KR20170111792A - Polycarbonate resin composition and molded article comprising the same - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition and a molded article including the polycarbonate resin composition. More particularly, the present invention relates to a polycarbonate resin composition comprising 30 to 80% by weight of a polycarbonate resin and 10 to 20 g / 10 min of a melt index (300 DEG C, 1.2 kg) Characterized in that it comprises 10 to 60% by weight of a resin, 0.1 to less than 5% by weight of an impact modifier, 1 to less than 10% by weight of non-bonding type glass fibers and 1 to 20% A carbonate resin composition and a molded article containing the same.
INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polycarbonate resin composition excellent in low-strain characteristics and surface characteristics, and a molded article comprising the polycarbonate resin composition, while providing the same or higher melt index, impact strength and flame retardancy.

Description

TECHNICAL FIELD [0001] The present invention relates to a polycarbonate resin composition and a molded article including the polycarbonate resin composition.

The present invention relates to a polycarbonate resin composition and a molded article including the polycarbonate resin composition. More particularly, the present invention relates to a polycarbonate resin composition excellent in low melting point, impact strength and flame retardancy, .

BACKGROUND ART Polycarbonate resins are well known as amorphous thermoplastic resins having high impact resistance at room temperature, excellent mechanical properties such as impact strength, excellent thermal properties such as flame retardance and heat resistance, and high dimensional stability. And the like, and further studies are being conducted to realize more excellent physical properties by reinforcing them with inorganic fillers.

Due to the above characteristics, the polycarbonate resin is widely used for various applications such as a housing material for electrical and electronic products such as TVs, OA devices and IT devices. In recent years, the polycarbonate resin has been used as a portable IT device such as a smart phone and a tablet PC Is used as a housing material of the housing.

In this regard, the housing of the tablet PC is required to be larger and slimmer than a smart phone. However, when a non-reinforced polycarbonate resin used in a smart phone is used, there is a problem that a warp phenomenon becomes serious. In order to prevent such deformation, the inorganic filler such as bonding type glass fiber is introduced There is a disadvantage that the impact strength is extremely lowered, the filler rises to the surface, the gloss disappears, the surface becomes rough, and the appearance becomes poor. Accordingly, development of a housing material excellent in physical properties such as surface characteristics and impact strength while being prevented from being deformed is required.

KR 2015-0102858 A

An object of the present invention is to provide a polycarbonate resin composition which has a melt index, impact strength and flame retardancy equal to or higher than those of the prior art, but which is excellent in low strain characteristics and surface characteristics.

Another object of the present invention is to provide a molded article comprising the polycarbonate resin composition.

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

In order to achieve the above object, the present invention provides a thermoplastic resin composition comprising 10 to 60% by weight of a polycarbonate resin having 30 to 80% by weight of a polycarbonate resin, a melt index (300 DEG C, 1.2 kg) of 8 to 20 g / To less than 5% by weight of non-bonding type glass fibers, 1 to less than 10% by weight of non-bonding type glass fibers and 1 to 20% by weight of phosphorus flame retardant.

The present invention also provides a molded article comprising the polycarbonate resin composition.

INDUSTRIAL APPLICABILITY According to the present invention, it is possible to provide a polycarbonate resin composition excellent in low-strain characteristics and surface characteristics, and a molded article comprising the polycarbonate resin composition, while providing the same or higher melt index, impact strength and flame retardancy.

FIG. 1 is a photograph of a surface profile of a low strain characteristic (grade 4) and a surface characteristic (grade 4) obtained by observing a thin film specimen of Example 1 according to the present invention with a 3D microscope.
FIG. 2 is a photograph of a surface profile of a low strain characteristic (grade 5) and a surface characteristic (grade 1) obtained by observing a thin film specimen of Comparative Example 3 which does not comply with the present invention with a 3D microscope.
FIG. 3 is a photograph of a surface photograph of a low strain characteristic (first grade) and a surface characteristic (grade 5) obtained by observing a thin film specimen of Comparative Example 5 which does not comply with the present invention with a 3D microscope.

Hereinafter, the present invention will be described in detail.

The present inventors have found that, when a polycarbonate resin having a specific melt index and a low-content non-crystalline glass fiber are simultaneously introduced into a polycarbonate resin, the physical properties equivalent to those of a non-reinforced material And the present invention was completed on the basis thereof.

The polycarbonate resin composition according to the present invention will be described in detail as follows.

Wherein the polycarbonate resin composition comprises 30 to 80% by weight of a polycarbonate resin, 10 to 60% by weight of a copolycarbonate resin having a melt index (300 DEG C, 1.2 kg) of 8 to 20 g / 10 min, an impact modifier of 0.1 to less than 5 1 to less than 10% by weight of a non-bonding type glass fiber and 1 to 20% by weight of a phosphorus flame retardant.

