WO2016089170A1

WO2016089170A1 - Flame retardant polycarbonate-based resin composition and moulded article from same

Info

Publication number: WO2016089170A1
Application number: PCT/KR2015/013245
Authority: WO
Inventors: 이무석; 이률
Original assignee: 주식회사 엘지화학
Priority date: 2014-12-04
Filing date: 2015-12-04
Publication date: 2016-06-09

Abstract

The present invention relates to a flame retardant polycarbonate-based resin composition and to a moulded article from same. According to the present invention, a polycarbonate-based resin composition having improved flame retardancy while also having outstanding heat resistance and impact resistance and a moulded article formed from same are provided.

Description

[Name of invention]

Flame retardant polycarbonate resin composition and molded article thereof

[Cross Citation with Related Application (s)]

This application is the Korean Patent Application No. 10-2014-0173005 dated December 4, 2014 and

Claiming the benefit of priority based on Korean Patent Application No. 10-2015-0171776 filed December 3, 2015, all content disclosed in the literature of the relevant Korean patent applications is incorporated as part of this specification. Technical Field

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. [Technique to become background of invention]

Polycarbonate resins are thermoplastic resins formed by the condensation 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 construction, building materials and optical components.

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 di-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 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 chemical resistance and the layer strength of the polycarbonate resin are improved.

On the other hand, the general polycarbonate resin has a poor flame retardancy of ν-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 should be used to manufacture 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 1, metal salt flame retardants, phosphorus flame retardants, and the like. By the way, bromine-based flame retardants are classified as environmental hormones or carcinogens, and their use is regulated, and phosphorus-based flame retardants having excellent flame retardant performance for the price are most frequently adopted.

However, when the flame retardant is applied, the layered toughness and heat resistance of the polycarbonate resin are relatively lowered, so that the prescription content is limited. Accordingly, until now, there has been a limit to compromise the balance of other physical properties with an appropriate level while securing the flame retardancy of the polycarbonate resin.

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 a technology for improving these physical properties at the same time is urgently required. [Content of invention]

Problem to be solved

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

In addition, the present invention is to provide a molded article formed from the polycarbonate resin composition.

[Measures of problem]

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

A polycarbonate resin comprising an aromatic polycarbonate-based crab 1 repeating unit, a copolycarbonate resin comprising the aromatic polycarbonate-based crab 1 repeating unit, and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, and

An organo metal salt flame retardant;

The one repeating unit each independently includes a repeating unit represented by the following Formula 1; The crab 2 repeating unit is provided with a flame-retardant polycarbonate-based resin composition comprising a repeating unit represented by the following formula (3):

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 C ₁₀ alkylene unsubstituted or substituted with phenyl, C _3-15 cycloalkylene, unsubstituted or substituted with d-10 alkyl, S, SO, S02, or CO;

In Chemical Formula 3,

X ² are each independently C _1-10 alkylene,

丫¹ is each 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, 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 the present specification, there is also provided a molded article formed from the flame retardant polycarbonate resin composition. Hereinafter, a flame retardant polycarbonate resin composition and molded articles thereof according to specific embodiments of the present invention will be described in 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 an ordinal number such as 'r' and 'second' are used for the purpose of distinguishing one component from another component 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,

A polycarbonate resin comprising an aromatic polycarbonate-based repeating unit, a copolycarbonate resin comprising the aromatic polycarbonate-based repeating unit and an aromatic polycarbonate-based second repeating unit having at least one siloxane bond, and

An organo metal salt flame retardant;

The first repeating units each independently include a repeating unit represented by the following Formula 1;

The second repeating unit is provided with a flame-retardant polycarbonate-based resin composition comprising a repeating unit represented by the following formula (3):

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

Z is Cwo alkylene unsubstituted or substituted with phenyl, C _3-15 cycloalkylene unsubstituted or substituted with 10 alkyl, O, S, SO, SO ₂ , or CO;

In Chemical Formula 3,

Each X ² is independently Cwo alkylene

γ ¹ are each independently hydrogen, C _1-6 alkyl, halogen, hydroxy, 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 ᅳ ₂₀ aryl,

n2 is an integer of 10-200. As a result of continuous research 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 the expression of particularly significantly improved heat resistance and layer strength.

