KR102073254B1 - Polycarbonate based resin composition with flame resistance and molded articles thereof - Google Patents

Abstract

The present invention relates to a flame retardant polycarbonate resin composition and molded articles thereof. According to the present invention, there is provided a polycarbonate-based resin composition having excellent heat resistance and impact resistance and improved flame retardancy and a molded article formed therefrom.

Description

POLYCARBONATE BASED RESIN COMPOSITION WITH FLAME RESISTANCE AND MOLDED ARTICLES THEREOF

The present invention relates to a polycarbonate resin composition and molded articles thereof. More specifically, the present invention relates to a polycarbonate-based resin composition having excellent heat resistance and impact resistance and improved flame retardancy, and a molded article formed therefrom.

Polycarbonate resins are thermoplastic resins formed by the polycondensation of aromatic diols such as bisphenol A and carbonate precursors such as phosgene, and have excellent impact strength, numerical stability, heat resistance, transparency, and the like. It is applied to a wide range of fields such as, building materials, optical components, etc.

Recently, in order to apply such polycarbonate resin to more various fields, many studies have been attempted to obtain desired physical properties by copolymerizing aromatic diol compounds having different structures to introduce different units into the main chain of polycarbonate.

In particular, research into introducing a polysiloxane structure into the main chain of polycarbonate is also in progress. However, most of the technologies are not only economically efficient due to high production cost, but also have a limitation in that the yellowness index (hereinafter referred to as YI) is lowered when the polycarbonate resin is improved in chemical resistance or impact strength.

On the other hand, the general polycarbonate resin has a poor flame retardancy of the V-2 grade according to the UL 94 V Test (vertical burning test) standard. However, high flame retardancy of the V-0 grade is usually required for exterior materials and automotive parts of electric and electronic products. Therefore, a flame retardant must be used to produce a polycarbonate resin product that satisfies the flame retardancy of the V-0 grade.

Flame retardants generally applied to polycarbonate resins include brominated flame retardants, metal salt flame retardants, phosphorus flame retardants and the like. Among them, bromine-based flame retardants are classified as environmental hormones or carcinogens, and their use is regulated, and metal salt flame retardants have a high price.

Phosphorus-based flame retardants are the most selected for their excellent flame retardant performance. However, since the general phosphorus flame retardant reduces the impact resistance and heat resistance of the polycarbonate resin, its prescription content is limited. As a result, there has been a limit to compromise the balance between the physical properties of the polycarbonate resin and other physical properties at an appropriate level.

As such, the flame retardancy of the polycarbonate-based resin is in a trade-off relationship with other physical properties, and a situation in which technology for improving these physical properties at the same time is urgently required.

The present invention is to provide a polycarbonate-based resin composition having excellent heat resistance and impact resistance while having improved flame retardancy.

Moreover, this invention is providing the molded article formed from the said polycarbonate-type resin composition.

In order to solve the above problems, in the present specification,

Polycarbonate resin consisting of an aromatic polycarbonate-based first repeating unit;

A copolycarbonate resin including the aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond; And

Phosphate Ester Flame Retardant

It includes, a flame retardant polycarbonate-based resin composition is provided.

In the present specification, there is also provided a molded article formed from the flame retardant polycarbonate resin composition.

Hereinafter, a flame retardant polycarbonate-based resin composition and molded articles thereof according to specific embodiments of the present invention will be described in more detail.

Prior to this, the terminology used herein is for reference only to specific embodiments and is not intended to limit the invention. As used herein, the singular forms “a,” “an” and “the” include plural forms as well, unless the phrases clearly indicate the opposite.

Also, as used herein, the meaning of 'comprise' or 'contains' embodies a particular characteristic, region, integer, step, operation, element or component, and other specific characteristics, region, integer, step, operation, element, or It does not exclude the addition of ingredients.

In this specification, terms including ordinal numbers such as 'first' and 'second' are used for the purpose of distinguishing one component from other components and are not limited by the ordinal number. For example, within the scope of the present invention, the first component may also be referred to as the second component, and similarly, the second component may be referred to as the first component.

I. Polycarbonate Resin Composition

According to one embodiment of the invention,

Polycarbonate resin consisting of an aromatic polycarbonate-based first repeating unit;

A copolycarbonate resin including the aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond; And

Phosphate Ester Flame Retardant

It includes, a flame retardant polycarbonate-based resin composition is provided.

As a result of continuous studies by the present inventors, it has been confirmed that the copolycarbonate resin in which a specific siloxane bond is introduced into the polycarbonate backbone complements the physical properties of the polycarbonate resin, thereby enabling particularly improved expression of heat resistance and impact strength.

Furthermore, the phosphate ester flame retardant is excellent in compatibility while minimizing the deterioration of the intrinsic properties of the polycarbonate resin and the copolycarbonate resin, and in particular, it is possible to express high flame retardancy of V-0 grade according to the UL 94 V Test. Was confirmed.

Hereinafter, the components that may be included in the flame retardant polycarbonate-based resin composition according to an embodiment of the present invention will be described in detail.

(1) polycarbonate resin

The polycarbonate resin is a base resin included in the flame retardant polycarbonate-based resin composition, and comprises an aromatic polycarbonate-based first repeating unit.

Specifically, the aromatic polycarbonate-based first repeating unit is formed by the reaction of a diol compound and a carbonate precursor, and may preferably include a repeating unit represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁴ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.

Preferably, R ¹ to R ⁴ are each independently hydrogen, methyl, chloro, or bromo.

