KR102060635B1 - Polycarbonate resin composition and thin film article made from the same - Google Patents

Abstract

The present disclosure relates to a polycarbonate resin composition and a thin film molded article manufactured therefrom, and more particularly, to a) 50 to 90% by weight of a polycarbonate resin derived from bisphenol A; b) 8 to 40% by weight of polycarbonate-polyorganosiloxane copolymer; c) 1 to 6 weight percent flow modifier; And d) 1 to 4% by weight of the core-shell impact modifier; and a polycarbonate resin composition comprising a thin film molded article prepared therefrom.
According to the present invention, there is little gas generated during molding, excellent appearance characteristics, excellent fluidity and chemical resistance, there is an effect of providing a polycarbonate resin composition and thin film molded article prepared therefrom optimized for thin film molding.

Description

Polycarbonate resin composition and thin film molded article manufactured therefrom {POLYCARBONATE RESIN COMPOSITION AND THIN FILM ARTICLE MADE FROM THE SAME}

The present invention relates to a polycarbonate resin composition and a thin film molded article manufactured therefrom. More specifically, the present invention relates to a polycarbonate resin composition optimized for thin film molding because of less gas generation during molding and excellent appearance characteristics, excellent fluidity and chemical resistance. It relates to a thin film molded article produced therefrom.

Polycarbonate resins are thermoplastic resins produced by reacting bisphenol A with phosgene. The polycarbonate resins are known to be transparent because they are amorphous, have excellent heat resistance and electrical insulation, and have the highest impact strength among thermoplastic resins. In addition, polycarbonate resins are known as engineering plastics that are extremely small in dimensional change due to moisture absorption and stable in physical properties even with temperature change, and thus resistant to environmental changes.

Such polycarbonate resins are widely used in housings of electronic products, but have a disadvantage in that low-temperature impact strength and chemical resistance are not sufficient to be applied to mobile phone housings due to the use environment characteristics such as low temperature exposure and painting.

Therefore, conventionally, an impact modifier was applied to a polycarbonate resin to improve low temperature impact strength, but it was not easy to form a thin film due to a change in the design of a mobile phone. There is a problem that occurs due to cracks.

Therefore, there is an urgent need to develop a polycarbonate resin having excellent high flow rate, that is, thin film formability and excellent chemical resistance, low temperature impact strength, and appearance characteristics, which can be applied to recent mobile phone design changes.

Korean Patent Publication No. 2009-0052447 (published May 26, 2009)

In order to solve the problems of the prior art as described above, the present invention provides a polycarbonate resin composition optimized for thin film molding, and excellent thin film generation, less gas generation during molding, excellent fluidity and chemical resistance, and a thin film molded article manufactured therefrom. It aims to do it.

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

In order to achieve the above object, the present disclosure is a) 50 to 90% by weight of a polycarbonate resin derived from bisphenol A; b) 8 to 40% by weight of polycarbonate-polyorganosiloxane copolymer; c) 1 to 6 weight percent flow modifier; And d) 1 to 4% by weight of the core-shell impact modifier; provides a polycarbonate resin composition comprising a.

In addition, the present disclosure provides a thin film molded article manufactured from the polycarbonate resin composition.

According to the present disclosure, there is little gas generation during molding, and thus excellent appearance characteristics, excellent fluidity and chemical resistance, and there is an effect of providing a polycarbonate resin composition optimized for thin film molding and a thin film molded article manufactured therefrom.

Hereinafter, the polycarbonate resin composition of the present disclosure and the thin film molded article manufactured therefrom will be described in detail.

The present inventors endeavored to develop a high-flow chemical resistant polycarbonate material for mobile phones, as a result of hybridization of polysiloxane-polycarbonate copolymer and general polycarbonate resin to control the balance of chemical resistance and fluidity, By optimizing the content of the impact modifier to maximize the low-temperature impact strength and chemical resistance, and at the same time adding a flow modifier, the gas generated is minimized, the appearance characteristics are greatly improved, and the high-flow chemical polycarbonate material optimized for thin film molding is manufactured. After confirming that, based on this, the description was completed.