In particular, the copolycarbonate resin can minimize the degradation of the physical properties of the resin composition due to the addition of the organometallic salt-based flame retardant, while excellent in heat resistance and layer resistance

It was confirmed that it is possible to provide a polycarbonate-based resin composition having a high flame retardancy of the V-0 grade according to the UL 94 V Test. 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 polycarbonate-based resin composition, and is composed of 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 the following Chemical Formula 1:

In Chemical Formula 1

z is c _1-10 alkylene unsubstituted or substituted with phenyl, unsubstituted or d_

C _3-15 cycloalkylene, O, S, SO, SO ₂ , or CO substituted with 10 alkyl.

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

Also preferably Z is straight or branched Μ ₀ 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, Ζ is cyclonucleic acid-1,1-diyl, 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) cyclonucleic acid, 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, 1,2-bis (4-hydroxyphenyl) -1 -Phenylethane, bis (4-hydroxyphenyl) diphenylmethane, and alpha, omega-bis [3- (o- Hydroxyphenyl) propyl] polydimethylsiloxane may be derived from one or more aromatic dialkyl compounds.

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 triphosgen are polymerized, the repeating unit of Formula 1 may be represented by the following Formula 1-1:

Examples of the carbonate precursor include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclonuclear carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, and dinaphthyl carbonate. , At least one selected from the group consisting of bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and bishaloformate, 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 More than 28,000. In addition, the said 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 has a melt index (Ml) 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 the physical properties of the composition May be preferred. In particular, it may be more preferable that the polycarbonate resin includes two or more kinds of polycarbonate resins having different melt indexes (Ml) in terms of stable expression of physical properties of the composition. For example, when the polycarbonate resin composition contains two kinds of polycarbonate resin having different melt index (Ml), having a melt index (Ml) of 5 g / 10 minutes to 15 g / 10 minutes, Having a melt index (Ml) of 16 g / 10 min to 25 g / 10 min can be preferably applied. For example, when the polycarbonate resin composition includes two kinds of polycarbonate resins having different melt indexes (Ml), the polycarbonate resin may be used as the polycarbonate resin based on 100 parts by weight of the first polycarbonate resin. It is advantageous for the expression of the above-mentioned effect to include 150 to 350 parts by weight of a 2 polycarbonate resin having a higher melt index than the resin.

Preferably, the content of the second polycarbonate resin is 150 parts by weight or more, or 160 parts by weight or more, or 170 parts by weight or more based on 100 parts by weight of the first polycarbonate resin. In addition, the content of the second polycarbonate resin is 350 parts by weight or less, or 300 parts by weight or less, or 290 parts by weight or less, or 285 parts by weight or less based on 100 parts by weight of the 11 polycarbonate resin.

(2) Copolycarbonate resin

The copolycarbonate resin is an aromatic polycarbonate having an aromatic polycarbonate-based first repeating unit and at least one siloxane bond as a component added to improve the physical properties of the above-described polycarbonate resin, in particular, the heat resistance and the impact strength. Carbonate-based crabs include two repeat units.

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 crab 1 repeating unit is formed by the reaction of a dialkyl compound and a carbonate precursor, and may preferably include the repeating unit represented by the above-mentioned Formula 1.

In Chemical Formula 1,

Z is unsubstituted or substituted with phenyl c _1-10 alkylene, unsubstituted or

C _3-15 cycloalkylene substituted with 10 alkyl, O, S, SO, SO ₂ , or CO.

