COPOLYCARBONATE RESIN COMPOSITION AND ARTICLE INCLUDING THE SAME

Abstract

The present invention relates to a copolycarbonate resin composition having improved mechanical properties such as impact resistance and chemical resistance while maintaining resin flowability, and an article including the same.

Claims

1. A copolycarbonate resin composition comprising: a copolycarbonate resin including an aromatic polycarbonate-based first repeating unit and one or more aromatic polycarbonate-based second repeating unit having at least one siloxane bond; and a polysiloxane polymer containing a hydrocarbon-based functional group having 2 or more carbon atoms.

2. The copolycarbonate resin composition of claim 1, wherein: the polysiloxane polymer contains 0.001 mol % to 10 mol % of the hydrocarbon-based functional group having 2 or more carbon atoms.

3. The copolycarbonate resin composition of claim 1, wherein: the polysiloxane polymer includes a polysiloxane repeating unit including the hydrocarbon-based functional group having 2 or more carbon atoms and a polydimethylsiloxane repeating unit.

4. The copolycarbonate resin composition of claim 1, wherein: the hydrocarbon-based functional group includes one or more selected from the group consisting of an aliphatic hydrocarbon functional group, a cycloaliphatic hydrocarbon functional group and an aromatic hydrocarbon functional group.

5. The copolycarbonate resin composition of claim 4, wherein: the aliphatic hydrocarbon functional group includes a straight chain or branched chain alkyl group; or vinyl-based functional group.

6. The copolycarbonate resin composition of claim 5, wherein: the vinyl-based functional group includes a functional group represented by the following Chemical Formula 11: ##STR00019## wherein * denotes a bonding position, and R.sub.8, R.sub.9 and R.sub.10 are independently of one another, hydrogen; a straight chain or branched chain alkyl group having 1 to 20 carbon atoms; an aryl group having 6 to 20 carbon atoms; an alkenyl group having 2 to 20 carbon atoms; an alkoxy group having 1 to 20 carbon atoms; a cycloalkyl group having 3 to 20 carbon atoms; a ketone group; or an ester group.

7. The copolycarbonate resin composition of claim 1, wherein: the polysiloxane repeating unit containing the hydrocarbon-based functional group having 2 or more carbon atoms includes a repeating unit represented by the following Chemical Formula 12: ##STR00020## wherein * denotes a bonding position, and, at least one of R.sub.11 and R.sub.12 is a hydrocarbon-based functional group having 2 or more carbon atoms, and the other one is a methyl group.

8. The copolycarbonate resin composition of claim 3, wherein: a mole ratio of the polysiloxane repeating unit including the hydrocarbon functional group having 2 or more carbon atoms to the polydimethylsiloxane repeating unit is 0.00001 to 0.1.

9. The copolycarbonate resin composition of claim 1, wherein: the polysiloxane polymer further includes a hydrocarbon-based functional group having 2 or more carbon atoms bonded to an end of the polysiloxane polymer.

10. The copolycarbonate resin composition of claim 1, wherein: the polysiloxane polymer containing the hydrocarbon-based functional group having 2 or more carbon atoms includes a compound represented by the following Chemical Formula 14: ##STR00021## wherein m is an integer of 10 to 20, and n is an integer of 6000 to 11500, and D is a hydrocarbon-based functional group having 2 or more carbon atoms.

11. The copolycarbonate resin composition of claim 1, wherein: a content of the polysiloxane polymer containing the hydrocarbon-based functional group having 2 or more carbon atoms is 0.01 wt % to 10 wt %, based on a total weight of the copolycarbonate resin composition.

12. The copolycarbonate resin composition of claim 1, wherein: the polysiloxane polymer containing the hydrocarbon-based functional group having 2 or more carbon atoms has a weight average molecular weight of 100,000 g/mol to 1,000,000 g/mol.

13. The copolycarbonate resin composition of claim 1, wherein: the aromatic polycarbonate-based first repeating unit includes a repeating unit represented by the following Chemical Formula 1: ##STR00022## wherein R.sub.1 to R.sub.4 are independently of one another hydrogen, C.sub.1-10 alkyl, C.sub.1-10 alkoxy, or halogen, and Z 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.

14. The copolycarbonate resin composition of claim 13, wherein: the repeating unit represented by Chemical Formula 1 is derived from any 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)diphenyl methane and ,-bis[3-(o-hydroxyphenyl)propyl]polydimethylsiloxane.