The polycarbonate resin composition of the present disclosure comprises a) 50 to 90% by weight of a polycarbonate resin derived from bisphenol A; b) 8 to 40% by weight of polycarbonate-polyorganosiloxane copolymer; c) 1 to 6 weight percent flow modifier; And d) 1 to 4% by weight of the core-shell impact modifier.

Examples of the polycarbonate resin composition include a) 51 to 90 wt% of a polycarbonate resin derived from bisphenol A; b) 10 to 40% by weight of polycarbonate-polyorganosiloxane copolymer; c) 1 to 5 weight percent flow modifier; And d) 1 to 4% by weight of the core-shell impact modifier; and within this range, less gas is generated during molding, so that the appearance characteristics are excellent, the fluidity and the chemical resistance are excellent, and thus the thin film is optimized.

As another example, the polycarbonate resin derived from a) bisphenol A may be 58 to 87% by weight, or 80 to 87% by weight, and has excellent effects of chemical resistance, molding processability, and physical property balance within this range.

The polycarbonate resin derived from a) bisphenol A may have, for example, a melt index (300, 1.2 kg) of 15 to 30 g / 10 minutes, or 20 to 30 g / 10 minutes, and preferably 21 to 29 g / 10. In this range, the chemical resistance, molding processability and physical property balance are excellent in this range.

In addition, the a) polycarbonate resin derived from bisphenol A is, for example, a polycarbonate resin (a-1) derived from bisphenol A having a melt index (300, 1.2 kg) of 8 to 20 g / 10 minutes and a melt index (300, 1.2). kg) may be a mixture of the polycarbonate resin (a-2) derived from bisphenol A having 21 to 40 g / 10 minutes, and the chemical resistance, the molding processability and the physical property balance are excellent in this range.

As another example, the polycarbonate resin derived from a) bisphenol A may be a polycarbonate resin (a-1) derived from bisphenol A having a melt index (300, 1.2 kg) of 8 to 15 g / 10 minutes and a melt index (300, 1.2). kg) may be a mixture of the polycarbonate resin (a-2) derived from bisphenol A having 25 to 35 g / 10 minutes, and the chemical resistance, the molding processability and the physical property balance are excellent in this range.

The polycarbonate resin (a-1) may be, for example, 1 to 25% by weight, 5 to 25% by weight, or 10 to 22% by weight with respect to the polycarbonate resin composition, and chemical resistance and moldability within this range. And the physical property balance is excellent effect.

The (a-2) polycarbonate resin may be 58 to 80% by weight, 60 to 80% by weight, or 65 to 75% by weight with respect to the polycarbonate resin composition, for example, chemical resistance, molding processability within this range And the physical property balance is excellent effect.

The polycarbonate resin derived from a) bisphenol A has a weight average molecular weight of, for example, 1,000 to 100,000 g / mol, 5,000 to 50,000 g / mol, 20,000 to 40,000 g / mol, 20,000 to 35,000 g / mol, or 22,000 to 31,000 g / mol, and within this range there is an excellent effect of chemical resistance, molding processability and balance of physical properties.

In this description, the weight average molecular weight can be measured by the GPC method as a PC standard.

The b) polycarbonate resin derived from bisphenol A is not particularly limited in the case of a polymer commonly referred to as a polycarbonate resin derived from bisphenol A, but is, for example, a polycarbonate resin including a bisphenol A or a derivative thereof and a carbonate precursor. The carbonate precursor is, for example, dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis (Diphenyl) carbonate, carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide and bishaloformates.

As used herein, the derivative of bisphenol A refers to a compound in which at least one hydrogen or the like of bisphenol A is substituted with an alkyl group, a halogen group, or the like.

B) The polycarbonate-polyorganosiloxane copolymer may be, for example, 10 to 35% by weight, 10 to 25% by weight, or 10 to 15% by weight, and within this range, chemical resistance, molding processability, and physical property balance may be Excellent effect.