The polycarbonate resin is not particularly limited, but may be a homopolycarbonate resin containing no comonomer such as a siloxane compound, and may be, for example, a resin polymerized including a bisphenol-based monomer and a carbonate precursor.

Examples of the non-sprinol-based monomer include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A; BPA), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ) Propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2 (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) ) Propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane and?,? Polydimethylsiloxane And an acid.

The carbonate precursor may be at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis Diphenyl carbonate), carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformate.

The polycarbonate resin may have a melt index (300 DEG C, 1.2 kg) of 8 to 20 g / 10 min, 8 to 18 g / 10 min, or 10 to 15 g / 10 min, , Moldability and impact strength are excellent. The melt index refers to the melt index measured under the standard measurement ASTM D1238 (300 DEG C, 1.2 kg).

The polycarbonate resin may be contained in an amount of 30 to 80% by weight, 35 to 70% by weight, or 35 to 68% by weight based on the polycarbonate resin composition, and has an excellent flowability and impact strength within this range .

The above-mentioned copolycarbonate resin having a melt index (300 ° C, 1.2 kg) of 8 to 20 g / 10 min constitutes the base resin in the polycarbonate resin composition together with the above polycarbonate resin. In this case, the polycarbonate resin contains only polycarbonate resin The impact strength is excellent and the content of the impact modifier is reduced, and the flame retardancy is excellent.

The copolycarbonate resin may include at least one repeating unit selected from the group consisting of an aromatic polycarbonate first repeating unit and a repeating unit represented by an aromatic polycarbonate second repeating unit having at least one siloxane bond have.

The aromatic polycarbonate-based first recurring unit may be formed by a reaction of a bisphenol-based monomer and a carbonate precursor, and may include, for example, a repeating unit represented by the following general formula (1).

R ¹ , R ² , R ³ and R ⁴ are each independently hydrogen, an alkyl group having 1 to 10 carbon atoms, an alkoxy group having 1 to 10 carbon atoms or halogen, and Z is, for example, unsubstituted or phenyl group A substituted alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 15 carbon atoms substituted with an unsubstituted or alkyl group having 1 to 10 carbon atoms, O, S, SO, SO ₂ or CO.

Examples of the bisphenol-based monomer include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis Bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) ketone, 1,1- ), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z; BPZ) Propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3-chlorophenyl) Propane, 1,1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane and?,? Dimethylsilox And an acid.

The carbonate precursor may be at least one selected from the group consisting of dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditolyl carbonate, bis (chlorophenyl) carbonate, m-cresyl carbonate, dinaphthyl carbonate, bis Diphenyl carbonate), carbonyl chloride (phosgene), triphosgene, diphosgene, carbonyl bromide, and bishaloformate.

The aromatic polycarbonate-based second repeating unit having at least one siloxane bond may be formed, for example, by reaction of at least one siloxane compound with the carbonate precursor, and may include a repeating unit represented by the following formula (2) .

Wherein X ² may be respectively the date alkylene having 1 to 10 carbon atoms independently with one example, the Y ¹ are each independently for example hydrogen, an alkoxy group having 1 to 6 carbon alkyl group, a halogen, a hydroxyl group, having 1 to 6 carbon atoms or An aryl group having 6 to 20 carbon atoms, and R < ⁶ > is, for example, independently hydrogen; An alkyl group having 1 to 15 carbon atoms which is unsubstituted or substituted with oxiranyl, oxiranyl, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; halogen; An alkoxy group having 1 to 10 carbon atoms; Allyl group; A haloalkyl group having 1 to 10 carbon atoms; Or an aryl group having 6 to 20 carbon atoms, and n2 may be an integer of 10 to 200.

The Y ¹ may be hydrogen, for example.

R ⁶ is, for example, each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxiranylmethoxy) , Ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl or naphthyl.

As another example, each of R ⁶ may independently be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and specific examples thereof may be methyl.

N2 may be an integer of 30 to 60, and may be an integer of 20 or more, 25 or more, 30 or more, 40 or less, or 35 or less, for example, 50 or more, or 55 or more and 70 or less , 75 or less, or 60 or less.

The repeating unit represented by the formula (2) may be represented by the following formula (3).

Wherein R ⁶ are each independently for example hydrogen; An alkyl group having 1 to 15 carbon atoms which is unsubstituted or substituted with oxiranyl, oxiranyl, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; halogen; An alkoxy group having 1 to 10 carbon atoms; Allyl group; A haloalkyl group having 1 to 10 carbon atoms; Or an aryl group having 6 to 20 carbon atoms, and n2 may be an integer of 10 to 200.

