KR102006252B1 - Polycarbonate resin composition with excellent impact resistance and heat resistance, method for preparing the same and article comprising the same - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition having excellent impact resistance and heat resistance, and it is an object of the present invention to provide a polycarbonate resin composition excellent in impact resistance and excellent balance of physical properties such as fluidity while maintaining excellent heat resistance at a level equal to or higher than that of a conventional high heat resistant polycarbonate resin An excellent polycarbonate resin composition, a method for producing the same, and a molded article comprising the same.

Description

TECHNICAL FIELD [0001] The present invention relates to a polycarbonate resin composition having excellent impact resistance and heat resistance, a method for producing the polycarbonate resin composition, and a molded article including the polycarbonate resin composition,

The present invention relates to a polycarbonate resin composition having excellent impact resistance and heat resistance, and it is an object of the present invention to provide a polycarbonate resin composition excellent in impact resistance and excellent balance of physical properties such as fluidity while maintaining excellent heat resistance at a level equal to or higher than that of a conventional high heat resistant polycarbonate resin An excellent polycarbonate resin composition, a method for producing the same, and a molded article comprising the same.

Polycarbonate resins are widely used as electrical parts, machine parts and industrial resins because of their excellent heat resistance, mechanical properties (particularly impact strength) and transparency. Particularly, when a polycarbonate resin is used for a TV housing, a computer monitor housing, a copying machine, a printer, a notebook battery, and a case material for a lithium battery, which are highly heat-dissipated in the electric and electronic fields, mechanical properties as well as excellent heat resistance are required.

However, a general polycarbonate resin is selectively infiltrated into a specific solvent, has no resistance, and has good creep resistance against a static load. However, when the temperature and various environmental conditions are mated, the polycarbonate resin is relatively easily broken and the resistance against dynamic load is complicated .

Accordingly, researches for increasing the heat resistance of polycarbonate resins have been continuously conducted, and as a result, high heat-resistant polycarbonate resins have been developed (for example, U.S. Patent No. 5,070,177, U.S. Patent No. 4,918,149). Generally, such a high heat resistant polycarbonate has modified the bisphenol A to introduce a stereosubstituted substituent at the ortho position to increase the hydrolysis property and increase the heat distortion temperature.

However, such a conventional high heat-resistant polycarbonate resin has a problem that impact resistance is remarkably lower than that of a general polycarbonate resin.

An object of the present invention is to provide a polycarbonate resin composition excellent in impact resistance and excellent balance of physical properties such as fluidity while maintaining excellent heat resistance at a level equal to or higher than that of conventional high heat resistant polycarbonate resin, And to provide a molded article containing the same.

In order to solve the above technical problems, the present invention provides (1) a polycarbonate block copolymer; And (2) an antioxidant, wherein the polycarbonate block copolymer comprises (A) a polyester block having a structure represented by the following formula (1) as a repeating unit; And (B) a polycarbonate block, wherein the amount of the polyester block in the polycarbonate block copolymer is in the range of 1 wt% based on 100 wt% of the total weight of the monomer compound constituting the polycarbonate block copolymer By weight to less than 55% by weight, and the antioxidant is contained in an amount of more than 0.005 parts by weight to less than 4 parts by weight based on 100 parts by weight of the polycarbonate block copolymer.

[Chemical Formula 1]

In Formula 1,

R ₁ is independently a hydrogen atom; An alkyl group having 1 to 4 carbon atoms; A cycloalkyl group having 3 to 6 carbon atoms; A cycloalkylalkyl group having 4 to 10 carbon atoms; Or an aryl group having 6 to 10 carbon atoms,

X independently represents an oxygen atom or NR ₂ , wherein R ₂ is independently a hydrogen atom; An alkyl group having 1 to 4 carbon atoms; A cycloalkyl group having 3 to 10 carbon atoms which is substituted or unsubstituted with a substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms; Or an aryl group having 6 to 10 carbon atoms, which is substituted or unsubstituted with a substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms,

R ₃ independently represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, a cycloalkylene-alkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms,

m represents an integer of 2 to 50;

According to one embodiment of the present invention, the polyester block having the structure represented by the general formula (1) is obtained from ester oligomers prepared by the condensation reaction between the compound represented by the general formula (1-1) and the compound represented by the general formula It can be derived from:

[Formula 1-1]

[Formula 1-2]

In the above formulas 1-1 and 1-2,

R ₁ , X and R ₃ are as defined in the above formula (1)

Y independently represents a hydroxy group or a halogen atom.

