KR20150078280A - Copolymerized polycarbonate resin, method for preparing the same and article comprising the same - Google Patents

Abstract

A copolymerized polycarbonate resin of the present invention comprises: a repeating unit represented by the chemical formula 1; a repeating unit represented by the chemical formula 2; and a repeating unit represented by the chemical formula 3. The copolymerized polycarbonate resin has excellent chemical resistance, flame retardancy, low temperature impact resistance and the like. In the chemical formula 1, 2, and 3, R_1, R_2, R_3, R_4, R_5 and R_6 each independently represent a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, and a, b, c, d, e, and f are each independently an integer of 0 to 4.

Description

TECHNICAL FIELD [0001] The present invention relates to a copolymerized polycarbonate resin, a process for producing the same, and a molded article comprising the same. BACKGROUND ART [0002]

The present invention relates to a copolymerized polycarbonate resin, a process for producing the same, and a molded article comprising the same. More specifically, the present invention relates to a copolymerized polycarbonate resin having excellent chemical resistance, flame retardance and low temperature impact resistance, a method for producing the same, and a molded article comprising the same.

Polycarbonate resin is a typical thermoplastic material with a heat distortion temperature of 135 ° C or higher. It has excellent impact resistance, self-extinguishing property, dimensional stability, heat resistance and transparency and is widely used in electric / electronic exterior materials, office equipment, automobile parts, . Particularly, polycarbonate resin is widely used as an exterior material for electric / electronic products and a material for automobile parts which emit a lot of heat. In this case, more excellent flame retardancy is required. For this purpose, conventionally, a technique of improving flame retardancy by adding a flame retardant to a polycarbonate resin has been continuously developed (U.S. Patent No. 5,576,413).

However, when the low molecular weight flame retardant is used in excess, the flame retardancy can be improved, but the impact resistance and appearance characteristics may be deteriorated. Further, an impact modifier or the like may be used in order to improve the reduced impact resistance property, but in this case, the transparency of the polycarbonate resin may be lowered.

In addition, although the conventional polycarbonate resin is excellent in transparency and mechanical properties, there is a limitation in being used as an exterior material. When a plastic material is used as an exterior material, painting is often performed to express the appearance of the exterior. In this case, a coating liquid obtained by diluting the paint with various organic solvents is applied to the surface of the resin molded article and then dried. In this process, the organic solvents used as the diluent penetrate into the polycarbonate resin, thereby deteriorating transparency and mechanical properties. Therefore, in order to apply a polycarbonate resin to a product in which contact of various organic solvents easily occurs in a living environment, resistance to an organic solvent (chemical resistance) is required. For this purpose, a blending technique of a polycarbonate resin and another resin having chemical resistance has been studied.

However, when another resin is blended to improve the chemical resistance of the polycarbonate resin, impact resistance, transparency and the like may be lowered. In general, the polycarbonate resin may have a low impact resistance at a temperature lower than 0 ° C.

Therefore, there is a need to develop a copolymerized polycarbonate resin excellent in chemical resistance, flame retardance, low-temperature impact resistance, and the like without deteriorating inherent physical properties such as impact resistance and transparency.

An object of the present invention is to provide a copolymerized polycarbonate resin excellent in chemical resistance, flame retardancy and low-temperature impact resistance, a method for producing the same, and a molded article comprising the same.

Another object of the present invention is to provide a copolymerized polycarbonate resin excellent in impact resistance and transparency, a method for producing the same, and a molded article comprising the same.

The above and other objects of the present invention can be achieved by the present invention described below.

One aspect of the present invention relates to a copolymerized polycarbonate resin. Wherein the copolymerized polycarbonate resin comprises a repeating unit represented by the following formula (1): A repeating unit represented by the following formula (2); And a repeating unit represented by the following formula (3):

[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a and b are each independently an integer of 0 to 4;

(2)

Wherein R ₃ and R ₄ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, c and d are each independently an integer of 0 to 4;

(3)

Wherein R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; e and f are each independently an integer of 0 to 4;

In an embodiment, the content of the repeating unit represented by the formula (1) is 40 to 80 mol%, the content of the repeating unit represented by the formula (2) is 10 to 50 mol%, the content of the repeating unit represented by the formula May be 10 to 50 mol%.