Also preferably, Z is straight or branched C _1-10 alkylene unsubstituted or substituted with phenyl, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, Butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Also preferably, Z is cyclohexane-1,1-diyl, O, S, SO, SO ₂ , or CO.

As a non-limiting example, the repeating unit represented by Formula 1 may be bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxy Phenyl) 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)- Group consisting of 1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, and alpha, omega-bis [3- (o-hydroxyphenyl) propyl] polydimethylsiloxane The stand may be derived from at least one aromatic diol compound selected.

The term “derived from an aromatic diol compound” means that a hydroxyl group of the aromatic diol compound reacts with a carbonate precursor to form a repeating unit represented by Chemical Formula 1.

As a non-limiting example, when the aromatic diol compound bisphenol A and the carbonate precursor triphosgene are polymerized, the repeating unit of Formula 1 may be represented by the following Formula 1-1:

[Formula 1-1]

.

.

Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, At least one selected from the group consisting of bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate can be used, and preferably, triphosgene or phosgene can be used.

The polycarbonate resin may have a weight average molecular weight of 1,000 to 100,000 g / mol, preferably 5,000 to 50,000 g / mol. More preferably, the weight average molecular weight (g / mol) is at least 1,000, at least 5,000, at least 10,000, at least 21,000, at least 22,000, at least 23,000, at least 24,000, at least 25,000, at least 26,000, at least 27,000, or at least 28,000. The weight average molecular weight is 100,000 or less, 50,000 or less, 34,000 or less, 33,000 or less, or 32,000 or less.

In addition, the polycarbonate resin may have a melt index (MI) of 5 g / 10 minutes to 25 g / 10 minutes according to ASTM D1238 (300 ° C. and 1.2 kg load) in terms of stable expression of physical properties of the composition. Can be.

In particular, it may be more preferable that the polycarbonate resin includes two or more kinds of polycarbonate resins having different melt indexes (MI) in terms of stable expression of physical properties of the composition. For example, when the polycarbonate resin composition includes two kinds of polycarbonate resins having different melt indexes (MI), those having a melt index (MI) of 5 g / 10 minutes to 15 g / 10 minutes, Having a melt index (MI) of 16 g / 10 min to 25 g / 10 min can be preferably applied.

(2) Copolycarbonate  Suzy

The copolycarbonate resin is a component added to improve the physical properties of the above-described polycarbonate resin, in particular, to improve the heat resistance and the impact strength, and is an aromatic polycarbonate-based first repeating unit and an aromatic poly having at least one siloxane bond. It includes a carbonate-based second repeating unit.

That is, the copolycarbonate resin may be distinguished from the polycarbonate resin described above in that a polysiloxane structure is introduced into the main chain of the polycarbonate.

[ First  Repeating unit]

Specifically, the aromatic polycarbonate-based first repeating unit is formed by the reaction of a diol compound and a carbonate precursor, and may preferably include the repeating unit represented by Chemical Formula 1 described above.

[Formula 1]

In Chemical Formula 1,

R ¹ to R ⁴ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,

Z is an unsubstituted or beach, or a phenyl C _1-10 alkylene, unsubstituted or C _1-10 alkyl substituted by a C _3-15 cycloalkylene, O, S, SO, SO _2, CO or substituted.

Here, R ¹ to R ⁴ and Z may have the same or different structure as the group corresponding to the repeating unit constituting the polycarbonate resin described above.

As a non-limiting example, when the aromatic diol compound bisphenol A and the carbonate precursor triphosgene are polymerized, the repeating unit of Formula 1 may be represented by the following Formula 1-1:

[Formula 1-1]

.

.

Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl carbonate, At least one selected from the group consisting of bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate can be used, and preferably, triphosgene or phosgene can be used.

[Second repeating unit]

Meanwhile, the second polycarbonate-based repeating unit having at least one siloxane bond is formed by reacting at least one siloxane compound and a carbonate precursor, and preferably at least one repeat selected from the group consisting of the following Chemical Formulas 2 and 3 Units can include:

[Formula 2]

In Chemical Formula 2,

Each X ¹ is independently C _1-10 alkylene,

Each R ⁵ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C _1-10 alkoxy, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,

n1 is an integer from 10 to 200;

[Formula 3]

In Chemical Formula 3,

Each X ² is independently C _1-10 alkylene,

Each Y ¹ is independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C _6-20 aryl,

Each R ⁶ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C _1-10 alkoxy, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,

n2 is an integer of 10-200.

In Formula 2, X ¹ may be each independently C _2-10 alkylene, preferably C _2-4 alkylene, more preferably propane-1,3-diyl.

In Formula 2, R ⁵ is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo , Methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each of R ⁵ is independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably C _1-3 alkyl, and most preferably methyl.

In Formula 2, n1 is an integer of 10 to 200, preferably i) an integer of 30 to 60, ii) 20 or more, 25 or more, or 30 or more, 40 or less, or 35 or less, or iii) 50 or more, or 55 or more, and an integer of 70 or less, 65 or less, or 60 or less.

For example, the repeating unit of Formula 2 may be represented by the following Formula 2-1:

[Formula 2-1]

In Chemical Formula 2-1,

R ⁵ and n 1 are the same as defined in Chemical Formula 2, respectively.

In Formula 3, preferably, each of X ² is independently C _2-10 alkylene, more preferably C _2-6 alkylene, and most preferably isobutylene.

Preferably, in Formula 3, Y ¹ may be hydrogen.