According to another aspect of the present invention, there is provided a process for preparing a polyester block oligomer, comprising the steps of: (1) subjecting a compound represented by Formula 1-1 to a condensation reaction to obtain a polyester block oligomer; (2) copolymerizing the polyester block oligomer obtained in the step (1) with a polycarbonate oligomer to obtain a polycarbonate block copolymer; And (3) mixing the polycarbonate block copolymer obtained in the step (2) with an antioxidant.

According to another aspect of the present invention, there is provided a molded article comprising the polycarbonate resin composition of the present invention.

The polycarbonate resin composition according to the present invention is superior in impact resistance and excellent in heat resistance, and has excellent balance of physical properties such as transparency and fluidity, and is useful for office equipment, housings for electric and electronic products, Lt; / RTI >

Hereinafter, the present invention will be described in detail.

The polycarbonate resin composition of the present invention comprises (1) a polycarbonate block copolymer and (2) an antioxidant, and may further include a fluidizing agent.

(1) Polycarbonate block copolymer

The polycarbonate block copolymer contained in the polycarbonate resin composition of the present invention contains, as repeating units, (A) a polyester block and (B) a polycarbonate block.

(A) a polyester block

The polyester block contained as a repeating unit in the polycarbonate block copolymer contained in the polycarbonate resin composition of the present invention has a structure represented by the following formula (1)

[Chemical Formula 1]

In Formula 1,

R ₁ is independently a hydrogen atom; An alkyl group having 1 to 4 carbon atoms; A cycloalkyl group having 3 to 6 carbon atoms; A cycloalkylalkyl group having 4 to 10 carbon atoms; Or an aryl group having 6 to 10 carbon atoms, more specifically a hydrogen atom; An alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cycloalkylalkyl group having 6 to 9 carbon atoms; Or an aryl group having 6 carbon atoms,

X independently represents an oxygen atom or NR ₂ , wherein R ₂ is independently a hydrogen atom; An alkyl group having 1 to 4 carbon atoms (which may be, for example, methyl, ethyl, propyl or butyl); A cycloalkyl group having 3 to 10 carbon atoms which is unsubstituted or substituted with a substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms (e.g., cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane , Chloro cyclohexane, methylcyclopentane, 1-bromo-2-methyl-cyclopentane or 1-chloro-1-ethyl-cyclohexane; Or an aryl group having 6 to 10 carbon atoms (for example, phenyl, benzyl, tolyl or chlorophenyl) which is substituted or unsubstituted with a substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms,

R ₃ is independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, a cycloalkylene-alkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms, An alkylene group having 1 to 6 carbon atoms, a cycloalkylene group having 5 to 6 carbon atoms, a cycloalkylene-alkylene group having 6 to 9 carbon atoms, or an arylene group having 6 carbon atoms,

m represents an integer of 2 to 50, preferably an integer of 3 to 30, more preferably an integer of 5 to 20.

According to one embodiment of the present invention, the polyester block having the structure of Formula 1 may be prepared from a polyester block oligomer prepared by the condensation reaction between the compound represented by Formula 1-1 and the compound represented by Formula 1-2 below It may be derived.

[Formula 1-1]

[Formula 1-2]

In the above formulas 1-1 and 1-2,

R ₁ , X and R ₃ are as defined in the above formula (1)

Y independently represents a hydroxy group or a halogen atom (e.g. Cl, F or Br).

The reaction molar ratio of the compound of the formula 1-1 to the compound of the formula 1-2 may be, for example, 1: 0.5 to 1: 2, more specifically 1: 0.6 to 1: 1.5, but is not limited thereto.

The polyester block having the structure of Formula 1 may have a number average molecular weight (Mn) of 500 to 30,000 g / mol as measured by gel permeation chromatography (GPC), but is not limited thereto.

(B) Polycarbonate block

The polycarbonate block contained as a repeating unit in the polycarbonate block copolymer contained in the polycarbonate resin composition of the present invention can be obtained by reacting a polycarbonate oligomer with a polyester block oligomer having a structure represented by the above formula Is introduced into the copolymer.

There is no particular limitation on the method for producing the polycarbonate oligomer. For example, it may be produced by a phosgene method in which a divalent phenol compound and phosgene are mixed together, but the present invention is not limited thereto.