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

As a non-limiting example, when the aromatic di 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:

Examples of the carbonate precursors include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclonuclear 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]

On the other hand, the polycarbonate-based second repeating having at least one siloxane bond and one or more siloxane compound and the carbonate precursor is formed by reacting, preferably represented by the following formula (3) may include a repeating unit:

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,

n2 is an integer of 10-200. 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 are each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, medo Hydroxy, ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl, or naphthyl. Also preferably, each of R ⁶ is independently C _1-10 alkyl, more preferably C _1-6 alkyl, more preferably d_ 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 iN) 50 or more, or 55 or more, and may be 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]

In Chemical Formula 3-1,

R ⁶ and n 2 are the same as defined in Chemical Formula 3, respectively. And, according to an embodiment of the invention, the second repeating unit may further include a repeating unit represented by the following formula (2):

[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; d_ ₁₀ alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,

n1 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. Copolycarbonate further comprises a repeating unit represented by Formula 2 as the C 2 repeating unit so that the polycarbonate-based resin composition including the same has more improved heat resistance and impact resistance. In Formula 2, R ⁵ are each independently hydrogen, methyl, ethyl, propyl 3-phenylpropyl, 2-phenylpropyl, 3- (oxyranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy, ethoxy, propoxy, allyl, 2,2,2-trifluoro Roethyl, 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 d- 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 an integer of 35 or less, or i) 50 or more, or 55 or more, 70 or less, 65 or less, or an integer of 60 or less.

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

In Chemical Formula 2-1,

R ⁵ and n 1 are the same as defined in Chemical Formula 2, respectively. Preferably, the second repeating unit may include two or more repeating units selected from the group consisting of Chemical Formula 2 and Chemical Formula 3. More preferably, the second repeating unit includes a repeating unit represented by Formula 2 and a repeating unit represented by Formula 3 /

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

ᅳ 2 or more types of repeating units' as used in the present invention includes two or more types of repeating units having different structures, or the same structure, but different numbers of repeating units (n1 or n2) of silicon oxide in the structures of Formulas 2 and 3 To include two or more kinds it means.

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, Π) one represented by Formula 2 It means to include a repeating unit and the other repeating unit represented by the formula (2), or in) one repeating unit represented by the formula (3) and another repeating unit represented by the formula (3). Among the above examples, i) most preferably includes one repeating unit represented by Formula 2 and one repeating unit represented by Formula 3.

In each case including 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, 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:

In Chemical Formula 2-2,

X ¹ , R ⁵ and n ¹ are each as defined in Chemical Formula 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 term “derived from the siloxane compound” means that the hydroxyl group and the carbonate precursor of each of the siloxane compounds react to form a repeating unit represented by Formulas 2 and 3, respectively. In addition, the carbonate precursors that can be used to form the repeating units of Formulas 2 and 3 are the same as those described above for the carbonate precursors 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

C1

2-2

In Scheme 1,

) < ¹³ is c _2-10 alkenyl,

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

Scheme 2

3-2 In Scheme 2,

( ²³ 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. As the metal catalyst, it is preferable to use an R catalyst, and as the R catalyst, an Ashby catalyst, a Karlstedt catalyst, a Lamoreaux catalyst, a Speyer catalyst, a PtCI ₂ (C)] ), PtCI ₂ (benzonitrile) ₂ , and one or more selected from the group consisting of H ₂ RBr ₆ can be used. The metal catalyst is at least 0.001 parts by weight, at least 0.005 parts by weight, or at least 0.01 parts by weight, based on 100 parts by weight of the compound represented by the formula ", 13 or 15, at most 1 part by weight, at most 0.1 part by weight, or at 0.05 parts by weight. It can be used in parts or less.

In addition, the reaction temperature is preferably 80 to 10C C. . In addition, the reaction time is preferably 1 hour to 5 hours. In addition, in the reaction formulas 1 and 2, the compound represented by Formula C2 or C4 may be prepared by reacting organodisiloxane and organocyclosiloxane under an acid catalyst, and adjusting the content of the reactant to n1 and n2. Can be adjusted. The reaction temperature is preferably 50 to 70 ^° C. 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, nuxamethyldisiloxane and nuxaphenyldisiloxane may 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, one or more selected from the group consisting of H ₂ S0 ₄ , HCI0 ₄ , AICIs, SbCI _5j SnCI _4, and acidic clay may be used. In addition, the acid catalyst is 0.1 part by weight, 0.5 part by weight, or 1 part by weight or more, 10 parts by weight or less, 5 parts by weight or less, or 3 parts by weight or less based on 100 parts by weight of organocyclosiloxane.