R ⁶ in Formula 3 is each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, meth Methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each of R ⁶ may be independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably C _1-3 alkyl, and most preferably methyl.

In Formula 3, n2 is an integer of 10 to 200, preferably i) an integer of 30 to 60, ii) 20 or more, 25 or more, or 30 or more, 40 or less, or 35 or less, or iii) 50 or more, or 55 or more, and an integer of 70 or less, 65 or less, or 60 or less.

For example, the repeating unit of Formula 3 may be represented by the following Formula 3-1:

[Formula 3-1]

상기 화학식 3-1에서,

In Chemical Formula 3-1,

R ⁶ and n 2 are the same as defined in Chemical Formula 3, respectively.

According to an embodiment of the invention, the copolycarbonate resin may include one or more, preferably two or more repeating units selected from the group consisting of Formulas 2 and 3.

In the case of including two or more of the repeating units represented by Formulas 2 and 3, it was confirmed that the degree of improvement in room temperature impact strength, low temperature impact strength, and fluidity were significantly increased. This is due to the complementary result.

The term 'two or more repeating units' used in the present invention includes two or more repeating units having different structures or the same structure, but different repeating units (n1 or n2) of silicon oxide in the structures of Formulas 2 and 3 It means containing two or more kinds.

For example, "two or more kinds of repeating units" as used herein means: i) one repeating unit represented by Formula 2 and one repeating unit represented by Formula 3, ii) one represented by Formula 2 It means to include a repeating unit and the other repeating unit represented by the formula (2), or iii) one repeating unit represented by the formula (3) and the other repeating unit represented by the formula (3).

In each case comprising the two repeating units, the weight ratio between the two repeating units may be 1:99 to 99: 1. Preferably 3:97 to 97: 3, 5:95 to 95: 5, 10:90 to 90:10, or 15:85 to 85:15, and more preferably 20:80 to 80:20 Can be.

The repeating unit represented by Formula 2 and Formula 3 may be derived from a siloxane compound represented by Formula 2-2 and a siloxane compound represented by Formula 3-2, respectively:

[Formula 2-2]

In Chemical Formula 2-2,

X ¹ , R ⁵ and n ¹ are each as defined in Chemical Formula 2;

[Formula 3-2]

In Chemical Formula 3-2,

X ² , Y ¹ , R ⁶ and n 2 are the same as defined in Chemical Formula 3, respectively.

The meaning of 'derived from the siloxane compound' means that the hydroxyl groups of the respective siloxane compounds react with each other to form a repeating unit represented by Formulas 2 and 3, respectively. In addition, the carbonate precursor that can be used to form the repeating units of Formulas 2 and 3 is the same as described above for the carbonate precursor that can be used to form the repeating units of Formula 1.

In addition, the compounds represented by Formulas 2-2 and 3-2 may be prepared by the methods of Schemes 1 and 2, respectively:

Scheme 1

In Scheme 1,

X ^1a is C _2-10 alkenyl,

X ¹ , R ⁵ and n ¹ are each as defined in Chemical Formula 2;

Scheme 2

In Scheme 2,

X ^2a is C _2-10 alkenyl,

X ² , Y ¹ , R ⁶ and n 2 are the same as defined in Chemical Formula 3, respectively.

The reactions of Schemes 1 and 2 are preferably carried out under a metal catalyst. It is preferable to use a Pt catalyst as the metal catalyst, and as a Pt catalyst, an Ashby catalyst, a Karlstedt catalyst, a Lamoreaux catalyst, a Speyer catalyst, a PtCl ₂ (COD), One or more selected from the group consisting of PtCl ₂ (benzonitrile) ₂ , and H ₂ PtBr ₆ can be used. The metal catalyst is 0.001 part by weight, 0.005 part by weight, or 0.01 part by weight or more, 1 part by weight, 0.1 part by weight, or 0.05 part by weight based on 100 parts by weight of the compound represented by Formula 11, 13, or 15. It can be used in parts or less.

In addition, the reaction temperature is preferably 80 to 100 ℃. In addition, the reaction time is preferably 1 hour to 5 hours.

In addition, in the reaction schemes 1 and 2, the compound represented by the formula (C2 or C4) can be prepared by reacting the organodisiloxane and organocyclosiloxane under an acid catalyst, by adjusting the content of the reactant to n1 and n2 I can regulate it. As for the said reaction temperature, 50-70 degreeC is preferable. In addition, the reaction time is preferably 1 hour to 6 hours.

As the organodisiloxane, one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, hexamethyldisiloxane and hexaphenyldisiloxane can be used. As the organocyclosiloxane, an organocyclotetrasiloxane can be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like.

The organodisiloxane may be 0.1 part by weight or more, or 2 parts by weight or more, 10 parts by weight or less, or 8 parts by weight or less, based on 100 parts by weight of the organocyclosiloxane.

As the acid catalyst, at least one selected from the group consisting of H ₂ SO ₄ , HClO ₄ , AlCl ₃ , SbCl ₅ , SnCl _4, and acidic clay may be used. The acid catalyst may be used in an amount of 0.1 parts by weight, 0.5 parts by weight, or 1 part by weight, 10 parts by weight, 5 parts by weight, or 3 parts by weight or less based on 100 parts by weight of organocyclosiloxane. have.

By adjusting the content of the repeating units represented by Formulas 2 and 3, it is possible to improve the physical properties of the copolycarbonate resin. Here, the weight ratio of the repeating unit corresponds to the weight ratio of the siloxane compound used for the copolycarbonate polymerization, for example, the siloxane compound represented by the formulas (2-2) and (3-2).