The divalent phenol compound used in the preparation of the polycarbonate oligomer may be, for example, a compound represented by the following formula (2).

(2)

In Formula 2,

L is a straight, branched or cyclic alkylene group having no functional group; Or a linear, branched or cyclic alkylene group containing at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, phenyl, isobutylphenyl or naphthyl, A linear alkylene group having 3 to 10 carbon atoms, a branched alkylene group having 3 to 10 carbon atoms, or a cyclic alkylene group having 3 to 10 carbon atoms;

R ₄ and R ₅ are each independently a halogen atom; Or a straight, branched or cyclic alkyl group;

m and n are each independently an integer of 0 to 4, preferably 0 or 1;

The compound of formula (2) is, for example, bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) phenylmethane, bis Ethyl-1,1-bis (4-hydroxyphenyl) propane, 1-phenyl-1, Bis (4-hydroxyphenyl) ethane, 1-naphthyl-1,1-bis (4-hydroxyphenyl) (4-hydroxyphenyl) decane, 2-methyl-1,1-bis (4-hydroxyphenyl) propane, 2,2- Bis (4-hydroxyphenyl) butane, 2,2-bis (4-hydroxyphenyl) pentane, 2,2- Bis (3-fluoro-4-hydroxyphenyl) propane, 4-methyl-2,2-bis (4-hydroxyphenyl) Pentane, 4,4-bis (4-hydroxyphenyl) heptane, diphenyl-bis (4-hydroxyphenyl) Resorcinol, Hydroquinone, 4,4'-dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy- Dihydroxy-3,3'-dichlorodiphenyl ether, bis (3,5-dimethyl-4-hydroxyphenyl) ether, bis (3,5- Hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p, p Dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxyphenyl, 1,1-bis (4-hydroxyphenyl) cyclohexane, 1,1- (3,5-dimethyl-4-hydroxyphenyl) cyclohexane, 1,1-bis (3,5-dichloro-4-hydroxyphenyl) cyclohexane, (4-hydroxyphenyl) decane, 1,1-bis (4-hydroxyphenyl) cyclododecane, 4-bis (4-hydroxyphenyl) propane, 1,4-bis (4-hydroxyphenyl) butane, 1,4-bis (4-hydroxyphenyl) isobutane, 2,2- (3,5-dimethyl-4-hydroxyphenyl) methane, bis (3,5-dichloro-4-hydroxyphenyl) methane, 2,2- 4-hydroxyphenyl) propane, 2,2-bis (3,5-dibromo-4-hydroxyphenyl) propane, Bis (4-hydroxyphenyl) sulfone], bis (3,5-dimethyl-4-hydroxyphenyl) Hydroxyphenyl) sulfone, bis (3-chloro-4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfone, bis Bis (3,5-dibromo-4-hydroxyphenyl) sulfoxide, 4,4'-dihydroxybenzophenone, 3,3 ', 5,5'-tetramethyl-4,4'-dihydroxybenzo Phenol, 4,4'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, and 2,6-dihydroxynaphthalene. Representative examples include 2,2-bis (4-hydroxyphenyl) propane (bisphenol A). Other dihydric phenols can be found in U.S. Patents US 2,999,835, US 3,028,365, US 3,153,008, US 3,334,154, and US 4,131,575, and the dihydric phenols may be used singly or in combination with one another Can be used in combination.

According to one embodiment of the present invention, the divalent phenol compound (for example, bisphenol A) is added to an aqueous alkaline solution, and the resultant mixture is mixed with an organic solvent (for example, dichloromethane) To prepare an oligomeric polycarbonate wherein the molar ratio of the phosgene to the divalent phenol compound can be maintained in the range of about 1: 1 to 1.5: 1, preferably about 1: 1 to 1.2: 1, The molecular weight of the oligomeric polycarbonate produced may be from 1,000 to 2,000.

According to another embodiment of the present invention, the divalent phenol compound (for example, bisphenol A) is added to an alkaline aqueous solution, and the resultant mixture is mixed with an organic solvent (for example, dichloromethane) (Wherein the molar ratio of phosgene: divalent phenol compound may be maintained in the range of about 1: 1 to 1.5: 1, preferably about 1: 1 to 1.2: 1), wherein the molecular weight modifier and catalyst The polycarbonate oligomer can be formed.

The polycarbonate oligomerization reaction may generally be carried out at a temperature in the range of about 15 < 0 > C to 60 < 0 > C. For adjusting the pH of the reaction mixture, alkali metal hydroxides may be introduced into the reaction mixture. The alkali metal hydroxide may be, for example, sodium hydroxide.