B) The polycarbonate-polyorganosiloxane copolymer has, for example, a weight average molecular weight of 10,000 to 100,000 g / mol, 15,000 to 60,000 g / mol, 20,000 to 50,000 g / mol, 25,000 to 35,000 g / mol, or 30,000 to It may be 33,000 g / mol, and within this range is excellent in rigidity, chemical resistance, impact resistance and appearance characteristics, there is an effect that can be enlarged and slimmed molded article.

The b) polycarbonate-polyorganosiloxane copolymer is not particularly limited in the case of the conventional polycarbonate-polyorganosiloxane copolymer, for example, a polymer prepared by condensation polymerization of polycarbonate resin and polyorganosiloxane, or It may be a polymer prepared by interfacial polymerization of an aromatic diol compound, a carbonate precursor, and a polyorganosiloxane.

In addition, a) the polycarbonate-polyorganosiloxane copolymer may be, for example, a polymer having a polysiloxane structure introduced into the main chain of the polycarbonate, and the polycarbonate main chain may be formed by, for example, reacting an aromatic diol compound with a carbonate precursor. have.

Examples of the aromatic diol compound include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis ( 4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, bisphenol A, 2,2-bis (4-hydroxyphenyl) butane, 1 , 1-bis (4-hydroxyphenyl) cyclohexane, 2,2-bis (4-hydroxy-3,5-dibromophenyl) propane, 2,2-bis (4-hydroxy-3,5 -Dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4 -Hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis ( At least one member selected from the group consisting of 4-hydroxyphenyl) diphenylmethane, and a, ω-bis [3- (ο-hydroxyphenyl) propyl] polydimethylsiloxane The.

The polyorganosiloxane is not particularly limited, but may be at least one selected from the group consisting of polydimethylsiloxane, polydiethylsiloxane, polymethylphenylsiloxane, and the like.

For example, the polyorganosiloxane may be included in an amount of 5 to 20% by weight, or 6 to 10% by weight based on the a) polycarbonate-polyorganosiloxane copolymer, and has excellent chemical resistance and impact resistance within this range. It works.

B) The polycarbonate-polyorganosiloxane copolymer may include a first repeating unit represented by the following Formula 1 and a second repeating unit represented by the following Formula 3 as a specific example.

[Formula 1]

In Formula 1, R1 to R4 are each independently hydrogen, C1-10 alkyl, C1-10 alkoxy, or halogen, Z is C1-10 alkylene unsubstituted or substituted with phenyl, unsubstituted or C1- C3-15 cycloalkylene, O, S, SO, SO2, or CO substituted with 10 alkyl. Here, the R1 to R4 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 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, One or more 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.

[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, and R 6 is each independently Hydrogen; C1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C1-10 alkoxy, or C6-20 aryl; halogen; C1-10 alkoxy; Allyl; C1-10 haloalkyl; Or C6-20 aryl, 15 n2 is an integer from 10 to 200.

In Formula 3, preferably, each of X2 is independently C2-10 alkylene, more preferably C2-6 alkylene, and most preferably isobutylene. Preferably, in Formula 3, Y1 may be hydrogen.

R 6 in Formula 3 is 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 6 is independently C 1-10 alkyl, more preferably C 1-6 alkyl, more preferably C 1-3 alkyl, 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]

In Formula 3-1, R6 and n2 are the same as defined in Formula 3, respectively. In addition, according to an embodiment of the present invention, the second repeating unit may further include a repeating unit represented by Formula 2 below:

[Formula 2]

In Chemical Formula 2, each X 1 is independently C 1-10 alkylene, and each R 5 is independently hydrogen; C1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C1-10 alkoxy, or C6-20 aryl; halogen; C1-10 alkoxy; Allyl; C1-10 haloalkyl; Or C6-20 aryl, n1 is an integer from 10 to 200.

In Formula 2, X1 may be each independently C2-10 alkylene, preferably C2-4 alkylene, more preferably propane-1,3-diyl.