R ⁶ is, for example, each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxiranylmethoxy) , Ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl or naphthyl.

As another example, each of R ⁶ may independently be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and specific examples thereof may be methyl.

N2 may be an integer of 30 to 60, and may be an integer of 20 or more, 25 or more, 30 or more, 40 or less, or 35 or less, for example, 50 or more, or 55 or more and 70 or less , 75 or less, or 60 or less.

As another example, the copolycarbonate resin may further include at least one repeating unit selected from the group consisting of repeating units represented by the following formula (4).

X ¹ is, for example, independently an alkylene group having 1 to 10 carbon atoms, and R ⁵ is, for example, independently hydrogen; An alkyl group having 1 to 15 carbon atoms which is unsubstituted or substituted with oxiranyl, oxiranyl, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; halogen; An alkoxy group having 1 to 10 carbon atoms; Allyl group; A haloalkyl group having 1 to 10 carbon atoms; Or an aryl group having 6 to 20 carbon atoms, and n1 may be an integer of 10 to 200.

The X ¹ may be, for example, an alkylene group having 2 to 10 carbon atoms or 2 to 4 carbon atoms, and may be, for example, propane-1,3-diyl.

R ⁵ is, for example, independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxiranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy , Ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl or naphthyl.

As another example, each of R ⁵ may independently be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and specific examples thereof may be methyl.

N1 may be an integer of 30 to 60, and may be an integer of 20 or more, 25 or more, 30 or more, 40 or less, or 35 or less, for example, 50 or more, or 55 or more, and 70 or less , 75 or less, or 60 or less.

The repeating unit represented by the formula (4) may be represented by the following formula (5).

R ⁵ is, for example, independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxiranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy , Ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl or naphthyl.

As another example, each of R ⁵ may independently be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and specific examples thereof may be methyl.

N1 may be an integer of 30 to 60, and may be an integer of 20 or more, 25 or more, 30 or more, 40 or less, or 35 or less, for example, 50 or more, or 55 or more, and 70 or less , 75 or less, or 60 or less.

As another example, the copolycarbonate resin may include at least two kinds selected from the group consisting of repeating units represented by the general formula (2) and / or the general formula (3), in which case the normal temperature impact strength, It has excellent effect.

The two or more kinds of repeating units include two or more repeating units having different structures within the scope of the above formulas (2) to (5), or the same structure, but the number of repeating units of silicon oxide in the structure of formula (2) ) Are different from each other.

For example, the two or more repeating units may be selected from the group consisting of i) one repeating unit represented by the formula (2) and another repeating unit represented by the formula (2), or ii) one repeating unit represented by the formula (4) Quot; means one containing another repeating unit represented by the formula (4).

In the case where each of the copolycarbonate resins contains two repeating units of the repeating units represented by the above formulas (2) and (4), the weight ratio between the two repeating units is, for example, 1:99 to 99: : 97 to 97: 3, 5:95 to 95: 5, 10:90 to 90:10, 15:85 to 85:15, or 20:80 to 80:20, , Low-temperature impact strength and fluidity.

The repeating unit represented by the formula (2) or (4) may be derived from the siloxane compound represented by the following formula (6) and the siloxane compound represented by the following formula (7), respectively.

Wherein X ² may be respectively the date alkylene having 1 to 10 carbon atoms independently with one example, the Y ¹ are each independently for example hydrogen, an alkoxy group having 1 to 6 carbon alkyl group, a halogen, a hydroxyl group, having 1 to 6 carbon atoms or An aryl group having 6 to 20 carbon atoms, and R < ⁶ > is, for example, independently hydrogen; An alkyl group having 1 to 15 carbon atoms which is unsubstituted or substituted with oxiranyl, oxiranyl, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; halogen; An alkoxy group having 1 to 10 carbon atoms; Allyl group; A haloalkyl group having 1 to 10 carbon atoms; Or an aryl group having 6 to 20 carbon atoms, and n2 may be an integer of 10 to 200.

The Y ¹ may be hydrogen, for example.

R ⁶ is, for example, each independently hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxiranylmethoxy) , Ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl or naphthyl.

As another example, each of R ⁶ may independently be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and specific examples thereof may be methyl.

N2 may be an integer of 30 to 60, and may be an integer of 20 or more, 25 or more, 30 or more, 40 or less, or 35 or less, for example, 50 or more, or 55 or more and 70 or less , 75 or less, or 60 or less.