[ Copolycarbonate  Composition and Manufacturing Method of Resin]

In the copolycarbonate resin, the molar ratio of the aromatic polycarbonate-based first repeating unit and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond is 1: 0.0001 to 1: 0.01, or 1: 0.0005 to 1: 0.008 Or 1: 0.001 to 1: 0.006, and the weight ratio may be 1: 0.001 to 1: 1, or 1: 0.005 to 1: 0.1, or 1: 0.01 to 1: 0.03.

In addition, the copolycarbonate resin may include 90 to 99.999% by weight of the first repeating unit and 0.001 to 10% by weight of the second repeating unit. That is, when the content of the second repeating unit is excessively reduced, it may be difficult to sufficiently realize the improvement of the room temperature impact strength, the low temperature impact strength and the fluidity properties by the second repeating unit. On the other hand, if the content of the second repeating unit is excessively increased, the flowability and molding processability may decrease while the molecular weight of the copolycarbonate resin is excessively increased.

In addition, the copolycarbonate resin may have a weight average molecular weight of 1,000 to 100,000 g / mol, preferably 5,000 to 50,000 g / mol. Within the weight average molecular weight range, appropriate ductility and YI of the copolycarbonate resin can be ensured. More preferably, the weight average molecular weight (g / mol) is at least 1,000, at least 5,000, at least 10,000, at least 21,000, at least 22,000, at least 23,000, at least 24,000, at least 25,000, at least 26,000, at least 27,000, or at least 28,000. The weight average molecular weight is 100,000 or less, 50,000 or less, 34,000 or less, 33,000 or less, or 32,000 or less.

The content of the copolycarbonate resin may vary depending on the physical properties of the composition to be adjusted. For example, the copolycarbonate resin may be included in 10 to 100 parts by weight based on 100 parts by weight of the polycarbonate resin. Preferably, the content of the copolycarbonate resin is at least 10 parts by weight, or at least 20 parts by weight, or at least 30 parts by weight, or at least 45 parts by weight, or at least 47.5 parts by weight. In addition, the content of the copolycarbonate resin is 100 parts by weight or less, or 75 parts by weight or less, or 60 parts by weight or less, or 55 parts by weight or less, or 49 parts by weight or less.

That is, the copolycarbonate resin is at least 10 parts by weight, or at least 20 parts by weight, or at least 30 parts by weight, or at least 45 parts by weight, or 47.5 parts by weight, based on 100 parts by weight of the polycarbonate resin in order to express physical properties. It is preferable to be contained more than a part. However, when the copolycarbonate resin is added in an excessive amount, the transparency of the composition may be lowered, and an effect of improving heat resistance and impact strength may be lowered or may be lowered. Therefore, the copolycarbonate resin is preferably contained in 100 parts by weight or less, or 75 parts by weight or less, or 60 parts by weight or less, or 55 parts by weight or less, or 49 parts by weight or less based on 100 parts by weight of polycarbonate resin. .

Meanwhile, according to an embodiment of the present invention, the copolycarbonate resin may be prepared using the aromatic diol compound, the carbonate precursor, and one or more siloxane compounds.

Upon polymerization of the compounds, the at least one siloxane compound is at least 0.1 wt%, at least 0.5 wt%, at least 1 wt%, or at least 1.5 wt% based on 100 wt% of the total of the aromatic diol compound, the carbonate precursor and the at least one siloxane compound. 20 wt% or less, 10 wt% or less, 7 wt% or less, 5 wt% or less, 4 wt% or less, 3 wt% or less, or 2 wt% or less can be used. In addition, the aromatic diol compound is at least 40% by weight, at least 50% by weight, or at least 55% by weight and at least 80% by weight, 70% by weight relative to 100% by weight of the total of the aromatic diol compound, the carbonate precursor and the at least one siloxane compound. Up to 65 weight percent. Further, the carbonate precursor is at least 10% by weight, at least 20% by weight, or at least 30% by weight, at most 60% by weight, at most 50% by weight, based on 100% by weight of the aromatic diol compound, the carbonate precursor and the at least one siloxane compound. Or 40 wt% or less.

In addition, as the polymerization method, for example, an interfacial polymerization method can be used. In this case, the polymerization reaction is possible at atmospheric pressure and low temperature, and the molecular weight can be easily controlled. The interfacial polymerization is preferably carried out in the presence of an acid binder and an organic solvent. In addition, the interfacial polymerization may include, for example, after pre-polymerization, a coupling agent, and then polymerizing again. In this case, a high molecular weight copolycarbonate may be obtained.

The materials used for the interfacial polymerization are not particularly limited as long as the materials can be used for the polymerization of polycarbonate, and the amount of the materials used may be adjusted as necessary.

As the acid binder, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine can be used.

The organic solvent is not particularly limited as long as it is a solvent usually used for polymerization of polycarbonate, and examples thereof include halogenated hydrocarbons such as methylene chloride and chlorobenzene.

In addition, the interfacial polymerization is a reaction such as a tertiary amine compound such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compound, quaternary phosphonium compound, etc. to promote the reaction. Accelerators may further be used.

The reaction temperature of the interfacial polymerization is preferably 0 to 40 ° C, and the reaction time is preferably 10 minutes to 5 hours. In the interfacial polymerization reaction, the pH is preferably maintained at 9 or more or 11 or more.