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 is calculated by the weight ratio of the siloxane compound used in the copolycarbonate polymerization, for example, the siloxane compound represented by the above formulas (2-2) and (3-2).

[Composition and Manufacturing Method of Copolycarbonate 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 weight ⁰ /. Said first repeating unit and 0.001 to 10 weight ⁰ /. That is, when the content of the second repeating unit is excessively reduced, it may be difficult to sufficiently realize room temperature stratification strength, low temperature stratification strength, and fluidity physical properties by the second repeating unit. On the other hand, when 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 More than 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 depends on the physical properties of the composition to be controlled. It may vary. 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 15 parts by weight, or at least 18 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 45 parts by weight or less, or 30 parts by weight or less.

That is, the copolycarbonate resin is preferably contained 10 parts by weight or more, or 15 parts by weight or more, or 18 parts by weight or more based on 100 parts by weight of the polycarbonate resin in order to express the physical properties improving effect. 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 layer strength may reach or may be lowered. Therefore, the coplecarbonate 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 45 parts by weight or less, or 30 parts by weight or less based on 100 parts by weight of polycarbonate resin. It is preferred to be included. Meanwhile, according to the 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.

In the polymerization of the compounds, the at least one siloxane compound is added to an aromatic diol compound, a carbonate precursor, and at least 100 increments of ⁰ /.

0.1 ⁰ /. Above, 0.5 parts by weight ⁰ /. Above, 1 weight% or higher, or 0.5 and 1 wt. ⁰ /. Above, 20 parts by weight ⁰ /. Or less, 10 parts by weight ^_0/0 or less, 7 parts by weight ^_0/0 or less , 5 parts by weight ^_0/0 or less, 4 parts by weight ^_0/0 or less, 3 parts by weight ^_0/0, alternatively no more than 2 parts by weight ⁰ /. may be used below. In addition, the aromatic di compound is 40 weight ⁰ / ^° or more, 50 weight ⁰ / ^° or more, or 55 weight ⁰ / ^° or more, based on 100 weight ⁰ /. Of the total amount of aromatic di compound, carbonate precursor and one or more siloxane compounds, 80 parts by weight ⁰ /. or less, it is possible to use less than 70 wt.%, or 65% increase. Further, the carbonate precursor is at least 10% by weight ⁰ /., At least 20% by weight ⁰ /., Or at least 30% by weight, based on a total of 100% by weight ⁰ /. Of the aromatic diol compound, the carbonate precursor and the at least one siloxane compound, 60% by weight ⁰ /. Or less, 50 weight ⁰ /。 or less, or 40 weight ⁰ /。 or less.

As the polymerization method, for example, an interfacial polymerization method can be used. In this case, polymerization reaction is possible at atmospheric pressure and low silver, and 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 halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used as an example.

In addition, the interfacial polymerization is a reaction. For the promotion, reaction agents such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide and tetra-n-butylphosphonium bromide, quaternary ammonium compounds and quaternary phosphonium compounds may be further used. .

The reaction silver of the interfacial polymerization is preferably 0 to 40 ^° C, the reaction time is preferably 10 minutes to 5 hours. Moreover, it is preferable to maintain pH at 9 or more or 11 or more during interfacial polymerization reaction.

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 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, nuxadecylphenol, 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 parts by weight or more, 0,1 parts by weight or more, or 1 part by weight and 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of aromatic diol compound. , The desired molecular weight within this range You can get it.

(3) flame retardant

The polycarbonate-based resin composition according to the embodiment of the present invention includes a flame retardant.

Preferably, the flame retardant may be an organometallic salt-based flame retardant.

Specifically, the organometallic salt-based flame retardant may be at least one compound selected from the group consisting of sulfonic acid alkali metal salts and sulfonic acid alkaline earth metal salts.