Copolycarbonate further comprises a repeating unit represented by the formula (2) as the second repeating unit so that the polycarbonate-based resin composition comprising the same has more improved heat resistance and impact resistance.

In Formula 2, each R 5 is 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 R 5 is independently C 1-10 alkyl, more preferably C 1-6 alkyl, more preferably C 1-3 alkyl, 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 Formula 2-1, R5 and n1 are the same as defined in 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 the room temperature impact strength, the low temperature impact strength, and the fluidity were significantly increased, and the degree of improvement of physical properties by each repeating unit was increased. This is due to the complementary effect.

As used herein, the term 'two or more repeating units' includes two or more repeating units having different structures or the same structure, but the number of repeating units (n 1 5 or n 2) of silicon oxide in the structures of Formulas 2 and 3 It means containing two or more different 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). 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 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, 25 wherein X1, R5, and n1 are as defined in Chemical Formula 2, respectively;

[Formula 3-2]

In Formula 3-2, X2, Y1, R6, and n2 are the same as defined in Formula 3, respectively.

The meaning of 'derived from the siloxane compound' means that the hydroxy group and the carbonate precursor of each of the siloxane compounds react to form a repeating unit represented by the 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, and X 1, R 5 and n 1 are each as defined in Formula 2;

Scheme 2

In Scheme 2, X2a is C2-10 alkenyl, and X2, Y1, R6, and n2 are each as defined in Chemical Formula 3.

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 PtCl2 (COD), and a PtCl2 At least one selected from the group consisting of (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, for example, one or more selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, hexamethyldisiloxane and hexaphenyldisiloxane can be used. As the organocyclosiloxane, an organocyclotetrasiloxane may be used as an example, and examples thereof include octamethylcyclotetrasiloxane, octaphenylcyclotetrasiloxane, and the like.

The organodisiloxane may be, for example, 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 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 unit 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 Formulas 2-2 and 3-2.

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 room temperature impact strength, low temperature impact 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.

The copolycarbonate resin may have, for example, a weight average molecular weight of 1,000 to 100,000 g / mol, preferably 5,000 to 50,000 g / mol. Appropriate ductility and YI of the copolycarbonate resin can be secured within the weight average molecular weight range. 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.

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% relative to a total of 100 wt% 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. Or up to 65 5% by weight. 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 halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used as an example.

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. Accelerators may additionally be used.

It is preferable that the reaction temperature of the said interfacial polymerization is 0-40 degreeC, and the reaction time of 10 minutes-5 hours is preferable. In addition, 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 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 is, for example, based on 100 parts by weight of the aromatic diol compound, 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 less, or 5 parts by weight or less. It is possible to obtain a desired molecular weight within this range.

C) the flow modifier may be, for example, 2 to 5% by weight, or 3 to 5% by weight, and has excellent chemical resistance within this range.

The c) the flow modifier may be at least one selected from the group consisting of polyethylene terephtalate (PET) and organophosphate ester compounds, for example, less gas generated during molding within this range, excellent appearance characteristics, fluidity and chemical resistance It is excellent in thin film forming products.

The organophosphate ester compound may be, for example, one or more selected from the group consisting of triphenylphosphate, bisphenol A diphenylphosphate, and resorcinol diphenyl phosphate. It is excellent in fluidity and chemical resistance, and has an effect of being optimized for thin film molding.

The d) core-shell impact modifier may be, for example, 2 to 4% by weight, and excellent chemical resistance and physical property balance within this range.

The d) core-shell impact modifier may be, for example, a MA-BD-based impact modifier, a silicone-acrylic impact modifier or a mixture thereof, and has an excellent balance of chemical resistance and physical properties within this range.

The MA-BD-based impact modifier may be a copolymer of a core-shell structure in which a methacrylate monomer is graft copolymerized to a conjugated diene rubber, for example, and has an excellent balance of chemical resistance and physical properties within this range.