As the molecular weight modifier, a monofunctional compound similar to the monomer used in the production of the polycarbonate may be used. The monofunctional material may be selected from, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumyl phenol, p- Phenol-based derivatives such as isononylphenol, or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) may be used.

As the catalyst, a polymerization catalyst and / or a phase transfer catalyst may be used. The polymerization catalyst may be, for example, triethylamine (TEA), and the phase transfer catalyst may be a compound of the following formula (3).

(3)

(R < ₆ & gt ^; ) ₄ Q ⁺ Z ^-

In the above formula (3), R ₆ independently represents an alkyl group having 1 to 10 carbon atoms,

Q may represent nitrogen or phosphorus,

Z may represent a halogen atom or -OR ₇ , wherein R ₇ may represent a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

The phase transfer catalysts include, for _{example, [CH 3 (CH 2)} 3] 4 NZ, [CH 3 (CH 2) 3] 4 PZ, [CH 3 (CH 2) 5] 4 NZ, [CH 3 (CH 2 ) ₆ ] ₄ NZ, [CH ₃ (CH ₂ ) ₄ ] ₄ NZ, CH ₃ [CH ₃ (CH ₂ ) ₃ ] ₃ NZ and CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NZ. Where Z may be Cl, Br or -OR < ₇ >. Here, R ₇ may be a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

The content of the phase transfer catalyst is preferably about 0.1 to 10% by weight of the reaction mixture. When the content of the phase-transfer catalyst is less than 0.1% by weight, the reactivity may be deteriorated. When the amount of the phase-transfer catalyst is more than 10% by weight, precipitation may occur in the precipitate, and the transparency of the resultant copolymer may be deteriorated.

After the polycarbonate oligomer is formed as described above, the organic phase dispersed in methylene chloride is washed with alkali and separated. Subsequently, the organic phase is washed with a 0.1N hydrochloric acid solution and then washed repeatedly with distilled water 2-3 times.

When the cleaning is completed, the concentration of the organic phase dispersed in methylene chloride is adjusted to a constant level, and granulation is performed using a predetermined amount of secondary distilled water at 40 to 80 ° C. If the temperature of the second distilled water is less than 40 캜, the assembling time may be excessively long due to a slower granulation speed, and it may be difficult to obtain a polycarbonate having a certain particle size if the temperature exceeds 80 캜. When the assembly is completed, it is preferable to dry firstly at 100 ° C to 110 ° C for 5 hours to 10 hours and secondly at 110 ° C to 120 ° C for 5 hours to 10 hours.

The viscosity average molecular weight of the prepared branched polycarbonate oligomer may preferably be 1,000 to 30,000, more preferably 1,000 to 15,000. If the viscosity average molecular weight is less than 1,000, the mechanical properties may be significantly deteriorated. If the average molecular weight is more than 30,000, the copolymerization reactivity may be deteriorated.

The polycarbonate block copolymer contained in the polycarbonate resin composition of the present invention can be obtained by a copolymerization reaction of the polyester block having the structure of the above formula (1) with the polycarbonate oligomer described above.

The polycarbonate block includes both a linear polycarbonate block, a branched polycarbonate block, and combinations thereof. According to one embodiment of the present invention, a linear polycarbonate block is predominant, but a branched polycarbonate block is also possible, and both may be used in combination.

The amount of the polyester block in the polycarbonate block copolymer is more than 1 wt% to less than 55 wt% (for example, 1.1 wt% or less), based on 100 wt% of the total weight of the monomer compounds constituting the polycarbonate block copolymer % To 54.9% by weight). If the relative content of the polyester block having the structure of the formula (1) is less than the lower limit of the above range, the heat resistance may be lowered. On the other hand, if the relative amount is less than the above range, the properties such as transparency, .

More specifically, the amount of the polyester block in the polycarbonate block copolymer may be at least 2 wt%, at least 3 wt%, or at least 3 wt%, based on the total weight of the monomer compounds constituting the polycarbonate block copolymer, And may be at least 4 wt%, at least 5 wt%, or at least 9 wt%, and may be at most 54 wt%, at most 53 wt%, at most 52 wt%, at most 51 wt%, at most 50 wt% .