In an embodiment, the molar ratio of the repeating unit represented by Formula 2 and the repeating unit represented by Formula 3 may be 1: 0.5 to 1.5.

In an embodiment, the copolymerized polycarbonate resin may have a weight average molecular weight of 15,000 to 50,000 g / mol.

In an embodiment, the copolymerized polycarbonate resin may have a visible light transmittance of 75% or more after immersing and drying a 2.5 mm thick flat plate specimen for 2 minutes in a diluent for undercoating of a polycarbonate resin.

In an embodiment, the copolymer polycarbonate resin may have a flame retardancy of V-0 or more of 3.2 mm thick specimen measured according to UL-94 specification.

In an embodiment, the copolymer polycarbonate resin may have a low-temperature Izod impact strength of 30 to 60 kgf · cm / cm in a 1/8 "thick specimen measured at -30 ° C. according to ASTM D256.

Another aspect of the present invention relates to a method for producing a copolymerized polycarbonate resin. The process comprises reacting a diol mixture comprising a diol represented by the following formula (4), a diol represented by the following formula (5), and a diol represented by the following formula (6) with a carbonate precursor:

[Chemical Formula 4]

Wherein R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a and b are each independently an integer of 0 to 4;

[Chemical Formula 5]

Wherein R ₃ and R ₄ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, c and d are each independently an integer of 0 to 4;

[Chemical Formula 6]

In Formula 6, R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; e and f are each independently an integer of 0 to 4;

In an embodiment, the content of the diol represented by the general formula (4) is 40 to 80 mol% in the total diol mixture, the content of the diol represented by the general formula (5) is 10 to 50 mol% The content of the diols shown may be from 10 to 50 mol% in the total diol mixture.

In an embodiment, the carbonate precursor may be a diaryl carbonate.

Another aspect of the present invention relates to a molded article formed from the copolymerized polycarbonate resin.

The present invention has the effect of providing a copolymerized polycarbonate resin excellent in chemical resistance, flame retardancy, low temperature impact resistance, impact resistance and transparency, a method for producing the same, and a molded article comprising the same.

Hereinafter, the present invention will be described in detail.

The copolymerized polycarbonate resin according to the present invention is a ternary copolymer comprising a repeating unit represented by the following formula (1), a repeating unit represented by the following formula (2), and a repeating unit represented by the following formula (3).

[Chemical Formula 1]

(2)

(3)

R ₁ , R ₂ , R ₃ , R ₄ , R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, such as methyl group, ethyl group, A, b, c, d, e and f are each independently an integer of 0 to 4, for example, an integer of 0 to 2.

In the specification of the present invention, "substituted" means that a hydrogen atom is replaced by a halogen group, an alkyl group having 1 to 10 carbon atoms, a haloalkyl group having 1 to 10 carbon atoms, an aryl group having 6 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms, ≪ / RTI >

In the copolymerized polycarbonate resin of the present invention, the content of the repeating unit represented by the general formula (1) may be 40 to 80 mol%, for example, 40 to 70 mol%, and the content of the repeating unit represented by the general formula To 50 mol%, for example, from 15 mol% to 40 mol%, and the content of the repeating unit represented by the above formula (3) may be 10 mol% to 50 mol%, for example, 15 mol% to 40 mol%. It is possible to obtain a copolymerized polycarbonate resin excellent in chemical resistance, flame retardance, low-temperature impact resistance, physical properties and the like without deterioration in transparency, impact resistance and the like within the above range.

In a specific example, the molar ratio of the repeating unit represented by the formula (2) and the repeating unit represented by the formula (3) may be 1: 0.5 to 1.5, for example, 0.8 to 1.2. Within the above range, the copolymerized polycarbonate resin can be more excellent in chemical resistance, low temperature impact resistance, flame retardancy and the like.