In addition, the interfacial polymerization may be performed by further including a molecular weight regulator. The molecular weight modifier may be added before the start of the polymerization, during the start of the polymerization or after the start of the polymerization.

Mono-alkylphenol may be used as the molecular weight modifier, and the mono-alkylphenol is, for example, p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecyl It is at least one selected from the group consisting of phenol, eicosylphenol, docosylphenol and triacontylphenol, preferably p-tert-butylphenol, in which case the molecular weight control effect is large.

The molecular weight modifier may be, for example, 0.01 part by weight, 0,1 part by weight, or 1 part by weight or more, 10 parts by weight or less, 6 parts by weight, or 5 parts by weight or less, based on 100 parts by weight of the aromatic diol compound. It is possible to obtain a desired molecular weight within this range.

(3) phosphate ester Flame retardant

The polycarbonate resin composition according to the embodiment of the present invention includes a phosphate ester compound as a flame retardant.

In particular, the phosphate ester flame retardant may include at least one compound selected from the group consisting of poly (phosphonate-co-carbonate) having a repetitive face of the formula (4) and a condensed phosphate ester represented by the formula (5) :

[Formula 4]

[Formula 5]

In Chemical Formula 5,

Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently a halogen-free aromatic group,

,

또는

이고; 상기 R⁷ 내지 R¹⁴는 각각 독립적으로 수소 원자 또는 C_1-5 알킬기이고; 상기 G는 직접 결합(direct binding), O, S, SO₂, C(CH₃)₂, CH₂, CHPh를 나타내고, 상기 Ph는 페닐기이고,Q is

,

or

ego; R ⁷ to R ¹⁴ are each independently a hydrogen atom or a C _1-5 alkyl group; G represents direct binding, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, wherein Ph is a phenyl group,

n is an integer of 1 or more,

k and m are each an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less.

The phosphate ester flame retardant enables the expression of high flame retardancy of the V-0 grade according to UL 94 V Test while minimizing the degradation of the intrinsic properties of the polycarbonate resin and the physical property improvement effect as the copolycarbonate resin is added. do.

The condensed phosphate ester represented by Formula 5 may include a mixture of condensed phosphate esters having different n or different structures.

In Formula 5, n is an integer of 1 or more, and an upper limit thereof is preferably 40 or less in terms of expression of flame retardancy; Preferably 1 to 10, more preferably 1 to 5.

In Chemical Formula 5, k and m are each an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less; Preferably each may be an integer of 0 or more and 1 or less, more preferably 1 respectively.

In Q of Formula 5, R ⁷ to R ¹⁴ are each independently a hydrogen atom or a C _1-5 alkyl group; Specifically hydrogen, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, neopentyl and the like; Preferably hydrogen, methyl or ethyl; More preferably hydrogen.

Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ of Formula 5 may each independently be a halogen-free aromatic group, specifically, an aromatic group having a benzene skeleton, a naphthalene skeleton, an indene skeleton, or an anthracene skeleton. The Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ may each be substituted with an organic moiety having 1 to 8 carbon atoms that does not contain a halogen. For example, Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently phenyl, tolyl, cresyl, xylyl, isopropylphenyl, butylphenyl, tert-butylphenyl, di-tert-butylphenyl, p-cumylphenyl and the like.

Preferably, the condensed phosphate ester represented by Formula 5 may be a compound represented by Formulas 5-1 to 5-4:

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

In Chemical Formulas 5-1 to 5-4, n is an integer of 1 or more.

Non-limiting examples, commercially available phosphate ester flame retardants include Nofia ^TM CO3000, Nofia ^TM CO6000 (above FRX Polymers, Inc.); PX-200, PX-201, PX-202, CR-733S, CR-741, CR747 (above DAIHACHI CHEMICAL INDUSTRY Co., Ltd.); FP-600, FP-700, FP-800 (ADEKA Co.), etc. are mentioned.

Such a phosphate ester flame retardant may be included in an amount of 0.5 to 20 parts by weight based on 100 parts by weight of the polycarbonate resin. Preferably, the content of the phosphate ester flame retardant is 0.5 part by weight or more, or 1 part by weight, or 3 parts by weight or 3.5 parts by weight or more based on 100 parts by weight of the polycarbonate resin. In addition, the content of the phosphate ester flame retardant is 20 parts by weight or less, or 15 parts by weight or less, or 10 parts by weight or less, or 8 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the polycarbonate resin.

That is, for the expression of flame retardant, the phosphate ester flame retardant is preferably contained in 0.5 parts by weight or more, or 1 part by weight, or 3 parts by weight or 3.5 parts by weight or more based on 100 parts by weight of the polycarbonate resin. . However, when the flame retardant is added in an excessive amount, the heat resistance and mechanical properties of the resin composition may be suddenly reduced, so that the phosphate ester flame retardant is 20 parts by weight or less, or 15 parts by weight or less with respect to 100 parts by weight of the polycarbonate resin. Or 10 parts by weight or less, or 8 parts by weight or less, or 5 parts by weight or less.

Furthermore, the content of the phosphate ester flame retardant is preferably controlled in a range that does not inhibit the effect of improving the heat resistance and impact strength according to the addition of the copolycarbonate resin.

Specifically, the phosphate ester flame retardant may be included in 1 to 20 parts by weight based on 100 parts by weight of the copolycarbonate resin. Preferably, the content of the phosphate ester flame retardant is at least 1 part by weight, at least 5 parts by weight, or at least 7 parts by weight based on 100 parts by weight of the copolycarbonate resin. In addition, the content of the phosphate ester flame retardant is 20 parts by weight or less, or 15 parts by weight or less, or 10 parts by weight or less based on 100 parts by weight of the copolycarbonate resin.

