Polycarbonate composition and article comprising the same

Abstract

The present invention relates to a polycarbonate composition including a polycarbonate and an impact reinforcing agent, and an inorganic filler to improve a mechanical property thereof, and a copolycarbonate to solve a problem of appearance defect caused by including the inorganic filler.

Claims

1. A polycarbonate composition comprising: a polycarbonate, an impact reinforcing agent, a copolycarbonate comprising an aromatic polycarbonate-based first repeating unit; and one or more aromatic polycarbonate-based second repeating units having siloxane bonds, and an inorganic filler, wherein the first repeating unit is represented by Chemical Formula 1 below, and the second repeating unit comprises a repeating unit represented by Chemical Formula 2 below and a repeating unit represented by Chemical Formula 3 below: ##STR00015## in the Chemical Formula 1, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently 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, ##STR00016## in the Chemical Formula 2, X.sub.1 is each independently C.sub.1-10 alkylene, R.sub.5 is each 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, ##STR00017## in the Chemical Formula 3, X.sub.2 is each independently C.sub.1-10 alkylene, Y.sub.1 is each independently hydrogen, C.sub.1-6 alkyl, halogen, hydroxy, C.sub.1-6 alkoxy, or C.sub.6-20 aryl, R.sub.6 is each 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 composition of claim 1, wherein: the polycarbonate composition comprises 1 to 13 parts by weight of the polycarbonate, 1 part by weight of the impact reinforcing agent, 1 to 6 parts by weight of the copolycarbonate, and 0.5 to 4 parts by weight of the inorganic filler.

3. The polycarbonate composition of claim 1, wherein: the polycarbonate comprises a repeating unit represented by Chemical Formula 4 below: ##STR00018## in the Chemical Formula 4, R.sub.1, R.sub.2, R.sub.3 and R.sub.4 are each independently 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.

4. The polycarbonate composition of claim 1, wherein: the impact reinforcing agent is a methylmethacrylate-butadiene-styrene-based copolymer, a styrene-acrylonitrile-based copolymer, an acrylonitrile-butadiene-styrene-based copolymer, or mixtures thereof.

5. The polycarbonate composition of claim 1, wherein: the polycarbonate composition comprises 5 to 13 parts by weight of the polycarbonate.

6. The polycarbonate composition of claim 1, wherein: the polycarbonate has a weight average molecular weight of 1,000 to 100,000.

7. The polycarbonate composition of claim 1, wherein: the copolycarbonate has a weight average molecular weight of 1,000 to 100,000.

8. The polycarbonate composition of claim 1, further comprising: 0.5 to 4 parts by weight of a flame retardant.

9. The polycarbonate composition of claim 8, wherein: the flame retardant is a phosphorus-based flame retardant.

10. The polycarbonate composition of claim 9, wherein: the phosphorus-based flame retardant is bisphenol-A bis(diphenyl phosphate).

11. The polycarbonate composition of claim 1, wherein: the inorganic filler is talc, wollastonite, mica, or mixtures thereof.

12. An article manufactured by the polycarbonate composition of claim 1.

Description

DETAILED DESCRIPTION OF THE EMBODIMENTS

(1) Below, preferred embodiments will be provided in order to assist in the understanding of the present disclosure. However, these 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

AP-PDMS(n=34)

(2) ##STR00013##

(3) After 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 2.40 g (17.8 mmol) of tetramethyldisiloxane were mixed, 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. The repeating unit (n) of the terminal-unmodified polyorganosiloxane obtained as described above was 34 when confirmed through .sup.1H NMR.

(4) 4.81 g (35.9 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 under condition of 120 C. and 1 torr. The terminal-modified polyorganosiloxane obtained as described above was designated as AP-PDMS(n=34). AP-PDMS was pale yellow oil, the repeating unit (n) was 34 when confirmed through .sup.1H NMR using Varian 500 MHz, and further purification was not required.

Preparation Example 2

MBHB-PDMS(m=58)

(5) ##STR00014##

(6) After 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.5 g (11 mmol) of tetramethyldisiloxane were mixed, 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. The repeating unit (m) of the terminal-unmodified polyorganosiloxane obtained as described above was 58 when confirmed through .sup.1H NMR.

(7) 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 under condition of 120 C. and 1 torr. The terminal-modified polyorganosiloxane obtained as described above was designated as MBHB-PDMS(m=58). MBHB-PDMS was pale yellow oil, the repeating unit (m) was 58 when confirmed through .sup.1H NMR using Varian 500 MHz, and further purification was not required.

Preparation Example 3

SiPC

(8) 1784 g of water, 385 g of NaOH and 232 g of bisphenol A (BPA) were added to a polymerization reactor, and dissolved with mixing under N.sub.2 atmosphere. 4.3 g of para-tert butylphenol (PTBP) and a mixed solution of 5.91 g of AP-PDMS(n=34) prepared by Preparation Example 1 and 0.66 g of MBHB-PDMS(m=58) prepared by Preparation Example 2 (a weight ratio of 90:10) were dissolved in methylene chloride (MC) and then added to the mixture. Subsequently, 128 g of TPG (triphosgene) was dissolved in MC and the dissolved TPG solution was added thereto and reacted for 1 hour while maintaining pH of the TPG solution at 11 or more. After 10 minutes, 46 g of TEA (triethylamine) was added thereto to carry out a coupling reaction. After a total reaction time of 1 hour and 20 minutes, pH was lowered to 4 to remove TEA, and then pH of the produced polymer was adjusted to neutral pH of 6 to 7 by washing three times with distilled water. The polymer thus obtained was re-precipitated in a mixed solution of methanol and hexane, and then dried at 120 C. to obtain a final copolycarbonate (Mw=31,500), which was designated as SiPC.