The conjugated diene rubber may be, for example, butadiene rubber or styrene-butadiene rubber, and the methacrylate monomer may be, for example, alkyl methacrylate having 1 to 10 carbon atoms of an alkyl group or aryl meta having 6 to 10 carbon atoms of an aryl group. It may be a acrylate, and in particular, may be at least one selected from the group consisting of methyl methacrylate, butyl methacrylate, benzyl methacrylate, and the like.

The MA-BD-based impact modifiers may be, for example, EM series of LG Chemical, for example, EM500, EM500A and EM505.

The silicone-acrylic impact modifier may be, for example, a copolymer of a core-shell structure in which an acrylate-based monomer and a methacrylate-based monomer are graft copolymerized to a silicone-based rubber, and have excellent chemical resistance and impact strength within this range. There is.

The silicone-acrylic impact modifier may include, for example, 30 to 80% by weight of acrylate monomers, 10 to 50% by weight of methacrylate monomers, and 5 to 20% by weight of silicone monomers. Molding workability and impact strength is excellent.

The silicone monomer is not particularly limited in the case of a conventional silicone rubber component monomer, and for example, hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcyclopentasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotri It may be at least one selected from the group consisting of siloxane, tetramethyltetraphenylcyclotetrasiloxane, octaphenylcyclotetrasiloxane and the like.

The acrylate monomer may be, for example, an alkyl acrylate having 1 to 10 carbon atoms of an alkyl group or an aryl acrylate having 6 to 10 carbon atoms of an aryl group. Specific examples thereof include methyl acrylate, butyl acrylate, benzyl acrylate, and the like. It may be one or more selected from the group consisting of.

The methacrylate monomer may be, for example, alkyl methacrylate having 1 to 10 carbon atoms of an alkyl group or aryl methacrylate having 6 to 10 carbon atoms of an aryl group. Specific examples thereof include methyl methacrylate and butyl methacrylate. And benzyl methacrylate may be one or more selected from the group consisting of.

The silicone-acrylic impact modifier may be, for example, Metablen series of MRC, for example, Metablen S-2001 and S-2006.

The polycarbonate resin composition may have, for example, a melt index (300, 1.2 kg) of 15 to 30 g / 10 minutes, 20 to 30 g / 10 minutes, or 21 to 29 g / 10 minutes, and chemical resistance within this range. It is effective in molding processability and impact strength.

For example, the polycarbonate resin composition may have an impact strength (1/4 ″) of 40 to 80 kgcm / cm, 50 to 75 kgcm / cm, or 55 to 72 kgcm / cm, and excellent chemical resistance within this range. It works.

The polycarbonate resin composition may have, for example, chemical resistance (ESCR TEST, CH ₃ OH / CH ₃ COCH ₃ = 4/6) of 20 seconds or more, 23 seconds or more, or 25 seconds or more. And the physical property balance is excellent effect.

The polycarbonate resin composition may be, for example, for thin film molding.

The polycarbonate resin composition of the present disclosure may be a thermal stabilizer, a lubricant, a processing agent, a plasticizer, a coupling agent, a light stabilizer, a mold release agent, a dispersant, an antidropping agent, a weather stabilizer, an antioxidant, and a commercialization, if necessary, within a range that does not adversely affect physical properties. At least one selected from the group consisting of a pigment, a dye, an antistatic agent, an antiwear agent, a filler, a flame retardant, and an antibacterial agent, based on 100 parts by weight of the total polycarbonate resin composition of the present disclosure, 0.1 to 20 parts by weight, 0.1 to 10 parts by weight, Or it may further comprise 1 to 5 parts by weight.

Method for producing a polycarbonate resin composition of the present disclosure is, for example: a) 50 to 90% by weight of a polycarbonate resin derived from bisphenol A; b) 8 to 40% by weight of polycarbonate-polyorganosiloxane copolymer; c) 1 to 6 weight percent flow modifier; And d) 1 to 4% by weight of the core-shell impact modifier; melt kneading and extruding the mixture.