(4) other ingredients

Flame retardant polycarbonate-based resin composition according to an embodiment of the present invention, if necessary, impact modifiers such as methacrylate / butadiene / styrene (MBS) copolymer, acrylonitrile / butadiene / styrene (ABS) copolymer; drip inhibitors such as polytetrafluoroethylene (PTFE); Surfactants; Nucleating agent; Coupling agents; Fillers; Plasticizers; Lubricant; Antibacterial agents; Release agents; Heat stabilizers; Antioxidants; UV stabilizers; Compatibilizers; coloring agent; Antistatic agents; Pigments; dyes; Additives such as a flame retardant may further be included.

The content of such additives may vary depending on the physical properties to be imparted to the composition. For example, the additive may be included in an amount of 0.05 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin.

However, in order to prevent the heat resistance, impact strength, flame retardancy, etc. of the flame retardant polycarbonate resin composition from being lowered by the application of the additive, the total content of the additive is 20 parts by weight based on 100 parts by weight of the polycarbonate resin. It is preferable that it is below or 15 weight part.

II. Polycarbonate Resin Molded Products

According to another embodiment of the present invention, a molded article formed from the flame retardant polycarbonate-based resin composition is provided.

The molded article is an article obtained by molding by a method such as extrusion, injection, or casting using the polycarbonate-based resin composition described above as a raw material. The molding method and its conditions can be appropriately selected and adjusted according to the type of molded article.

As a non-limiting example, the molded article may be obtained by mixing and extruding the polycarbonate-based resin composition to prepare pellets, and then drying and injecting the pellets.

In particular, the molded article is excellent in heat resistance and impact strength as it is formed from the polycarbonate resin composition may have a high flame retardancy of V-0 grade according to UL 94 V Test.

The polycarbonate-based resin composition and the molded article thereof according to the present invention may have excellent flame resistance and excellent heat resistance and impact strength, in particular, V-0 grade according to UL 94 V Test.

Hereinafter, preferred embodiments are presented to aid the understanding of the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto.

Production Example  One

Preparation of Polyorganosiloxane (AP-PDMS, n = 34)

: 47.6 g (160 mmol) of octamethylcyclotetrasiloxane and 2.4 g (17.8 mmol) of tetramethyldisiloxane are mixed, and then the mixture is mixed with 100 parts by weight of octamethylcyclotetrasiloxane and 1 part by weight of acidic clay (DC-A3). Into a 3L flask with a reaction at 60 ℃ for 4 hours. After completion of the reaction, it was diluted with ethyl acetate and filtered quickly using celite. The repeating unit (n1) of the unmodified polyorganosiloxane thus obtained was found to be 34 by ¹ H NMR.

4.81 g (35.9 mmol) of 2-allylphenol and 0.01 g (50 ppm) of Karlstedt's platinum catalyst were added to the terminal unmodified polyorganosiloxane, and reacted at 90 ° C. for 3 hours. After the reaction was completed, unreacted siloxane was removed by evaporation at 120 ° C. under a condition of 1 torr. The terminal modified polyorganosiloxane thus obtained was named AP-PDMS (n1 = 34). AP-PDMS is a light yellow oil, and it was confirmed that the repeating unit (n1) was 34 by ¹ H NMR using a Varian 500 MHz, and no further purification was necessary.

Production Example  2

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

: 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.5 g (11 mmol) of tetramethyldisiloxane were mixed, and then the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane and 1 part by weight of acidic clay (DC-A3). Into a 3L flask with a reaction at 60 ℃ for 4 hours. After completion of the reaction, the mixture was diluted with ethyl acetate and filtered quickly using Celite. The repeating unit (n2) of the terminal unmodified polyorganosiloxane thus obtained was found to be 58 by ¹ H NMR.

6.13 g (29.7 mmol) of 3-methylbut-3-enyl 4-hydroxybenzoate and Karlstedt's platinum catalyst (Karstedt's) were obtained in the terminal unmodified polyorganosiloxane obtained above. 0.01 g (50 ppm) of platinum catalyst was added and reacted at 90 ° C. for 3 hours. After the reaction was completed, unreacted siloxane was removed by evaporation at 120 ° C. under a condition of 1 torr. The terminal modified polyorganosiloxane thus obtained was named MBHB-PDMS (n2 = 58). MBHB-PDMS is a light yellow oil, it was confirmed that the repeating unit (n2) is 58 by ¹ H NMR using a Varian 500MHz, no further purification was necessary.

Production Example  3

Preparation of Copolycarbonate Resin

: 1784 g of water, 385 g of NaOH and 232 g of BPA (bisphenol A) were added to a polymerization reactor, and the mixture was dissolved under N ₂ atmosphere. Here, a mixed solution of 4.3 g of PTBP (para-tert butylphenol), 4.72 g of AP-PDMS (n1 = 34) according to Preparation Example 1, and 0.52 g of MBHB-PDMS (n2 = 58) according to Preparation Example 2 was added to MC (methylene chloride). ) And dissolved. Then, 128 g of TPG (triphosgene) was dissolved in MC for 1 hour while maintaining the pH at 11 or more, followed by reaction for 10 hours, and 46 g of TEA (triethylamine) was added thereto for a coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and washed three times with distilled water to adjust the pH of the produced polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a mixed solution of methanol and hexane, and then dried at 120 ° C. to finally obtain a copolycarbonate resin (Mw = 30,500).