15. The copolycarbonate resin composition of claim 13, wherein: the repeating unit represented by Chemical Formula 1 is the following Chemical Formula 1-1: ##STR00023##

16. The copolycarbonate resin composition of claim 1, wherein: the aromatic polycarbonate-based second repeating unit includes one or more repeating groups selected from the group consisting of repeating units represented by the following Chemical Formula 2 to 4: ##STR00024## wherein X.sub.1 is C.sub.1-10 alkylene, R.sub.5 is 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 n1 is an integer of 10 to 200, ##STR00025## wherein X.sub.2 is C.sub.1-10 alkylene, Y.sub.1 is hydrogen, C.sub.1-6 alkyl, halogen, hydroxy, C.sub.1-6 alkoxy or C.sub.6-20 aryl, R.sub.6 is 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 n2 is an integer of 10 to 200, ##STR00026## wherein X.sub.3 is C.sub.1-10 alkylene, Y.sub.2 is C.sub.1-10 alkoxy, R.sub.7 is 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 n3 is an integer of 10 to 200.

17. The copolycarbonate resin composition of claim 16, wherein: the repeating unit represented by Chemical Formula 2 is the following Chemical Formula 2-1: ##STR00027##

18. The copolycarbonate resin composition of claim 16, wherein: the repeating unit represented by Chemical Formula 3 is the following Chemical Formula 3-1: ##STR00028##

19. The copolycarbonate resin composition of claim 16, wherein: the repeating unit represented by Chemical Formula 4 is the following Chemical Formula 4-1: ##STR00029##

20. The copolycarbonate resin composition of claim 1, wherein: the copolycarbonate resin including the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond includes 0.001 wt % to 10 wt % of the second repeating unit.

21. The copolycarbonate resin composition of claim 1, wherein: the copolycarbonate resin including the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond has a weight average molecular weight of 1,000 g/mol to 100,000 g/mol.

22. An article comprising the copolycarbonate resin composition of claim 1.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

[0146] The present invention will be described in detail in the following Examples. However, the following Examples only illustrate the present invention, and the description of the present invention is not limited by the following Examples.

Preparation Examples 1 to 4

Preparation Example 1: Preparation of Polyorganosiloxane (AP-PDMS, n1=34)

[0147] 47.6 g (160 mmol) of octamethylcyclotetrasiloxane and 2.4 g (17.8 mmol) of tetramethyldisiloxane were mixed, and then the mixture was added to a 3 L flask together with 1 part by weight of acid clay (DC-A3) relative to 100 parts by weight of octamethylcyclotetrasiloxane, and reacted at 60 C. for 4 hours. After completing the reaction, it was diluted with ethyl acetate, and rapidly filtered using celite. The number of the thus-obtained repeating unit (n1) of unmodified polyorganosiloxane was 34 as confirmed by .sup.1H NMR.

[0148] To the obtained end-unmodified polyorganosiloxane, 4.81 g (35.9 mmol) of 2-allylphenol and 0.01 g (50 ppm) of Karstedt's platinum catalyst were added, and reacted at 90 C. for 3 hours. After completing the reaction, unreacted siloxane was evaporated under a condition of 120 C. and 1 torr, thereby being removed. The thus-obtained end-modified polyorganosiloxane was named as AP-PDMS (n1=34). AP-PDMS was light yellow oil, the number of the repeating unit (n1) was 34, as confirmed by .sup.1H NMR using Varian 500 MHz, and no further purification was needed.

Preparation Example 2: Preparation of Polyorganosiloxane (MBHB-PDMS, n2=58)

[0149] 47.60 g (160 mmol) of octamethylcyclotetrasiloxane, and 1.5 g (11 mmol) of tetramethyldisiloxane were mixed, and then the mixture was added to a 3 L flask together with 1 part by weight of acid clay (DC-A3) relative to 100 parts by weight of octamethylcyclotetrasiloxane, and reacted at 60 C. for 4 hours. After completing the reaction, it was diluted with ethyl acetate, and rapidly filtered using celite. The number of the thus-obtained repeating unit (n2) of end-unmodified polyorganosiloxane was 58 as confirmed by .sup.1H NMR.

[0150] To the obtained end-unmodified polyorganosiloxane, 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, and reacted at 90 C. for 3 hours. After completing the reaction, unreacted siloxane was evaporated under a condition of 120 C. and 1 torr, thereby being removed. The thus-obtained end-modified polyorganosiloxane was named as MBHB-PDMS (n2=58). MBHB-PDMS was light yellow oil, the number of the repeating unit (n2) was 58, as confirmed by .sup.1H NMR using Varian 500 MHz, and no further purification was needed.