Preparation Example 4

PC

(9) 1784 g of water, 385 g of NaOH and 232 g of bisphenol A (BPA) were added to a polymerization reactor, and dissolved with mixing under N.sub.2 atmosphere. 4.7 g of para-tert butylphenol (PTBP) was dissolved in methylene chloride (MC) and added to the mixture. Subsequently, 128 g of TPG (triphosgene) was dissolved in MC and the dissolved TPG solution was added thereto and reacted for 1 hour while maintaining pH of the TPG solution at 11 or more. After 10 minutes, 46 g of TEA (triethylamine) was added thereto to carry out a coupling reaction. After a total reaction time of 1 hour and 20 minutes, pH was lowered to 4 to remove TEA, and then pH of the produced polymer was adjusted to neutral pH of 6 to 7 by washing three times with distilled water. The polymer thus obtained was re-precipitated in a mixed solution of methanol and hexane, and then dried at 120 C. to obtain a final polycarbonate (Mw=29,000), which was designated as PC.

Examples and Comparative Examples

(10) Each polycarbonate resin composition was prepared by mixing the SiPC prepared by Preparation Example 3, the PC prepared by Preparation Example 4, an impact reinforcing agent, a phosphorus-based flame retardant (BDP), talc and other additives (Irganox 1076 0.1 wt %, Irgafos 0.2 wt %) were mixed at a weight ratio as shown in Table 1 below.

(11) TABLE-US-00001 TABLE 1 Com- Com- Com- parative parative parative Example 1 Example 2 Example 1 Example 2 Example 3 PC 53 wt % 48 wt % 73 wt % 78 wt % Impact 5 wt % 5 wt % 5 wt % 5 wt % 5 wt % Reinforcing Agent.sup.1) BDP.sup.2) 12 wt % 12 wt % 12 wt % 12 wt % 12 wt % Si-PC 20 wt % 20 wt % 70 wt % Talc 5 wt % 10 wt % 5 wt % 5 wt % .sup.1)Impact Reinforcing Agent: a mixture (weight ratio = 3:2) of MBS (EM 500, LG Chem.) and SAN (AN-24%, ST-76%) .sup.2)BDP: Bisphenol-A bis(diphenyl phosphate)

Experimental Example

(12) Each polycarbonate resin composition of Examples and Comparative Examples was pelletized using a 30 mm twin-screw extruder provided with a vent, and injection-molded at a cylinder temperature of 300 C. and a mold temperature of 80 C. using an N-20C injection molding machine of JSW, LTD., to manufacture each specimen. Physical properties of the above specimens were measured as follows.

(13) 1) flexure strength (kg/cm.sup.2): measured with specimen of in accordance with ASTM 0638.

(14) 2) IZOD impact strength (kg.Math.cm/cm): measured with specimen of in accordance with ASTM D256.

(15) 3) flame retardancy: evaluated in accordance with UL 94V. Specifically, five specimens having a thickness of 1.0 mm required for a flame retardancy test were prepared, and evaluated as follows.

(16) First, a flame having a height of 20 mm was in contact with each specimen for 10 seconds, and then a combustion time (t1) of the specimen was measured, and a combustion aspect was recorded. Then, after the primary flame-contact, the combustion was terminated, and a flame was in contact with each specimen for another 10 seconds (secondary flame-contact). Next, a combustion time (t2) and a glowing time (t3) of the specimen were measured, and a combustion aspect was recorded. The above-described flame retardancy test was equally applied to five specimens, and the specimens were evaluated as shown in Table 2 below.

(17) TABLE-US-00002 TABLE 2 Flame Retardancy Rating V-0 V-1 V-2 Each combustion time (t1 or t2 of Not more Not more Not more each specimen) than than than 10 sec 30 sec 30 sec Total combustion time of five Not more Not more Not more specimens (sum of t1 and t2 of than than than five specimens) 50 sec 250 sec 250 sec Combustion time and Glowing time Not more Not more Not more after secondary flame-contact (sum than than than of t2 and t3 of each specimen) 30 sec 60 sec 60 sec Whether particle causing flame is None None None dropped.

(18) 4) Whiteness (evaluation of appearance, yellow index (YI)): A disc specimen (1.5 mm) was injection-molded, and an L value was measured by using a color-difference meter, and appearance was further confirmed with the naked eye.

(19) The results were shown in Table 3 below.

(20) TABLE-US-00003 TABLE 3 Com- Com- Com- parative parative parative Example 1 Example 2 Example 1 Example 2 Example 3 Flexure 31,000 33,000 32,000 29,000 25,000 Strength IZOD 25 20 8 21 50 Impact Strength Flame 1.0 mm, 1.0 mm, 1.0 mm, 1.0 mm, 1.0 mm, Retardancy V-0 V-0 V-0 V-0 V-0 Color (L*) 3.9 4.0 3.8 3.9 3.5 Appearance X

(21) As shown in Table 3, it could be confirmed that examples showed remarkably higher flexure strength and IZOD impact strength than those of comparative examples, and also presented remarkably excellent appearance.

(22) Therefore, it could be confirmed that when the inorganic filler and the copolycarbonate are simultaneously included in the PC resin as described in the present invention, the appearance defect may be suppressed while simultaneously improving the mechanical property.