In an embodiment, the copolymerized polycarbonate resin may have a weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) of 15,000 to 50,000 g / mol, for example, 20,000 to 40,000 g / mol. Within this range, the moldability of the copolymerized polycarbonate resin can be excellent.

The copolymerized polycarbonate resin of the present invention can be produced by a conventional polycarbonate resin production method, and examples thereof include a diol represented by the following formula (4), a diol represented by the following formula (5), and a diol represented by the following formula ≪ / RTI > with a carbonate precursor.

[Chemical Formula 4]

[Chemical Formula 5]

[Chemical Formula 6]

Wherein R ₁ , R ₂ , R ₃ , R ₄ , R ₅ , R ₆ , a, b, c, d, e and f are as defined in the above Chemical Formulas 1, 2 and 3 .

(4-hydroxyphenyl) propane, 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis Bis (3,5-diisopropyl-4-hydroxyphenyl) propane, 2,2-bis (3,5-dibutyl- -Hydroxyphenyl) propane, and the like, but are not limited thereto. For example, 2,2-bis (4-hydroxyphenyl) propane (BPA, bisphenol A) can be used.

The diol represented by the general formula (5) includes 4,4'-biphenol, 2,2'-dimethyl-4,4'-biphenol, 3,3'-dimethyl- ', 6,6'-tetramethyl-4,4'-biphenol, and the like, but are not limited thereto. For example, 4,4'-biphenol can be used.

The diol represented by the above-mentioned formula (6) is preferably selected from the group consisting of bis (4-hydroxyphenyl) methane, bis (3-methyl-4-hydroxyphenyl) methane, bis (3,5-diethyl-4-hydroxyphenyl) methane, bis (3,5-diisopropyl-4-hydroxyphenyl) methane, bis But the present invention is not limited thereto. For example, bis (4-hydroxyphenyl) methane (BPF, bisphenol F), bis (3,5-dimethyl-4-hydroxyphenyl) methane (TMBPF, tetramethylbisphenol F) and the like can be used.

In an embodiment, the content of the diol represented by the general formula (4) may be 40 to 80 mol%, for example, 40 to 70 mol%, and the content of the diol represented by the general formula (5) 10 to 50 mol%, for example, 15 to 40 mol%, and the content of the diol represented by the formula (6) may be 10 to 50 mol%, for example, 15 to 40 mol%, of the total diol mixture. It is possible to obtain a copolymerized polycarbonate resin excellent in chemical resistance, flame retardancy, low-temperature impact resistance, physical properties and the like without deterioration in transparency, impact resistance and the like in the above range.

The carbonate precursor used in the present invention may be a conventional carbonate precursor used in the production of polycarbonate. Examples of the carbonate precursor include phosgene, triphosgene, diaryl carbonate, mixtures thereof and the like. Carbonate can be used. Examples of the diaryl carbonate include, but are not limited to, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate and the like. These may be used alone or in combination of two or more, preferably diphenyl carbonate may be used.

The molar ratio of the diol mixture to the carbonate precursor (diol mixture / carbonate precursor) may be, for example, 0.7 to 1.0, preferably 0.80 to 0.98. In this range, the unreacted monomers can be reduced and excellent mechanical properties can be obtained.

In an embodiment, the reaction of the diol mixture and the carbonate precursor (transesterification reaction) may be carried out by a melt polymerization method, an interfacial polymerization method, a solution polymerization method or the like, preferably by a melt polymerization method. The reaction may be carried out at a temperature of 150 to 330 ° C, for example 160 to 280 ° C, specifically 190 to 260 ° C, at normal pressure or reduced pressure. The above temperature range is preferable for decreasing the reaction rate and the side reaction. The transesterification reaction may be carried out under reduced pressure of 100 torr or less, for example, 75 torr or less, specifically 30 torr or less, more specifically 1 torr or less for at least 10 minutes or more, for example, 15 minutes to 24 hours, For 15 minutes to 12 hours is preferable in reducing the reaction rate and the side reaction.