For example, alkali metals include lithium, sodium, potassium, rubidium, and cesium; Alkaline earth metals include beryllium, magnesium, calcium, strontium, and barium.

As a non-limiting example, the preferred organometallic flame retardant may be an alkali metal salt of perfluoroalkylsulfonic acid. Specifically, the alkali metal salt of perfluoroalkyl sulfonate is calcium trifluoromethane sulfonate, potassium perfluorobutane sulfonate, potassium perfluoronucleate sulfonate, potassium perfluorooctane sulfonate, sodium pentafluoroethane sulfonate, and perfluoro Sodium butane sulfonate, sodium perfluorooctane sulfonate, lithium trifluoromethane sulfonate, lithium perfluorobutane sulfonate, lithium perfluoroheptane sulfonate, cesium trifluoromethane sulfonate, perfluorobutane sulfonate, perfluorooctane At least one compound selected from the group consisting of cesium sulfonate, perfluorouronusulfonic acid sulfonate, perfluorobutanesulfonate rubidium, and perfluoronucleosulfonate rubidium. Among them, potassium perfluorobutane sulfonate can be preferably used. On the other hand, the flame retardant may be included in 0.01 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin. Preferably, the content of the flame retardant is 0.01 parts by weight or more, or 0.05 parts by weight or more, or 0.1 parts by weight or more based on 100 parts by weight of the polycarbonate resin. In addition, the content of the flame retardant is 10 parts by weight or less, or 5 parts by weight or less, or 3 parts by weight or less, or 1 part by weight with respect to 100 parts by weight of the polycarbonate resin.

That is, the flame retardant for the expression of flame retardant polycarbonate resin 100 0.01 parts by weight or more, or 0.05 parts by weight or more, or 0.1 parts by weight or more, preferably included. However, when the flame retardant is added in an excessive amount, since the heat resistance and mechanical properties of the resin composition may be drastically reduced, the phosphate ester flame retardant may be 10 parts by weight or less, or 5 parts by weight or less based on 100 parts by weight of the polycarbonate resin. Or 3 parts by weight or less, or 1 parts by weight or less. Furthermore, the content of the flame retardant is preferably controlled in a range that does not inhibit the effect of improving the heat resistance and the layer strength according to the addition of the copolycarbonate resin.

Specifically, the flame retardant may be included in 0.1 to 10 parts by weight based on 100 parts by weight of the copolycarbonate resin. Preferably, the content of the flame retardant is 0.1 parts by weight or more, or 0.5 parts by weight or more based on 100 parts by weight of the copolycarbonate resin. In addition, the content of the flame retardant is 10 parts by weight or less, or 5 parts by weight or less, or 3 parts by weight or less, or 1 part by weight or less based on 100 parts by weight of the copolycarbonate resin.

(4) other ingredients

In the flame-retardant polycarbonate resin composition according to embodiments of the invention, as needed, methacrylate / butadiene / styrene (MBS) copolymer, acrylonitrile / butadiene / styrene (ABS) impact, such as a copolymer beam ⁷ ^ ^"I l ^(im Pact modifier) polytetrafluoroethylene

Drip inhibitors such as (PTFE); Surfactants; Nucleating agent; Coupling agents; Layered I; Plasticizer; Lubricant; Antibacterial agents; Mold 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 0.01 to 10 parts by weight based on 100 parts by weight of the polycarbonate resin.

However, in order to prevent the heat resistance, the layer strength, the 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 of 100 parts by weight of the polycarbonate resin. It is preferable that it is below a weight part, or 15 weight part or less, or 10 weight part or less. 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 the method of extrusion, injection, casting or the like 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 dry and inject the pellet prepared as a pellet.