The polycarbonate block copolymer has a viscosity average molecular weight (Mv), as measured in a methylene chloride solution, of preferably 10,000 to 200,000, more preferably 10,000 to 150,000, even more preferably 15,000 to 70,000. If the viscosity average molecular weight of the polycarbonate block copolymer is less than 10,000, mechanical properties may be significantly deteriorated. If the viscosity average molecular weight is more than 200,000, a problem may arise in processing the resin due to an increase in melt viscosity.

The polycarbonate block copolymer may be prepared by preparing a polycarbonate oligomer as described above, and then copolymerizing the produced polycarbonate oligomer with a polyester block having the structure of Formula 1.

In one embodiment, the polycarbonate block copolymer comprises (1) a polycondensation reaction between the compound represented by Formula 1-1 and the compound represented by Formula 1-2 to form a polyester block having the structure of Formula 1 Obtaining an oligomer; And (2) copolymerizing the polyester block oligomer obtained in the step (1) with a polycarbonate oligomer. Preferably, the step (2) may be carried out in the presence of a polymerization catalyst.

As the polymerization catalyst, for example, basic catalysts such as alkali metal hydroxides, alkylammonium salts, alkylamines and the like can be used.

According to one embodiment of the present invention, a polyester block having the structure represented by the formula (1) is added to the organic phase-water mixture containing the polycarbonate oligomer thus prepared, Polycarbonate block copolymers of the invention can be prepared. The molecular weight regulator and the polymerization catalyst are as described above.

Also, according to one embodiment, the organic phase in which the produced copolymer is dispersed in methylene chloride is subjected to alkali washing and separation, followed by washing the organic phase with 0.1N hydrochloric acid solution, and then repeating the organic phase two to three times with distilled water After the washing is completed, the concentration of the organic phase dispersed in methylene chloride is adjusted to a constant level, and granulation is performed using a predetermined amount of pure water at 40 ° C to 80 ° C. If the pure water temperature is less than 40 ° C, the assembling speed is decreased and the assembling time may become very long. If the pure water temperature exceeds 80 ° C, it may become difficult to obtain the shape of the copolymer at a constant size. When the assembly is completed, it is preferable to dry first at 100 ° C to 110 ° C for 5 hours to 10 hours and secondly at 110 ° C to 120 ° C for 5 hours to 10 hours.

(2) Antioxidants

The polycarbonate resin having high heat resistance is generally subjected to high-temperature molding in excess of 300 캜. At such a high temperature, yellowing due to deterioration or generation of gas due to resin decomposition occurs, the transmittance is lowered, the color is deteriorated, the physical properties are lowered, and the molded article is adversely affected.

In order to prevent deterioration due to oxidation under such a high-temperature environment, the polycarbonate resin composition of the present invention includes an antioxidant.

In the polycarbonate resin composition of the present invention, an antioxidant commonly used in this field can be used without any particular limitation, and a phosphite compound can be preferably used.

According to one embodiment of the present invention, as the antioxidant, an antioxidant of Dover Chemical represented by the following Chemical Formula 4 may be used, but is not limited thereto.

[Chemical Formula 4]

In the polycarbonate resin composition of the present invention, an antioxidant is contained in an amount of from 0.005 parts by weight to less than 4 parts by weight (for example, from 0.006 parts by weight to 3.9 parts by weight) based on 100 parts by weight of the polycarbonate block copolymer. If the content of the antioxidant in the polycarbonate resin composition is less than the above range, the transmittance of the molded article may be lowered, the color may be deteriorated, and the physical properties may be lowered.

More specifically, the amount of the antioxidant in the polycarbonate resin composition is 0.01 part by weight or more, 0.05 parts by weight or more, 0.1 parts by weight or more, 0.15 parts by weight or more, or 0.2 parts by weight or more based on 100 parts by weight of the polycarbonate block copolymer And may be up to 3.5 parts by weight, up to 3 parts by weight, up to 2.5 parts by weight, up to 2 parts by weight, up to 1.5 parts by weight or up to 1 part by weight.

(3)

In addition to the above-described components, the polycarbonate resin composition of the present invention may further include a fluidizing agent to improve fluidity.

The polycarbonate resin composition of the present invention may contain a fluidizing agent conventionally used in this field without any particular limitation, preferably a phosphate ester compound.

In one embodiment of the present invention, at least one selected from a phosphoric acid ester compound represented by the following general formula (5), a phosphoric acid ester compound represented by the following general formula (6), or a mixture thereof may be used as the fluidizing agent, but the present invention is not limited thereto.