Production Example  4

Preparation of Polycarbonate Resin

(1) 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to a polymerization reactor, mixed and dissolved in an N ₂ atmosphere. Then, 128 g of TPG (triphosgene) was dissolved in MC for 1 hour while maintaining the pH at 11 or more, followed by reaction for 10 hours, and 46 g of TEA (triethylamine) was added thereto for a coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and washed three times with distilled water to adjust the pH of the produced polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a methanol and hexane mixed solution, which was then dried at 120 ° C. to give a final polycarbonate resin (Mw = 31000; MI = 10 g / 10 min under a temperature of 300 ° C. and a load of 1.2 kg). Got.

(2) 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to a polymerization reactor, mixed and dissolved in an N ₂ atmosphere. Then, 128 g of TPG (triphosgene) was dissolved in MC for 1 hour while maintaining the pH at 11 or more, followed by reaction for 10 hours, and 46 g of TEA (triethylamine) was added thereto for a coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and washed three times with distilled water to adjust the pH of the produced polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a methanol and hexane mixed solution, which was then dried at 120 ° C. to give a final polycarbonate resin (Mw = 26000; MI = 22 g / 10 min at a temperature of 300 ° C. and a load of 1.2 kg). Got.

Example  And Comparative example

Each component was added to the composition of Table 1, followed by melting and kneading extrusion to prepare pellets. After drying the prepared pellets for 6 hours at 70 ℃, it was injected to prepare a specimen for evaluation of physical properties.

The components used in each Example and Comparative Example are as follows.

(A-1) Polycarbonate resin according to Preparation Example 4 (MI 10 g / 10 minutes)

(A-2) Polycarbonate resin according to Preparation Example 4 (MI 22 g / 10 min)

(B-1) Copolycarbonate resin according to Preparation Example 3 (PC 8000-05, LG Chem.)

(B-2) polysiloxane-polycarbonate resin (TRIREX ST6-3022PJ, SAMYANG Co.)

(C-1) Phosphate ester flame retardant (FP-600, ADEKA Co.)

(C-2) Phosphate Ester Flame Retardant (PX-200, DAIHACHI CHEMICAL INDUSTRY Co., Ltd.)

(C-3) Phosphate Ester Flame Retardant (Nofia ^TM CO3000, FRX Polymers, Inc.)

(C-4) Phosphate Ester Flame Retardant (Nofia ^TM CO6000, FRX Polymers, Inc.)

(D-1) Impact modifier (MBS copolymer, EM505, LG Chem.)

(D-2) Impact modifier (ABS copolymer, AT-05, NIPPON A & L)

(D-3) dropping inhibitor (PTFE, XFLON-G, POCERA Co.)

(D-4) Antioxidant (SONGNOX 1076, SONGWON Co.)

(D-5) Antioxidant (PEP-36, ADEKA Co.)

(D-6) lubricant (PETS, FACI Co.)

(D-7) UV stabilizer (TINUVIN 329, BASF)

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 A-1 30.0 30.0 30.0 30.0 - - - - 30.0 30.0 A-2 33.1 33.1 62.1 64.1 63.1 63.6 63.1 63.1 33.6 30.6 B-1 30.0 30.0 - - 30.0 30.0 30.0 - 30.0 30.0 B-2 - - - - - - - 30.0 - - C-1 - - 3.5 - - - - - - - C-2 - 2.5 - 2.5 2.5 2.0 - 2.5 2.0 - C-3 - - - - - - 2.5 - - 5.0 C-4 2.5 - - - - - - - - - D-1 - - 2.5 1.5 - - - - - - D-2 3 3 0.5 0.5 3 3 3 3 3 3 D-3 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 D-4 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 D-5 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 D-6 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 D-7 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05

Test Example

Physical properties of the specimens formed from the compositions of Examples and Comparative Examples were measured in the following manner, and the results are shown in Table 2 below.

(1) Impact strength (IZOD): It measured by 1/4 inch (Notched Izod, kg.cm/cm) and 1/8 inch (Notched Izod, kg.cm/cm) at 23 degreeC based on ASTMD256.

(2) Melt index (MI): It measured based on ASTMD1238 (300 degreeC, 1.2 kg conditions).

(3) Tensile strength (TS) and tensile elongation (TE): Measured according to ASTM D638 (50 mm / min).

(4) Flexural modulus (FM) and flexural strength (FS): Measured according to ASTM D790 (10 mm / min).

(5) Heat Deflection Temperature (HDT): Measured according to ASTM D648 (18.5 kgf, 120 ° C / h).

(6) Vicat softening temperature (VST): measured according to ASTM D 1525 (50N, 50 ° C / h).

(7) Flame retardant rating: Measured according to the UL 94 V Test (vertical burning test, 1.6mm).