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

【Effects of the Invention】

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

[Specific contents to carry out invention]

Hereinafter, preferred embodiments are presented to aid in understanding the present invention. However, the following examples are only for illustrating the present invention, and the present invention is not limited thereto. Preparation Example 1

: 47.6 g (160 mmol) of octamethylcyclotetrasiloxane, tetramethyldisiloxane 2.4 Lu (g. 17.8 mm) was mixed, and the mixture was added to 100 parts by weight of octamethylcyclotetrasiloxane with 1 part by weight of acidic clay (DC-A3) in a 3L flask and reacted at 60 ^° C. for 4 hours. After completion of 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. and 1 torr. The terminal modified polyorganosiloxane thus obtained was named AP-PDMS (n1 = 34). AP-PDMS is a light yellow oil, it was confirmed that the repeat unit (n1) was 34 by ¹ H NMR using a Varian 500MHz, no further purification was required. Preparation Example 2

: After mixing 47.60 g (160 mmol) of octamethylcyclotetrasiloxane and 1.5 g (1 1 mm) of tetramethyldisiloxane, the mixture was mixed with 100 parts by weight of octamethylcyclotetrasiloxane (DC-A3). 1) into a 3L flask with 1 part by weight and reacted at 60 ^° C for 4 hours. After completion of reaction, the mixture was diluted with ethyl acetate and filtered rapidly with 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) 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. and 1 torr. Terminal denaturation thus obtained The polyorganosiloxane was named MBHB-PDMS (n 2 = 58). MBHB-PDMS was light yellow oil, and the repeat unit (n2) was 58 by ¹ H NMR using a Varian 500 MHz. No further purification was necessary. Preparation Example 3

Preparation of Copolycarbonate Resin

: 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphen A) were added to a polymerization reactor, and the mixture was dissolved under N ₂ atmosphere. A mixed solution of 4.3 g of PTBP (para-tert butylphenol) and 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 added. 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 then 46 g of TEA (triethylamine) was added for 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 thus obtained polymer was obtained by reprecipitation of methane in a nucleic acid mixture solution and then dried at 120 ° C. to finally obtain a copolycarbonate resin (Mw = 30,500). Preparation Example 4

(1) Into the polymerization reactor, 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisbis A) were mixed and dissolved under 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 then 46 g of TEA (triethylamine) was added for 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 nucleic acid mixture solution, which was then dried at 120 ^° C. to give a final polycarbonate resin (Mw = 31000; Ml = 10 g / 10 under a silver degree of 300 ^° C. and a load of 1.2 kg). Min).

(2) 1784 g of water, 385 g of NaOH, and 232 g of BPA (bisphenol A) were added to the polymerization reactor, and the mixture was dissolved under N ₂ atmosphere. Then 128 g of TPG (triphosgene) After dissolving, adding and reacting for 1 hour while maintaining the pH at 11 or more, and after 10 minutes, 46 g of TEA (triethylamine) was added to conduct a coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and the resulting polymer was 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 nucleic acid mixture solution, which was then dried at 120 ^° C. to give a final polycarbonate resin (Mw = 26000; Ml = 22 g / 10 at a temperature of 30 C C and a load of 1.2 kg). Min). Examples and Comparative Examples

To the pellets were prepared by the addition of each component in the composition of Table 1 and then melted and shaken. After drying the prepared pellets for 6 hours at 70 ^° C, 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 (MM 0 g / 10 minutes)

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

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

Chem.)

(C-1) Organometallic Salt Flame Retardant (HX98, MITENI S.p.A.)

(C-2) organophosphorus flame retardant (FP-600, ADEKA Co.)

(C-3) organophosphorus flame retardant (PX-200, DAIHACHI CHEMICAL INDUSTRY Co.,

Ltd.)

(D-1) Lamellar Reinforcement (MBS copolymer, EM505, LG Chem.)

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

(D-3) Drip Inhibitor (PTFE, XFLON-G, POCERA Co.)

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

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

(D-6) lubricant (Licowax E, CLARIANT)

(D-7) UV stabilizer (TINUVIN 329, BASF) Table 1

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) Lamellar strength (IZOD): measured at 1/4 inch (Notched Izod, kg cm / cm) and 1/8 inch (Notched Izod, kg cm / cm) under 23 ^° C according to ASTM D256.