[Chemical Formula 5]

In Formula 5,

R ₈ , R ₉ , R ₁₀ and R ₁₁ each independently represent a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms; A substituted or unsubstituted cycloalkyl group having 3 to 6 carbon atoms; Substituted or unsubstituted aryl groups having 6 to 20 carbon atoms (e.g., cresyl, phenyl, xylanyl, propylphenyl, butylphenyl, or chlorinated or brominated derivatives thereof); Or a substituted or unsubstituted aralkyl group having 7 to 20 carbon atoms, wherein the substituent may be at least one selected from a halogen atom or an alkyl group having 1 to 4 carbon atoms,

X is a mononuclear aromatic group having 6 to 30 carbon atoms or a polynuclear aromatic group (for example, diphenylphenol, bisphenol A, resorcinol, hydroquinone or a chlorinated or brominated derivative thereof)

n may each independently be an integer of 0 or 1, preferably 1,

N may be an average value of 0 to 10, preferably 0.3 to 8, more preferably 0.5 to 5.

[Chemical Formula 6]

In Formula 6,

R ₈ , R ₉ , R ₁₀ , R ₁₁ , n and N are the same as defined in Formula 5,

R ₁₂ and R ₁₃ are each independently an alkyl group having 1 to 4 carbon atoms (preferably a methyl group) or a halogen atom (preferably a chlorine atom or a bromine atom)

Y is an alkylidene of 1 to 7 carbon atoms, an alkylene of 1 to 7 carbon atoms, a cycloalkylene of 5 to 12 carbon atoms, a cycloalkylidene of 5 to 12 carbon atoms, -O-, -S-, -SO-, -SO ₂ - or -CO-, preferably an alkylidene of 1 to 7 carbon atoms, more preferably isopropylidene or methylene,

 a represents an integer of 0 to 2;

In one embodiment of the present invention, the phosphoric acid ester compound used as the fluidizing agent may be a mixture of monophosphate (N = 0), oligophosphate (N = 1 to 10 average value) or monophosphate and oligophosphate.

In one embodiment of the present invention, preferred examples of the phosphoric acid ester compound used as the fluidizing agent include resorcinol bis (diphenylphosphate), bisphenol-A bis (diphenylphosphate), or resorcinol bis Dimethyl phenyl phosphate).

In one embodiment of the present invention, a fluidizing agent of DAIHACHI Chemical represented by the following general formula (7) can be used as the fluidizing agent, but is not limited thereto.

(7)

When the fluidizing agent is contained in the polycarbonate resin composition of the present invention, the content thereof may be, for example, 0.05 to 2 parts by weight based on 100 parts by weight of the polycarbonate block copolymer. If the content of the fluidizing agent is too small, the effect of improving fluidity due to the addition of the fluidizing agent may be insignificant. On the other hand, if the amount is too large, mechanical properties such as impact strength may be deteriorated.

More specifically, the amount of the fluidizing agent in the polycarbonate resin composition may be 0.05 parts by weight or more, 0.1 parts by weight or more, 0.15 parts by weight or more, or 0.2 parts by weight or more based on 100 parts by weight of the polycarbonate block copolymer, 2 parts by weight or less, 1.5 parts by weight or less, or 1 part by weight or less.

According to another aspect of the present invention, there is provided a process for preparing a polyester block oligomer, comprising the steps of: (1) subjecting a compound represented by Formula 1-1 to a condensation reaction to obtain a polyester block oligomer; (2) copolymerizing the polyester block oligomer obtained in the step (1) with a polycarbonate oligomer to obtain a polycarbonate block copolymer; And (3) mixing the polycarbonate block copolymer obtained in the step (2) with an antioxidant.

The concrete method of producing the polycarbonate block copolymer through the steps (1) and (2) is as described above. In the step (3), the polycarbonate block copolymer and the antioxidant are mixed, Without limitation, using methods and apparatus commonly used in the art.

According to another aspect of the present invention, there is provided a molded article comprising the polycarbonate resin composition of the present invention.

The method for molding the polycarbonate resin composition of the present invention into a molded product is not particularly limited, and for example, extrusion or injection molding methods and apparatus generally used in the plastic molding field can be used.

Hereinafter, the present invention will be described in more detail with reference to examples and comparative examples. However, the scope of the present invention is not limited thereto.