Preparation Example 3: Preparation of Copolycarbonate Resin

[0151] 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to a polymerization reactor, and mixed and dissolved under N.sub.2 atmosphere. A mixed solution of 4.3 g of PTBP (para-tert butylphenol), 4.73 g of AP-PDMS (n1=34) prepared in the Preparation Example 1, and 0.53 g of MBHB-PDMS (n2=58) prepared in the Preparation Example 2 was dissolved with MC (methylene chloride), and added thereto. Next, 128 g of TPG (triphosgene) was dissolved in MC to maintain the pH at 11 or more, added for 1 hour to be reacted, and then after 10 minutes, 46 g of TEA (triethylamine) was added thereto, thereby carrying out a coupling reaction. After a total reaction time of 1 hour and 20 minutes, pH was lowered to 4, thereby removing TEA, and the pH of the produced polymer was adjusted to neutral at pH 6-7 by washing with distilled water three times. The thus-obtained polymer was reprecipitated in a mixed solution of methanol and hexane, and dried at 120 C., thereby obtaining a final copolycarbonate resin.

Preparation Example 4: Preparation of Polycarbonate Resin

[0152] 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to a polymerization reactor, and mixed and dissolved under N.sub.2 atmosphere. Next, 128 g of TPG (triphosgene) was dissolved in MC to maintain the pH at 11 or more, added for 1 hour to be reacted, and then after 10 minutes, 46 g of TEA (triethylamine) was added thereto, thereby carrying out a coupling reaction. After a total reaction time of 1 hour and 20 minutes, pH was lowered to 4, thereby removing TEA, and the pH of the produced polymer was adjusted to neutral at pH 6-7 by washing with distilled water three times. The thus-obtained polymer was reprecipitated in a mixed solution of methanol and hexane, and dried at 120 C., thereby obtaining a final copolycarbonate resin.

Preparation Example 5: Preparation of Copolycarbonate Resin

[0153] 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to a polymerization reactor, and mixed and dissolved under N.sub.2 atmosphere. 4.3 g of PTBP (para-tert butylphenol) and 4.73 g of AP-PDMS (n1=34) prepared in Preparation Example 1 were dissolved with MC (methylene chloride) and added thereto. Next, 128 g of TPG (triphosgene) was dissolved in MC to maintain the pH at 11 or more, added for 1 hour to be reacted, and then after 10 minutes, 46 g of TEA (triethylamine) was added thereto, thereby carrying out a coupling reaction. After a total reaction time of 1 hour and 20 minutes, pH was lowered to 4, thereby removing TEA, and the pH of the produced polymer was adjusted to neutral at pH 6-7 by washing with distilled water three times. The thus-obtained polymer was reprecipitated in a mixed solution of methanol and hexane, and dried at 120 C., thereby obtaining a final copolycarbonate resin.

Examples 1 to 3: Preparation of Copolycarbonate Resin Composition

Example 1

[0154] To the copolycarbonate resin prepared in the Preparation Example 3, SF3900C (KCC, vinyl group content: 0.07 mol %) was added at a content of 1 wt %, and mixed with a mixer.

[0155] Thereafter, 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 pentaerythritol tetrastearate relative to 1 parts by weight of the copolycarbonate resin composition were added thereto, and extruded at 300 C. using a vent attached D30 mm twin-screw extruder, thereby preparing a copolycarbonate resin composition in a pellet form.

Example 2

[0156] A copolycarbonate resin composition was prepared in the same manner as in Example 1, except that SF3900C (KCC, vinyl group content: 0.07 mol %) was added at a content of 2 wt %.

Example 3

[0157] A copolycarbonate resin composition was prepared in the same manner as in Example 1, except that SF3900C (KCC, vinyl group content: 0.07 mol %) was added at a content of 3 wt %.

Comparative Examples 1 to 4: Preparation of Copolycarbonate Resin Composition and Article

Comparative Example 1

[0158] A copolycarbonate resin composition was prepared in the same manner as in Example 1, except that SF3900C (KCC, vinyl group content: 0.07 mol %) was not added.

Comparative Example 2

[0159] A copolycarbonate resin composition was prepared in the same manner as in Example 1, except that SF3900C (KCC, vinyl group content: 0.07 mol %) was not added, and the polycarbonate resin prepared in Preparation Example 4 was used instead of the copolycarbonate resin prepared in Preparation Example 3.

Comparative Example 3

[0160] The copolycarbonate resin prepared in Preparation Example 5 was used.

Comparative Example 4

[0161] A copolycarbonate resin composition was prepared in the same manner as in Example 1, except that the polycarbonate resin prepared in Preparation Example 4 was used instead of the copolycarbonate resin prepared in Preparation Example 3.