In embodiments, the reaction may be carried out in the presence of a catalyst. As the catalyst, a catalyst used for a common ester exchange reaction can be used. For example, an alkali metal catalyst, an alkaline earth metal catalyst, or the like can be used. Examples of the alkali metal catalyst include, but are not limited to, LiOH, NaOH, and KOH. These may be used alone or in combination of two or more. The amount of the catalyst to be used may be 40 to 600 ppb (by weight), for example, 60 to 400 ppb with respect to the diol mixture. Sufficient reactivity can be obtained in the above range, and generation of by-products by side reactions can be minimized.

The copolymerized polycarbonate resin of the present invention can be obtained by immersing and drying a 2.5 mm thick flat plate specimen for 2 minutes in a diluent for undercoating of a polycarbonate resin and measuring visible light transmittance of 75% or more, for example, 85 to 95% have. In addition, the copolymerized polycarbonate resin may have a flame retardancy of V-0 or more of a 3.2 mm thick specimen measured in accordance with UL-94, and a 1/8 "thick specimen measured at -30 ° C in accordance with ASTM D256 The low temperature Izod impact strength may be 30 to 60 kgf · cm / cm, for example, 35 to 55 kgf · cm / cm.

The copolymer polycarbonate resin of the present invention is capable of improving chemical resistance, flame retardance, low temperature impact resistance, physical properties and the like without deteriorating transparency and impact resistance, and can be produced by melt polymerization. Therefore, the copolymerized polycarbonate resin can produce a molded article of excellent quality without adding ordinary additives such as an impact modifier and a flame retardant. For example, it can be used as an optical material such as an optical film, an exterior material for an electric / electronic product, an office machine, an automobile part, and the like.

For example, extrusion molding, injection molding, vacuum molding, cast molding, compression molding, blow molding, calender molding and the like can be applied to the molding method. These are well known to those of ordinary skill in the art to which the present invention pertains.

Hereinafter, the present invention will be described in more detail by way of examples, but these examples are for illustrative purposes only and should not be construed as limiting the present invention.

Example

Example  1 to 4 and Comparative Example  1 to 3: Preparation of Copolymerized Polycarbonate Resin

(4-hydroxyphenyl) propane (BPA), 4,4'-biphenol (BP), bis (4-hydroxyphenyl) methane (BPF) and 104 to 105 moles of diphenyl carbonate (DPC), 200 ppb of KOH (relative to the total amount of the diol mixture) per 100 moles of the diol mixture containing bis (3,5-dimethyl-4-hydroxyphenyl) methane (TMBPF) Were sequentially added to the reactor, and then oxygen in the reactor was removed using nitrogen. The temperature of the reactor was raised to 160 캜, and the temperature was raised again to 190 캜 and reacted for 6 hours. After 6 hours, the temperature of the reactor was raised to 220 캜 and maintained at a pressure of 100 torr for 1 hour. Next, the temperature of the reactor was raised to 260 캜, held at a pressure of 20 torr for 1 hour, lowered to 0.5 torr, and maintained for 1 hour to prepare a molten copolymerized polycarbonate resin. The weight average molecular weight of the copolymerized polycarbonate resin thus prepared was measured by GPC (gel permeation chromatography). The results are shown in Table 1 below.

Example Comparative Example One 2 3 4 One 2 3 BPA content (mol%) 60 40 60 40 75 75 75 BP content (mol%) 20 30 20 30 - - 25 BPF content (mol%) 20 30 - - 25 - - TMBPF content (mol%) - - 20 30 - 25 - Weight average molecular weight (g / mol) 23,100 23,500 23,200 23,400 23,200 23,500 23,100

Example  5 to 8 and Comparative Example  4 ~ 10: Preparation and evaluation of specimen