X ¹ is, for example, independently an alkylene group having 1 to 10 carbon atoms, and R ⁵ is, for example, independently hydrogen; An alkyl group having 1 to 15 carbon atoms which is unsubstituted or substituted with oxiranyl, oxiranyl, an alkoxy group having 1 to 10 carbon atoms or an aryl group having 6 to 20 carbon atoms; halogen; An alkoxy group having 1 to 10 carbon atoms; Allyl group; A haloalkyl group having 1 to 10 carbon atoms; Or an aryl group having 6 to 20 carbon atoms, and n1 may be an integer of 10 to 200.

The X ¹ may be, for example, an alkylene group having 2 to 10 carbon atoms or 2 to 4 carbon atoms, and may be, for example, propane-1,3-diyl.

R ⁵ is, for example, independently selected from the group consisting of hydrogen, methyl, ethyl, propyl, 3-phenylpropyl, 2-phenylpropyl, 3- (oxiranylmethoxy) propyl, fluoro, chloro, bromo, iodo, methoxy , Ethoxy, propoxy, allyl, 2,2,2-trifluoroethyl, 3,3,3-trifluoropropyl, phenyl or naphthyl.

As another example, each of R ⁵ may independently be an alkyl group having 1 to 10 carbon atoms, an alkyl group having 1 to 6 carbon atoms, or an alkyl group having 1 to 3 carbon atoms, and specific examples thereof may be methyl.

N1 may be an integer of 30 to 60, and may be an integer of 20 or more, 25 or more, 30 or more, 40 or less, or 35 or less, for example, 50 or more, or 55 or more, and 70 or less , 75 or less, or 60 or less.

The meaning derived from the siloxane compound means that the hydroxyl group of each siloxane compound reacts with the carbonate precursor to form the repeating unit represented by each of the formulas (2) and (4). The carbonate precursor which can be used for the formation of the repeating unit represented by the general formula (2) or (4) may be the same carbonate precursor as the carbonate precursor which can be used for the formation of the repeating unit represented by the general formula (1).

The compounds represented by formulas (6) and (7) can be prepared, for example, by the following reaction schemes 1 and 2, respectively.

[Reaction Scheme 1]

X ^2a may be, for example, an alkenyl group having 2 to 10 carbon atoms.

[Reaction Scheme 2]

X ^1a may be, for example, an alkenyl group having 2 to 10 carbon atoms.

The reaction of the above Schemes 1 and 2 can be carried out, for example, under a metal catalyst. The metal catalyst may be, for example, a Pt catalyst such as an Ashby catalyst, a Karstedt catalyst, a Lamoreaux catalyst, a Speier catalyst, PtCl ₂ (COD), PtCl ₂ (Benzonitrile) ₂ and H ₂ PtBr ₆ . As another example, the metal catalyst may be used in an amount of 0.001 parts by weight or more, 0.005 parts by weight or more, or 0.01 parts by weight or more, and 1 part by weight or less, 0.1 parts by weight or less, Or less, or 0.05 parts by weight or less.

In the reaction, the reaction temperature may be, for example, 80 to 100 ° C, and the reaction time may be 1 to 5 hours.

The compounds represented by C2 and C4 in the above Schemes 1 and 2 can be prepared by reacting an organosiloxane and an organocyclosiloxane respectively under an acid catalyst, and by controlling the content of the reactant, n1 and n2 can be controlled have. At this time, the reaction temperature may be, for example, 50 to 70 ° C, and the reaction time may be 1 to 6 hours, for example.

The organosiloxane may be at least one member selected from the group consisting of tetramethyldisiloxane, tetraphenyldisiloxane, hexamethyldisiloxane, and hexaphenyldisiloxane.

The organosiloxane may be, for example, organosilicate tetrasiloxane. Specific examples thereof include at least one selected from the group consisting of octamethylcyclotetrasiloxane and octaphenylcyclotetrasiloxane.

The organosiloxane may be used in an amount of 0.1 part by weight or more, or 2 parts by weight or more, and 10 parts by weight or less, or 8 parts by weight or less, based on 100 parts by weight of the organosiloxane.

The acid catalyst may be at least one selected from the group consisting of H ₂ SO ₄ , HClO ₄ , AlCl ₃ , SbCl ₅ , SnCl ₄ and acidic white clay. Not less than 0.5 parts by weight, or not less than 1 part by weight, not more than 10 parts by weight, not more than 5 parts by weight, or not more than 3 parts by weight.

By controlling the content of the repeating units represented by the above formulas (2) and (4), the physical properties of the copolycarbonate resin can be improved. Here, the weight ratio of the repeating units may correspond to the weight ratio of the siloxane compound used in the copolycarbonate polymerization, for example, the siloxane compound represented by the general formulas (6) and (7).