Example 1 Example 2 Comparative Example 1 Comparative Example 2 Comparative Example 3 Comparative Example 4 Comparative Example 5 Comparative Example 6 Comparative Example 7 Comparative Example 8 IZOD
(1/4 ") 44.1 15.0 9.9 9.8 12.7 13.0 15.7 23.5 16.4 43.5 IZOD
(1/8 ") 83.3 77.6 60.9 65.6 67.1 67.9 71.2 72.6 81.7 82.2 MI 13.7 114.0 21.0 20.2 20.5 19.5 18.9 18.6 14.8 13.7 TS 615 635 637 629 628 622 609 614 621 618 TE 165.3 127.2 81.2 120.9 104.4 109.6 129.5 115.6 164.7 152.6 FM 24701 25255 26984 26172 26112 25949 25395 25800 25054 24701 FS 990 1024 1046 1028 1030 1029 1007 1018 1019 995 HDT 124.9 119.5 114.5 119.4 116.0 118.8 122.7 116.4 120.5 125.3 VST 139.5 133.1 128.2 134.3 131.4 133.8 137.8 131.6 134.6 138.7 Flame Retardant
ranking V-0 V-0 V-2 V-2 V-1 Burn-
out Burn-
out Burn-
out V-1 V-1

 As shown in Table 1, the polycarbonate-based resin composition according to Examples 1 and 2 was confirmed to have a high flame retardancy of V-0 grade according to the UL 94 V Test, while excellent in heat resistance and impact strength.

Claims (14)

Polycarbonate resin consisting of an aromatic polycarbonate-based first repeating unit;
A copolycarbonate resin including the aromatic polycarbonate-based first repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond; And
A phosphate ester flame retardant,
Each of the first repeating units independently includes a repeating unit represented by the following Formula 1,
The second repeating unit includes a repeating unit represented by the following Formula 2 and a repeating unit represented by the following Formula 2,
Flame retardant polycarbonate resin composition:
[Formula 1]

In Chemical Formula 1,
R ¹ to R ⁴ are each independently hydrogen, C _1-10 alkyl, C _1-10 alkoxy, or halogen,
Z is beach is unsubstituted or phenyl-substituted C _1-10 alkylene, or C _1-10 unsubstituted or substituted with a C _3-15 alkyl cycloalkylene, O, S, SO, SO _2, CO or a;
[Formula 2]

In Chemical Formula 2,
Each X ¹ is independently C _1-10 alkylene,
Each R ⁵ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C _1-10 alkoxy, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,
n1 is an integer from 10 to 200;
[Formula 3]

In Chemical Formula 3,
Each X ² is independently C _1-10 alkylene,
Each Y ¹ is independently hydrogen, C _1-6 alkyl, halogen, hydroxy, C _1-6 alkoxy or C _6-20 aryl,
Each R ⁶ is independently hydrogen; C _1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C _1-10 alkoxy, or C _6-20 aryl; halogen; C _1-10 alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,
n2 is an integer of 10-200.
The method of claim 1,
The phosphate ester flame retardant is a flame retardant polycarbonate comprising at least one compound selected from the group consisting of poly (phosphonate-co-carbonate) having a repeating face of the formula (4) and a condensed phosphate ester represented by the formula (5) Resin composition:
[Formula 4]

[Formula 5]

In Chemical Formula 5,
Ar ¹ , Ar ² , Ar ³ , and Ar ⁴ are each independently a halogen-free aromatic group,
Q is

,

or

ego; R ⁷ to R ¹⁴ are each independently a hydrogen atom or a C _1-5 alkyl group; G represents direct binding, O, S, SO ₂ , C (CH ₃ ) ₂ , CH ₂ , CHPh, wherein Ph is a phenyl group,
n is an integer of 1 or more,
k and m are each an integer of 0 or more and 2 or less, and (k + m) is an integer of 0 or more and 2 or less.
The method of claim 2,
The condensed phosphate ester represented by Formula 5 is represented by the following Formulas 5-1 to 5-4, flame retardant polycarbonate-based resin composition:
[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

In Chemical Formulas 5-1 to 5-4, n is an integer of 1 or more.
delete The method of claim 1,
The repeating unit of Chemical Formula 1 is represented by the following Chemical Formula 1-1, flame retardant polycarbonate resin composition:
[Formula 1-1]

.
delete The method of claim 1,
The repeating unit of Formula 2 is represented by the following formula 2-1, flame retardant polycarbonate-based resin composition:
[Formula 2-1]

In Chemical Formula 2-1,
R ⁵ and n 1 are the same as defined in Chemical Formula 2, respectively.
The method of claim 1,
The repeating unit of Chemical Formula 3 is represented by the following Chemical Formula 3-1, flame retardant polycarbonate-based resin composition:
[Formula 3-1]

In Chemical Formula 3-1,
R ⁶ and n 2 are the same as defined in Chemical Formula 3, respectively.
The method of claim 1,
The polycarbonate resin has a melt index (MI) of 5 g / 10 minutes to 25 g / 10 minutes at a temperature of 300 ℃ and a load of 1.2 kg, flame retardant polycarbonate-based resin composition.
The method of claim 1,
The polycarbonate resin comprises a flame retardant polycarbonate resin composition comprising two or more polycarbonate resins having different melt index (MI).
The method of claim 1,
Wherein the copolycarbonate resin comprises 90 to 99.999 wt% of the first repeating unit and 0.001 to 10 wt% of the second repeating unit.
The method of claim 1,
The polycarbonate resin and the copolycarbonate resin, each having a weight average molecular weight of 1,000 to 100,000 g / mol, flame-retardant polycarbonate-based resin composition.
The method of claim 1,
About 100 parts by weight of the polycarbonate resin,
10 to 100 parts by weight of the copolycarbonate resin, and
0.5 to 20 parts by weight of the phosphate ester flame retardant
Flame retardant polycarbonate-based resin composition comprising a.
A molded article formed from the flame-retardant polycarbonate-based resin composition of any one of claims 1, 2, 3, 5, 7, 8, 9, 10, 11, 12, and 13.