Experimental Example: Measurement of Physical Properties of Copolycarbonate Resin Composition Obtained in Examples and Comparative Examples

[0162] The copolycarbonate resin compositions obtained in the Examples and Comparative Examples were subjected to injection molding at a cylinder temperature of 300 C., and a mold temperature of 80 C., using an N-20C injection molding machine from JSW, Ltd., thereby manufacturing specimens.

[0163] Thereafter, the physical properties of the specimens were measured by the following methods, and the results are shown in Table 1.

[0164] 1. Melt flow rate (MFK)

[0165] It was measured according to ASTM D1238 (300 C., 1.2 kg condition).

[0166] 2. Weight average molecular weight

[0167] It was measured by GPC using a PC standard, using Agilent 1200 series.

[0168] 3. Impact strength at low temperature

[0169] 3-1. Impact strength at 30 C. (J/m)

[0170] It was measured 30 C. according to ASTM D256 ( inch, Notched Izod).

[0171] 3-2. Impact strength at 40 C. (J/m)

[0172] It was measured 40 C. according to ASTM D256 ( inch, Notched Izod).

[0173] 4. Chemical resistance

[0174] A specimen (thickness: 3.2 mm) for measuring tensile strength was manufactured according to ASTM D638, and the chemical resistance was measured based on JIG Strain R1.0 according to ASTM D543 (PRACTICE B).

[0175] Specifically, a cotton cloth (2 cm2 cm) was placed on the center of the specimen at room temperature (23 C.), and the time taken from the moment when 2 ml of a solvent (Nivea, aqua protect sun spraySPF 30, manufactured by Beiersdorf AG) was dropped to the cloth, to the point when each specimen was broken was measured, and evaluation was carried out, under the following criteria:

[0176] : 24 hours or more

[0177] : 1 to 24 hours

[0178] : 1 minute to 1 hour

[0179] x: 1 minute or less

TABLE-US-00001 TABLE 1 Compositions of Examples and Comparative Examples and Results of Experimental Example Com- Com- Com- Com- parative parative parative parative Classification Example 1 Example 2 Example 3 Example 1 Example 2 Example 3 Example 4 PC Preparation Preparation Preparation Preparation Preparation Preparation Preparation Example Example Example Example Example Example Example 3 3 3 3 4 5 4 Additive SF3900C SF3900C SF3900C SF3900C (1 wt %) (2 wt %) (3 wt %) (2 wt %) Melt flow rate 7 8 9 7 11 10 12 (g/10 min) Impact 1/8 747 750 740 731 136 638 580 strength inch, at low - temper- 30 ature C. (J/m) 1/4 225 253 282 190 113 123 260 inch, - 40 C. molecular 30,600 30,500 30,700 30,500 28,100 29,300 28,300 weight Chemical X X resistance

[0180] As shown in above Table 1, in the case of the copolycarbonate resin compositions of the Examples including the additive, it was confirmed that the time to be modified by the solvent is long, being 1 hour or more, and thus, the chemical resistance is excellent, however, in the case of the copolycarbonate resin compositions of Comparative Examples without the additive, the time to be modified by the solvent is short, being less than 1 hour, and thus, the chemical resistance was poorer than that of Examples.

[0181] In addition, when comparing the copolycarbonate resin compositions of Examples 1 to 3 with the copolycarbonate resin composition of Comparative Example 1, it was confirmed that those compositions identically include the silicon-containing copolycarbonate resin prepared in Preparation Example 3, however, the compositions of Examples 1 to 3 to which an additive is further added have increased values of the impact strength at low temperature. Further, as a result of including the silicon-containing copolycarbonate resin of Preparation Example 3 identically, the melt flow rate property was measured at the same level.

[0182] In the case of the copolycarbonate resin composition of Comparative Example 3, as it includes only the copolycarbonate resin prepared in Preparation Example 5 without an additive, it had low impact strength at low temperature, a high melt flow rate, and poor chemical resistance, as compared with that of Examples.

[0183] In the case of the copolycarbonate resin composition of Comparative Example 4, though it includes an additive together with the copolycarbonate resin prepared in Preparation Example 4, it used the polycarbonate resin obtained in Preparation Example 4, and thus, the impact strength at low temperature at inch, 30 C. was measured to be lower, and the melt flow rate was found to be higher than those of Examples.

[0184] Accordingly, it was confirmed that the copolycarbonate resin composition includes a certain copolycarbonate resin and an additive, thereby having increased impact resistance and chemical resistance together with the improved properties of the copolycarbonate resin (e.g., melt flow rate) depending on the additive.