The molar ratio of the aromatic polycarbonate-based first repeating unit of the copolycarbonate resin and the aromatic polycarbonate-based second repeating unit having at least one siloxane bond is, for example, from 1: 0.0001 to 1: 0.01, 1: 0.0005 to 1: 0.008 , Or from 1: 0.001 to 1: 0.006, and the weight ratio can be, for example, 1: 0.001 to 1: 1, 1: 0.005 to 1: 0.1, or 1: 0.01 to 1: 0.03, Impact strength, low temperature impact strength, chemical resistance and fluidity.

As another example, 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, and within this range, impact resistance at room temperature, low temperature impact strength, And excellent fluidity, and excellent flowability and moldability.

The copolycarbonate resin may be prepared using, for example, the bisphenol-based monomer, the carbonate precursor, and at least one siloxane compound.

In the polymerization of the above compounds, the at least one siloxane compound may be present in an amount of at least 0.1 wt%, at least 0.5 wt%, at least 1 wt%, or at least 1.5 wt%, based on 100 wt% of the total of the bisphenol-based monomer, carbonate precursor and at least one siloxane compound , Not more than 20 wt%, not more than 10 wt%, not more than 7 wt%, not more than 5 wt%, not more than 4 wt%, not more than 3 wt%, or not more than 2 wt% of the bisphenol- At least 40 wt%, at least 50 wt%, or at least 55 wt%, at least 80 wt%, at least 70 wt%, or at least 65 wt%, based on 100 wt% of the total sum of the bisphenol-based monomer, carbonate precursor and at least one siloxane compound. And the carbonate precursor may be used in an amount of 10 wt% or more and 20 wt% or less based on 100 wt% of the total amount of the bisphenol-based monomer, the carbonate precursor and the at least one siloxane compound. Or 30% by weight, and 60% by weight or less, 50% by weight or less, or 40% by weight or less.

As the polymerization method, for example, an interfacial polymerization method can be used. In this case, the polymerization reaction can be performed at normal pressure and low temperature, and the molecular weight can be easily controlled. The interfacial polymerization can be carried out, for example, in the presence of an acid binder and an organic solvent. In addition, the interfacial polymerization may include, for example, pre-polymerization followed by introduction of a coupling agent and then polymerizing again, in which case a high molecular weight copolycarbonate can be obtained.

The materials used in the interfacial polymerization are not particularly limited as long as they can be used for polymerization of polycarbonate, and the amount thereof can be adjusted as needed.

As the acid binding agent, for example, an alkali metal hydroxide such as sodium hydroxide, potassium hydroxide or the like 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. For example, halogenated hydrocarbons such as methylene chloride and chlorobenzene can be used.

The interfacial polymerization may be carried out in the same manner as in the reaction for promoting the reaction, such as a tertiary amine compound such as triethylamine, tetra-n-butylammonium bromide or tetra-n-butylphosphonium bromide, a quaternary ammonium compound or a quaternary phosphonium compound Additional accelerators may be used.

The reaction temperature of the interfacial polymerization may be, for example, 0 to 40 ° C, and the reaction time may be, for example, 10 minutes to 5 hours. In addition, during the interfacial polymerization reaction, the pH may be 9 or more or 11 or more, for example.

In addition, the interfacial polymerization can be carried out further including a molecular weight regulator, and the molecular weight regulator can be added before the initiation of polymerization, during the initiation of polymerization or after initiation of polymerization. Examples of the above-mentioned mono-alkylphenol include p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, Octadecylphenol, eicosylphenol, docosylphenol and triacontylphenol, preferably p-tert-butylphenol. In this case, the effect of controlling the molecular weight is great. The molecular weight modifier is included in an amount of 0.01 part by weight or more, 0,1 parts by weight or more, 1 part by weight or more, 10 parts by weight or less, 6 parts by weight or 5 parts by weight or less based on 100 parts by weight of the aromatic diol compound And the desired molecular weight can be obtained within this range.

For example, the copolycarbonate resin may have a weight average molecular weight of 1,000 to 100,000 g / mol, or 5,000 to 50,000 g / mol, and a proper ductility and yellow index (YI) There is an effect that can be done. As another example, the copolycarbonate resin may have a weight average molecular weight of at least 1,000 g / mol, at least 5,000 g / mol, at least 10,000 g / mol, at least 21,000 g / mol, at least 22,000 g / mol, at least 23,000 g / more than 25,000 g / mol, not less than 26,000 g / mol, not less than 27,000 g / mol, or not less than 28,000 g / mol, not more than 100,000 g / mol, not more than 50,000 g / mol, not more than 34,000 g / g / mol, or less than or equal to 32,000 g / mol.