(A) a copolymerized polycarbonate resin prepared in Examples 1 to 4 and Comparative Examples 1 to 3, (B) an aromatic polycarbonate resin (bisphenol A-type polycarbonate, manufactured by Tei Co., Bis-2,6-dimethylphenyl phosphate (PX-200)), (C) a flame retardant (manufactured by DAIHACHI, product name: PANLITE L-1250WP, weight average molecular weight: 25,000 g / mol) And / or (D) an impact modifier (manufactured by KUREHA CHEM., Product name: EXL 2602 (methyl methacrylate-butadiene-ethylacrylate copolymer)) was melted and kneaded and extruded to prepare pellets. The pellets were dried at 120 DEG C for 4 hours, and then extruded using an extruder (manufactured by Dongshin Hydraulic Co., Ltd., model name: DHC-180MC, molding temperature: 290 DEG C , Mold temperature: 70 ° C). The properties of the prepared specimens were evaluated by the following methods, and the results are shown in Table 2 below.

Property evaluation method

(1) Flame retardancy: Evaluated using a 3.2 mm thick specimen in accordance with UL-94 regulations.

(2) Impact resistance (unit: kgf · cm / cm): A notch was formed on a 1/8 "thick Izod specimen based on the evaluation method described in ASTM D256.

(3) Transparency (unit:%): The light transmittance (light transmittance) of a 3.2 mm thick specimen was measured using a Haze meter NDH 2000 instrument manufactured by Nippon Denshoku under ASTM D1003.

(4) Chemical resistance (Alcohols): Tensile specimens according to ASTM D638 were injection molded and subjected to environmental stress crack resistance (ASTM D543) under 2.1% strain, The profile alcohol was dropped, and 10 minutes later, a crack state of the specimen on the curved surface was observed (⊚: crack no, ◯: fine crack, Δ: large crack, ×: haze observed with crack ).

(5) Chemical resistance (transmittance after immersion of coating liquid, unit:%): A thin film of 2.5 mm thick plate (thinner, main components: methylisobutyl ketone, cyclohexanone and 2- ethoxyethanol) The specimen was immersed for 2 minutes, dried at 80 ° C for 30 minutes, and then the visible light transmittance (%) was measured using a haze meter (manufacturer: BYK-Gardner, model: Gmbh 4725).

(6) Impact resistance at low temperature (unit: kgf · cm / cm): The low temperature Izod impact strength of the 1/8 "thick specimen was measured at -30 ° C. according to ASTM D256.

Example Comparative Example 5 6 7 8 4 5 6 7 8 9 10 (A) Kinds Example 1 Example 2 Example 3 Example 4 - - - Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 3 Content (parts by weight) 100 100 100 100 - - - 100 100 100 85 (B) (parts by weight) - - - - 100 85 82 - - - - (C) (parts by weight) - - - - - 15 15 - - - 15 (D) (parts by weight) - - - - - - 3 - - - - Flammability V-0 V-0 V-0 V-0 V-2 Fail V-0 V-0 V-0 V-0 V-2 V-0 Impact resistance (kgf · cm / cm) 73.8 71.2 40.1 38.7 86.5 7.4 58.0 71.0 27.2 58.9 7.2 Low temperature impact resistance (kgf · cm / cm) 47.3 46.8 38.2 39.3 13.0 10.0 9.0 45.0 9.0 32.0 8.2 Transparency (%) 89.4 89.1 89.3 89.0 90.1 89.0 opacity 89.7 89.5 89.6 89.8 Chemical resistance Alcohol ◎ ◎ ◎ ◎ × × × × × ◎ ◎ Transmittance (%) after immersion in coating liquid 88 88 88 88 ~ 30 ~ 30 ~ 30 ~ 30 ~ 30 88 87

From the above results, it was found that when the copolymer polycarbonate resin of the present invention (Examples 1 to 4) was used (Examples 5 to 8), it was possible to provide a resin composition which is excellent in chemical resistance, flame retardancy, Balance and so on.