The thin film molded article of the present disclosure is characterized in that it is produced from the polycarbonate resin composition of the present disclosure.

The thin film molded article may be, for example, a mobile phone housing.

The thin film molded article may be, for example, a molded article having a thickness of 0.6 mm or less.

Hereinafter, preferred examples are provided to help the understanding of the present disclosure, but the following examples are merely exemplified by the present disclosure, and it is obvious to those skilled in the art that various changes and modifications can be made within the scope and spirit of the present disclosure. It is natural that such variations and modifications fall within the scope of the appended claims.

EXAMPLE

Specific specifications of each component (A to D) used in Examples 1 to 6 and Comparative Examples 1 to 3 are as follows.

<(A) Bisphenol A polycarbonate resin>

Bisphenol A poly with melt index (300 ° C, 1.2 kg load) 10 g / 10 min ((A) -1), 30 g / 10 min ((A) -2), and 60 g / 10 min ((A) -3) Carbonate resins were used (each LG Chem PC 1300-10, 1300-30, 1080, each weight average molecular weight is 31,000g / mol, 22,000g / mol, 19,000g / mol).

<(B) Siloxane  Copolymerized Polycarbonate Resin>

As the polymer of the polycarbonate resin and the polyorganosiloxane, LG Chem SPC8000-05, Samyang Corporation TRIREX ST6-3022PJ (1), or a siloxane copolymerized polycarbonate resin prepared by the following method was used.

<Preparation of siloxane copolymerized polycarbonate resin>

One. Of polyorganosiloxane (AP-PDMS, n = 34)  Produce

: 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 the repeat unit (n1) was found to be 34 by 1 H NMR using a Varian 500 MHz, and no further purification was necessary.

2. Polyorganosiloxane ( MBHB - PDMS , n2 = 58)  Produce

: 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) 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 was a light yellow oil, and the repeat unit (n2) was 58 by 1 H NMR using a Varian 500 MHz. No further purification was necessary.

3. Copolycarbonate  Preparation of 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 mixture 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 minutes, 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 siloxane copolymerized polycarbonate resin (Mw = 30,500).

<(C) -1 Rheology modifier : PET>

SK Chemicals SkyPET BB8055 was used.

<(C) -2 flow Modifier Phosphate Ester Compounds>

The Japanese Daihachi PX-200 was used.

<(D) -1 core-shell structure Impact modifier >

An MMA-BD-based impact modifier constituting the core-shell structure was used (EM505 by LG).

<(D) -2 core-shell structure Impact modifier >

A silicone-acrylic impact modifier constituting the core-shell structure was used (S2001 of MRC).

Example  1 to 6 and Comparative example  1 to 4

The components (A to E) were melt-kneaded under a 280 ° C. condition in a twin screw extruder according to the weight ratio of the following Table 1 and extruded to prepare a polycarbonate resin composition pellet. Molded into.

[Test Example]

The properties of the polycarbonate resin composition specimens prepared in Examples 1 to 6 and Comparative Examples 1 to 4 were measured by the following method, and the results are shown in Table 2 below.

Melt index (g / 10min): measured in g as measured in 10 minutes under a temperature of 300 ° C. and a load of 1.2 kg according to ASTM D1238.

* Impact strength (kgcm / cm): measured at 23 ℃ according to ASTM D256 (1/4 inch, Notched Izod).

* Chemical resistance (second): Pelletized using a Φ40㎜ twin screw extruder using the composition, and then injection molded at a cylinder temperature of 290 ℃ and a mold temperature of 80 ℃ using an ENGEL 80 ton injection molding machine to tensile test specimen for ASTM D638 evaluation Was injection molded and prepared. After fixing the specimen in an ESCR (Environmental Stress-Cracking Resistance) jig, a mixed solvent containing methanol and acetone in a weight ratio of 4: 6 was added dropwise to observe the crack occurrence time. Table 2 summarizes the results of chemical resistance evaluation by the time (seconds) at which the occurrence of cracks is observed.