For example, the copolycarbonate resin may have a melt index (300 ° C, 1.2 kg) of 8 to 20 g / 10 min, 8 to 18 g / 10 min, or 10 to 15 g / 10 min, The processability and the impact strength are excellent. The melt index refers to the melt index measured under the standard measurement ASTM D1238 (300 DEG C, 1.2 kg).

As another example, the copolycarbonate resin may be a polycondensation polymer of a polycarbonate resin containing a repeating unit represented by the formula (1) and a polyorganosiloxane.

The polyorganosiloxane is not particularly limited as long as it is capable of condensation polymerization with polycarbonate, and may be, for example, a polydialkylsiloxane. The polydialkylsiloxane may be, for example, a polydialkylsiloxane containing an alkyl group having 1 to 10 carbon atoms or 1 to 5 carbon atoms, and may be polydimethylsiloxane.

The copolycarbonate resin may be contained in an amount of 10 to 60% by weight, 15 to 55% by weight, or 20 to 50% by weight based on the polycarbonate resin composition. Within this range, the impact strength and flame retardancy are excellent have.

The impact modifier may be a core-shell structure impact modifier compatible with polycarbonate resin and exhibiting an impact reinforcing effect. For example, one kind selected from the group consisting of diene rubber, acrylate rubber and silicone rubber Or more of the rubber core; And a core-shell structure impact modifier in which a shell is formed by graft-polymerizing a vinyl-based unsaturated monomer wrapped around the core. In this case, the impact reinforcing effect, such as impact strength, is excellent even with a low content.

The diene rubber may be, for example, a diene rubber having 4 to 6 carbon atoms. Examples of the acrylate rubber include methyl (meth) acrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate monomer selected from the group consisting of n-butyl (meth) acrylate, 2-ethylhexyl (meth) acrylate and hexyl (meth) acrylate, For example, the silicone rubber may be one prepared from a cyclosiloxane. Specific examples of the silicone rubber include hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcycloheptasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetra Methyl tetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane. ≪ RTI ID = 0.0 > 1 < / RTI > It may be one prepared by including at least.

As the vinyl-based unsaturated monomer to be graft-polymerized on the rubber, for example, one or more kinds of aromatic vinyl monomers or monomers copolymerizable with the aromatic vinyl monomers may be used.

The aromatic vinyl monomer may be at least one selected from the group consisting of styrene,? -Methylstyrene,? -Methylstyrene, p-methylstyrene, p-t-butylstyrene and ethylstyrene.

Examples of the monomer copolymerizable with the aromatic vinyl monomer include a vinyl cyan compound, a (meth) acrylate, an alkyl (meth) acrylate having 1 to 12 carbon atoms, an alkyl or a phenyl nucleus substituted maleimide having 1 to 12 carbon atoms It may be more than one kind.

The impact modifier may be included in an amount of 0.1 to less than 5 wt%, 0.1 to 3 wt%, or 1 to 2 wt% based on the polycarbonate resin composition, and the impact modifier .

The glass fiber has a difference in compatibility with the base resin depending on the organic material coated on the surface of the glass fiber and has a high compatibility so that the base resin and the glass fiber are bonded to each other in the resin composition Refers to non-synthesis in which the base resin and glass fiber are not bonded to each other in the resin composition due to low compatibility.

That is, the non-bonding type glass fiber is different from the bonding type glass fiber in which a bonding organic material such as a coupling agent exists on the glass fiber surface, and the glass fiber surface is bonded to the polycarbonate resin Quot; means a glass fiber coated with an organic material that does not form a polycarbonate resin composition and forms a gap between the polycarbonate resin and the glass fiber in the polycarbonate resin composition.

The non-crystalline glass fiber may be, for example, chopped glass fiber whose surface is coated with polyolefin. The polyolefin coated on the surface of the glass fiber may be, for example, ethylene, propylene, 1-butene, Pentene, and isobutylene. In this case, the polycarbonate resin and the glass fiber do not bond to each other in the resin composition, so that pores are formed, so that the impact strength And low deformation characteristics.

The non-crystalline glass fiber may include, for example, 1 to less than 10% by weight, 1 to 8% by weight, or 1 to 5% by weight of the polycarbonate resin composition, and within this range, This has an excellent effect.

The phosphorus flame retardant means a flame retardant containing common phosphorus (P), and is not particularly limited as long as it can be used in a polycarbonate resin composition. For example, it may be in the form of a liquid, .

The phosphorus flame retardant may be, for example, bisphenol A bis (dialkylphosphate), bisphenol A bis (diarylphosphate) or a mixture thereof. The alkyl group may be, for example, an alkyl group having 1 to 20 carbon atoms or a carbon number of 1 to 15 And the aryl group may be, for example, an aryl group having 6 to 30 carbon atoms or 6 to 20 carbon atoms.

