 1.75 5.7 Example 1 Comparative 1090 980 6.8 3.1 Example 2 Comparative 820 230 0.93 15.9 Example 3 Comparative 800 520 6.3 4.3 Example 4 Comparative 720 460 1.98 10.9 Example 5

[0160] Referring to Table 2, it was confirmed that in Examples 1 to 5, high room-temperature impact strength and low-temperature impact strength, a low YI value, and relatively high flowability (MI) were simultaneously exhibited. On the contrary, it was confirmed that in Comparative Examples 1, 3, and 5, low-temperature impact strength was low. Particularly, as illustrated in Comparative Example 5, it was confirmed that in a case in which a structure of the copolycarbonate resin was different from that in Examples, low-temperature impact strength was deteriorated.

[0161] Further, it was confirmed that in Comparative Examples 2 and 4, flowability was poor, a YI value was high as compared to Examples, and in Comparative Example 4, low-temperature impact strength was also not sufficient.