On the other hand, when using a conventional aromatic polycarbonate resin alone (Comparative Example 4), flame retardancy, low-temperature impact resistance, chemical resistance, and the like were lowered. When using a conventional aromatic polycarbonate resin and a flame retardant (Comparative Example 5 ), The flame retardancy was improved, but the impact resistance, the low-temperature impact resistance, the chemical resistance and the like were lowered. When using the usual aromatic polycarbonate resin, the flame retardant and the impact modifier (Comparative Example 6) The impact resistance is not largely lowered, but the chemical resistance, low-temperature impact resistance, transparency, and the like are greatly reduced. In addition, when the copolycarbonate resin (Comparative Examples 1 and 2) in which BP (Formula 2) was not copolymerized (Comparative Examples 7 and 8) was used, it was found that the chemical resistance was lowered and the TMBPF- 2) (Comparative Example 8), the impact resistance at room temperature and low temperature was also lowered. In addition, when the copolymerized polycarbonate resin (Comparative Example 3) in which BPF or TMBPF (Formula 3) was not copolymerized was used (Comparative Example 9), it was found that the flame retardancy was lowered. When used with a flame retardant (Comparative Example 10) Flame retardancy can be improved, but the impact resistance at room temperature and low temperature is lowered.

It will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the spirit and scope of the invention as defined by the appended claims.

Claims (11)

A repeating unit represented by the following formula (1);
A repeating unit represented by the following formula (2); And
And a repeating unit represented by the following formula (3): < EMI ID =
[Chemical Formula 1]

Wherein R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a and b are each independently an integer of 0 to 4;
(2)

Wherein R ₃ and R ₄ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, c and d are each independently an integer of 0 to 4;
(3)

Wherein R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; e and f are each independently an integer of 0 to 4;
[2] The method according to claim 1, wherein the content of the repeating unit represented by the formula (1) is 40 to 80 mol%, the content of the repeating unit represented by the formula (2) is 10 to 50 mol% Is in the range of 10 to 50 mol%.
The copolymerized polycarbonate resin according to claim 1, wherein the molar ratio of the repeating unit represented by the formula (2) to the repeating unit represented by the formula (3) is 1: 0.5 to 1.5.
The copolymerized polycarbonate resin according to claim 1, wherein the copolymerized polycarbonate resin has a weight average molecular weight of 15,000 to 50,000 g / mol.
The copolymerized polycarbonate resin according to claim 1, wherein the copolymer polycarbonate resin has a visible light transmittance of 75% or more as measured after immersing and drying a 2.5 mm thick flat plate specimen on a diluent for undercoating of a polycarbonate resin for 2 minutes, Suzy.
The copolymerized polycarbonate resin according to claim 1, wherein the copolymer polycarbonate resin has a flame retardancy of V-0 or more of a 3.2 mm thick specimen measured according to UL-94 specification.
The copolymerized polycarbonate resin according to claim 1, wherein the copolymer polycarbonate resin has a low-temperature Izod impact strength of a 1/8 "thick specimen measured at -30 ° C according to ASTM D256 of 30 to 60 kgf · cm / cm. Carbonate resin.
Reacting a diol mixture comprising a diol represented by the following formula (4), a diol represented by the following formula (5), and a diol represented by the following formula (6) with a carbonate precursor:
[Chemical Formula 4]

Wherein R ₁ and R ₂ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, a and b are each independently an integer of 0 to 4;
[Chemical Formula 5]

Wherein R ₃ and R ₄ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms, c and d are each independently an integer of 0 to 4;
[Chemical Formula 6]

In Formula 6, R ₅ and R ₆ are each independently a substituted or unsubstituted alkyl group having 1 to 6 carbon atoms; e and f are each independently an integer of 0 to 4;
9. The method according to claim 8, wherein the content of the diol represented by Formula 4 is 40 to 80 mol% in the total diol mixture, the content of the diol represented by Formula 5 is 10 to 50 mol% And the content of the diol represented by the formula (6) is 10 to 50 mol% in the total diol mixture.
The process for producing a copolymerized polycarbonate resin according to claim 8, wherein the carbonate precursor is a diaryl carbonate.
A molded article comprising the copolymerized polycarbonate resin according to any one of claims 1 to 7.