(2) Melt Index (Ml): Measured according to ASTM D1238 (300 ^° C., 1.2 kg conditions).

(3) Tensile Strength (TS) and Tensile Elongation (TE): Measured according to ASTM D638 (50 mm / min).

(4) Flexural elasticity (FM) and flexural strength (FS) were 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) Flame retardant rating: Measured according to the UL 94 V Test (vertical burning test, 1.6mm).

Table 2

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

Claims

[Claim]

[Claim 1]

An organo metal salt flame retardant;

The one repeating unit each independently includes a repeating unit represented by the following Formula 1;

The second repeating unit comprises a repeating unit represented by the following formula (3), flame retardant polycarbonate-based resin composition:

In Chemical Formula 1

Z is C ₁₀ alkylene unsubstituted or substituted with phenyl, C _3-15 cycloalkylene unsubstituted or substituted with C ₁₀ alkyl, O, S, SO, SO ₂ , or CO;

[Formula 31]

In Chemical Formula 3,

Each X ² is independently Cwo 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; Cwo haloalkyl; Or C ₆ ᅳ ₂₀ aryl,

n2 is an integer of 10-200.

[Claim 2]

The method of claim 1,

The repeating unit of Chemical Formula 1 is represented by the following Chemical Formula 1-1, flame retardant polycarbonate-based resin

[Claim 3]

The method of claim 1,

The repeating unit of Chemical Formula 3 is represented by the following Chemical Formula 3-1, a difficult-to-fold polycarbonate resin composition:

In Chemical Formula 3-1,

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

[Claim 4]

The method of claim 1, The second repeating unit comprises a repeating unit represented by the following formula (2) and the repeating unit represented by the formula (3), flame-retardant polycarbonate-based resin composition:

In Chemical Formula 2,

Each X ¹ is independently C _1-10 alkylene

R ⁵ are each independently. Hydrogen; Unsubstituted or substituted with oxiranyl, oxiranyl substituted C _1-10 alkoxy or C _6-20 aryl; d. ₁₅ alkyl; halogen; d- ₁₀ alkoxy; Allyl; C _1-10 haloalkyl; Or C _6-20 aryl,

n1 is an integer of 10-200.

[Claim 5]

In paragraph 4

The repeating unit of Chemical Formula 2 is represented by the following Chemical Formula 2-1, flame retardant polycarbonate-based resin composition:

In Chemical Formula 2-1,

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

[Claim 6]

The method of claim 1,

The polycarbonate resin is 5 at a temperature of 300 ^° C and a load of 1.2 kg Flame retardant polycarbonate system with a melt index (Ml) of g / 10 min

[Claim 7]

The method according to claim 1,

The polycarbonate resin comprises two or more polycarbonate resins having different melt index (Ml), flame retardant polycarbonate-based resin composition.

[Claim 8]

The method of claim 1,

The polycarbonate resin comprises a flame retardant polycarbonate resin composition, based on 100 parts by weight of the first polycarbonate resin, 150 to 350 parts by weight of the crab 2 polycarbonate resin having a larger melt index than the crab 1 polycarbonate resin.

[Claim 9]

The method of claim 1,

Wherein the copolycarbonate resin comprises 90 to 99.999 weight% of the first repeating unit and 0.001 to 10 weight ⁰ /. Of the second repeating unit.

[Claim 10]

The method of claim 1,

The polycarbonate resin and the copolycarbonate resin, each flame retardant polycarbonate resin composition having a weight average molecular weight of 1,000 to 100,000 g / m.

[Claim 1 11]

According to claim 1,

The organometallic salt-based flame retardant is one or more compounds selected from the group consisting of sulfonic acid alkali metal salts and sulfonic acid alkaline earth metal salts, flame retardant Polycarbonate-based resin composition.

[Claim 12]

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

0.01 to 10 parts by weight of the organometallic salt flame retardant

Polycarbonate-based resin composition comprising a.

[Claim 13]

Molded article formed from the polycarbonate-based resin composition of claim I.