The phosphorus flame retardant may be contained in an amount of, for example, 1 to 20% by weight, 3 to 15% by weight, or 6 to 10% by weight based on the polycarbonate resin composition, and excellent balance of flame retardancy and physical properties within this range.

The polycarbonate resin composition may include 0.1 to 5% by weight, 0.1 to 3% by weight, or 0.1 to 1.5% by weight of polytetrafluoroethylene as an anti-dripping agent, The balance between flame retardancy and physical properties is excellent.

The polycarbonate resin composition may contain one or more selected from the group consisting of stabilizers, pigments, dyes, ultraviolet absorbers, antioxidants, colorants, release agents, lubricants, antistatic agents and plasticizers depending on the purpose, It may contain more than two kinds of additives.

For example, the polycarbonate resin composition preferably has a flame retardancy rating of 1.0 T and a V-1 rating or higher as measured by a vertical combustion test according to UL-94, and the total combustion time (裡 t1 + 裡 t2) 65 seconds or less, or 60 seconds or less.

The molded article according to the present invention is characterized by including the polycarbonate resin composition.

The molded article may be, for example, an injection molded article, and may be a housing of a tablet PC as a specific example.

It is to be understood that both the foregoing general description and the following detailed description of the present invention are exemplary and explanatory only and are not to be taken by way of illustration in the practice of the practice of this invention. And it is natural that such variations and modifications are included in the appended claims.

[Example]

Example  1 to 5 and Comparative Example  1 to 5

(% By weight) shown in the following Table 1 were mixed in a super mixer (manufactured by Mitsubishi Rayon Co., Ltd.) under the conditions shown in Table 1 below, using a polycarbonate resin (PC), a copolycarbonate resin (Si-PC), an impact modifier, super mixer. The mixture was melted and kneaded at 260 to 290 ° C using a twin-screw extruder, and extruded to prepare a resin composition in the form of a pellet. The prepared pelletized resin composition was dried at 80 ° C. for 8 hours or more and then injection molded to prepare specimens and thin film injection specimens. The specimens were allowed to stand at room temperature (20 to 26 ° C.) for 24 hours or longer, and their physical properties were measured.

The respective components in Table 1 are as follows.

* PC: homopolycarbonate resin having a melt index of 10 g / 10 min (300 DEG C, 1.2 kg)

* Si-PC: Copolycarbonate resin (trade name TRIREX® ST6-3022PJ manufactured by Samyang Corp.) having a melt index of 12.5 g / 10 min (300 ° C, 1.2 kg)

* Impact reinforcement: a core-shell silicone-acrylic impact modifier (product name S2100, manufactured by Mitsubishi Rayon)

* Non-crystallized glass fiber: Glass fiber coated with polyethylene (product name 415A, manufactured by Owens Corning)

* Combined Glass Fiber: Glass fiber coated with polyester (product name: 183F, manufactured by Owens Corning)

* Phosphorus flame retardant: bisphenol A bis (diphenylphosphate) (product name FP600, manufactured by Asahi Denka Co., Ltd.)

* Antifoaming agent: polytetrafluoroethylene (trade name: Xflon-G, manufactured by Porsera)

[Test Example]

The physical properties of the polycarbonate resin composition specimens obtained in Examples 1 to 5 and Comparative Examples 1 to 5 were measured by the following methods, and the results are shown in Table 1 below.

How to measure

Melt Index (g / 10 min): Measured according to standard measurement ASTM D1238 (300 ° C, condition of 1.2 kg).

* Impact strength (Notched Izod, kgf · cm / cm): Measured according to standard measurement ASTM D256 using 1/8 "specimen.

* Flame Retardancy (UL-94) and Total Burning Time (sec): Measured according to the UL-94 vertical burning evaluation method using a 1.0 mm thick specimen. And V-2. The sum of the first and second afterflame times (t1, t2) for the five test specimens was expressed as the total combustion time in seconds (V-0 rating is 50 sec or less, V-1 rating is 250 sec or less Should be).

* Low strain characteristics: The degree of warpage of the thin film injection specimen was observed using a 3D microscope, and the height displacement at the maximum strain point was compared to evaluate the strain at five stages (grade 1 (poor) to grade 5 (excellent)) Respectively.