division Example Comparative example One 2 3 4 5 6 One 2 3 4 A One 20 20 22 10 - 10 60 20 - 30 2 65 65 65 75 58 71 35 65 60 65 3 - - - - - - - - 27 - B 10 10 10 10 35 10 - 10 10 - C One 3 3 - 5 5 5 - 3 5 3 2 - - One - - - - - - - D One 2 - 2 2 2 4 - - 2 2 2 - 2 - - - - 5 - - -

division Example Comparative example One 2 3 4 5 6 One 2 3 4 Melt index 25 25 24 29 21 24 12 25 37 15 Impact strength 60 62 63 55 57 72 65 15 30 35 Chemical resistance (cracking time (seconds)) 26 28 20 23 25 24 10 15 10 15

As shown in Table 1, it was confirmed that the polycarbonate resin compositions (Examples 1 to 6) of the present disclosure were excellent in molding processability, impact strength and physical property balance, and particularly excellent in chemical resistance.

However, when out of the range according to the present description (Comparative Examples 1 to 4), it was confirmed that the physical property balance was broken and the chemical resistance was greatly poor.

Claims (12)

a) 50 to 90% by weight of polycarbonate resin derived from bisphenol A;
b) 8 to 40% by weight of polycarbonate-polyorganosiloxane copolymer;
c) 1 to 6 weight percent flow modifier; And
d) 1 to 4 weight percent of a core-shell impact modifier;
B) the polycarbonate-polyorganosiloxane copolymer has a weight average molecular weight of 30,000 to 33,000 g / mol, characterized in that it comprises a repeating unit of formula
Polycarbonate resin composition.

In Formula 3, X ² are each independently C 1-10 alkylene, Y ¹ are each independently hydrogen, C 1-6 alkyl, halogen, hydroxy, C 1-6 alkoxy or C 6-20 aryl, and R ⁶ is Each independently hydrogen; C1-15 alkyl unsubstituted or substituted with oxiranyl, oxiranyl substituted C1-10 alkoxy, or C6-20 aryl; halogen; C1-10 alkoxy; Allyl; C1-10 haloalkyl; Or C6-20 aryl, n2 is an integer from 10 to 200. The method of claim 1,
The polycarbonate resin composition comprises a) 58 to 87% by weight of a polycarbonate resin derived from bisphenol A; b) 10 to 40% by weight of polycarbonate-polyorganosiloxane copolymer; c) 1 to 5 weight percent flow modifier; And d) 1 to 4% by weight of the core-shell impact modifier.
Polycarbonate resin composition. The method of claim 1,
The polycarbonate resin derived from a) bisphenol A is characterized in that the melt index (300, 1.2kg) is 20 to 30 g / 10 minutes
Polycarbonate resin composition. delete The method of claim 1,
C) the flow modifier is at least one member selected from the group consisting of polyethylene terephtalate (PET) and organophosphate ester compounds
Polycarbonate resin composition. The method of claim 5,
The organophosphate ester compound is at least one member selected from the group consisting of triphenylphosphate, bisphenol A diphenylphosphate and resorcinol diphenyl phosphate.
Polycarbonate resin composition. The method of claim 1,
D) the core-shell impact modifier is a MA-BD-based impact modifier, silicone-acrylic impact modifier or a mixture thereof
Polycarbonate resin composition. The method of claim 1,
The polycarbonate resin composition is characterized in that the impact strength (1/4 ") is 40 to 80 kgcm / cm
Polycarbonate resin composition. The method of claim 1,
The polycarbonate resin composition is characterized in that the chemical resistance (CH ₃ OH / CH ₃ COCH ₃ = 4/6) is 20 seconds or more
Polycarbonate resin composition. The method of claim 1,
The polycarbonate resin composition is for forming a thin film of 0.6 mm or less thick
Polycarbonate resin composition. It is made from the polycarbonate resin composition according to any one of claims 1 to 3 and 5 to 10.
Thin film moldings. The method of claim 11,
The thin film molded product is characterized in that the mobile phone housing
Thin film moldings.