* Surface properties: The degree of gloss of the relative surfaces was visually compared and evaluated in five steps (grade 1 (poor) to grade 5 (excellent)) using a 3D microscope.

division Example Comparative Example One 2 3 4 5 One 2 3 4 5 PC 66.3 36.3 62.3 67.3 68.3 86.3 66.3 61.3 83.3 71.3 Si-PC 20 50 20 20 20 - 20 20 - 20 Impact modifier 2 2 2 One 2 2 2 2 5 2 Non-synthesis
Glass fiber 5 5 5 5 3 5 - 10 5 - Cohesiveness
Glass fiber - - - - - 5 - - - Phosphorus flame retardant 6 6 10 6 6 6 6 6 6 6 Anti-drop agent 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 0.7 * Properties Melt Index 10 7 13 11 11 12 10 10 12 12 Impact strength 25 35 18 18 31 20 19 17 23 65 Flammability V-1 V-1 V-0 V-1 V-1 V-1 V-1 V-1 V-2 V-1 all
Burning time
(? T1 +? T2) 63 54 27 55 66 102 71 60 Drip 75 Low strain characteristics 4 4 4 4 3 4 4 5 4 One Surface property 4 4 4 4 4 4 3 One 4 5

As shown in Table 1, in Examples 1 to 5 prepared according to the present invention, the flame retardancy of V-0 or V-1 was excellent while the melt index and impact strength were excellent, the total combustion time was short, There was no warpage even when injected, so the low deformation and surface characteristics were excellent.

On the other hand, Comparative Examples 1 and 4, which did not contain Si-PC, showed poor flame retardancy and total burning time, and Comparative Example 2 in which bonding fiberglass was incorporated instead of non-crystalline glass fiber had decreased impact strength and surface characteristics. In Comparative Example 3 in which non-crystallized glass fibers were contained in an excessive amount, the impact strength was lowered, particularly, the surface characteristics were remarkably lowered, and in Comparative Example 5 in which the non-crystallized glass fiber was not contained, the low strain characteristics were seriously degraded.

From this, the present inventors confirmed that it is possible to realize a polycarbonate resin composition having improved mechanical properties and flame retardancy, while being excellent in low strain characteristics, by containing a copolycarbonate resin having a specific melt index and a low amount of non- there was.

Claims (16)

10 to 60% by weight of a polycarbonate resin having a polycarbonate resin content of 30 to 80% by weight and a melt index (300 DEG C, 1.2 kg) of 8 to 20 g / 10 min, an impact modifier of 0.1 to less than 5% 1 to less than 10% by weight of non-bonding type glass fibers and 1 to 20% by weight of phosphorus flame retardant. The method according to claim 1,
Wherein the polycarbonate resin has a melt index (300 DEG C, 1.2 kg) of 8 to 20 g / 10 min. The method according to claim 1,
Wherein the polycarbonate resin composition is a polycarbonate resin composition wherein polycarbonate and a polyorganosiloxane are condensation-polymerized. The method of claim 3,
Wherein the polyorganosiloxane is a polydialkylsiloxane. The method of claim 3,
Wherein the polyorganosiloxane is contained in an amount of 1 to 15% by weight with respect to the copolycarbonate resin. The method according to claim 1,
Wherein the impact modifier is a core-shell structure impact modifier comprising a silicone-based rubber core and a shell surrounding the core and containing an acrylic compound. The method according to claim 6,
Wherein the silicone-based rubber core is selected from the group consisting of hexamethylcyclotrisiloxane, octamethylcyclotetrasiloxane, decamethylcycloheptasiloxane, dodecamethylcyclohexasiloxane, trimethyltriphenylcyclotrisiloxane, tetramethyltetraphenylcyclotetrasiloxane, and octaphenylcyclotetrasiloxane Wherein the polycarbonate resin composition comprises at least one member selected from the group consisting of: The method according to claim 6,
Wherein the acrylic compound is a (meth) acrylate, a (meth) acrylic acid alkyl ester compound, or a mixture thereof. The method according to claim 1,
Wherein the non-crystalline glass fiber is a chopped glass fiber whose surface is coated with polyolefin. 10. The method of claim 9,
Wherein the polyolefin is at least one selected from the group consisting of ethylene, propylene, 1-butene, 4-methyl-1-pentene and isobutylene. The method according to claim 1,
Wherein the phosphorus flame retardant is an aromatic phosphoric acid ester compound. 12. The method of claim 11,
Wherein the phosphorus flame retardant is bisphenol A bis (dialkyl phosphate), bisphenol A bis (diaryl phosphate) or a mixture thereof. The method according to claim 1,
Wherein the polycarbonate resin composition comprises 0.1 to 5% by weight of polytetrafluoroethylene. The method according to claim 1,
Wherein the polycarbonate resin composition has a flame retardancy grade measured by a vertical burning test according to UL-94 of not less than V-1 grade at a thickness of 1.0 T and a total burning time of not more than 70 seconds Composition. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 14. 16. The method of claim 15,
Wherein the molded article is a housing of a tablet PC.

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