[ Example ]

Manufacturing example  1: Phthalimidine series  Preparation of polyester block oligomer compounds

(0.6 mol) of N-phenyl 3,3-bis (4-hydroxyphenyl) phthalimidine (PBHPP) having the following general formula (8-1) g and then charged into a 20 L four-necked reactor. Terephthaloyl chloride (0.5 mol) of the following formula (8-2) was dissolved in 6,000 g of methylene chloride, and the mixture was added to the four-necked reactor . Sodium hydroxide (1.23 mol) was dissolved in distilled water to prepare a caustic soda aqueous solution (10%), which was dropped for 240 minutes and charged into the four-necked reactor. After the dropwise addition, the mixture was stirred for 60 minutes, phase separation was carried out, and the intermediate liquid layer was separated. The separated middle liquid layer was precipitated in ethanol, washed with distilled water and dried in an oven for 24 hours to obtain a phthalimidine-based polyester block oligomer (number average molecular weight = 6,000) represented by the following formula (8).

[Formula 8-1]

[Formula 8-2]

[Chemical Formula 8]

In the above formula (8), the n value was 11.

Manufacturing example  2: Preparation of polycarbonate oligomer

(2.63 moles) of bisphenol A was dissolved in 3,300 ml (184.6 g, 4.62 moles) of 5.6 wt% sodium hydroxide aqueous solution and then 260 g (2.63 moles) of phosgene was collected in methylene chloride in a 10 L four-necked flask. ) In a nitrogen atmosphere. The external temperature was maintained at 0 ° C. The reaction product having passed through the tubular reactor was subjected to interfacial reaction in a nitrogen atmosphere for about 10 minutes to prepare an oligomeric polycarbonate having a viscosity average molecular weight of about 1,000. 2,150 mL of the organic phase and 3,220 mL of the aqueous phase were collected in a mixture containing the oligomeric polycarbonate prepared above, and 13.83 g (92.1 mmol, 3.5 mol% based on bisphenol A) of p-tert-butylphenol (PTBP) (26.3 mmol, 1 mol% based on bisphenol A) of tetrabutyl ammonium chloride (TBACl) and 1 mL of an aqueous solution of 15 wt% triethylamine (TEA) were mixed and reacted for 30 minutes to obtain a polycarbonate oligomer Solution.

Manufacturing example  3: Preparation of polycarbonate block copolymer

To the polycarbonate oligomer solution obtained in Preparation Example 2, 400 g of the compound of the formula 8 obtained in Preparation Example 1 (20% by weight based on the total amount of the monomer compounds constituting the copolymer) was added, (2,830 g), 1,100 mL of a 1.1N aqueous solution of sodium hydroxide (20% by volume based on the total mixture) and 150 μL of 15% by weight triethylamine were mixed and reacted for 1 hour, Further, 1,670 [mu] L of 15 wt% triethylamine and 1,280 g of methylene chloride were added and reacted for 1 hour. After separating the layers, pure water was added to the organic phase whose viscosity was increased, followed by washing with alkali, followed by separation. Subsequently, the organic phase was washed with a 0.1 N hydrochloric acid solution and then washed twice or three times with distilled water. After the washing was completed and the concentration of the organic phase was kept constant, the organic phase was assembled using a predetermined amount of secondary distilled water at 76 ° C. After the assembly was completed, the polycarbonate block copolymer was firstly dried at 110 DEG C for 8 hours and then at 120 DEG C for 10 hours.

Manufacturing example  4: Preparation of polycarbonate block copolymer

Except that 100 g of the compound of the formula (8) obtained in Preparation Example 1 (5% by weight based on the total weight of the monomer constituting the copolymer) was added to the polycarbonate oligomer solution obtained in Preparation Example 2, A block copolymer was prepared in the same manner as in Example 3.

Manufacturing example  5: Preparation of polycarbonate block copolymer

Except that 1000 g of the compound of the formula 8 obtained in Preparation Example 1 (50% by weight based on the total weight of the monomer constituting the copolymer) was added to the polycarbonate oligomer solution obtained in Preparation Example 2, A block copolymer was prepared in the same manner as in Example 3.

Manufacturing example  6: Preparation of polycarbonate block copolymer

Except that 20 g of the compound of the formula (8) obtained in Preparation Example 1 (1% by weight based on the total weight of the monomer constituting the copolymer) was added to the polycarbonate oligomer solution obtained in Preparation Example 2, A block copolymer was prepared in the same manner as in Example 3.

Manufacturing example  7: Preparation of polycarbonate block copolymer

Except that 1100 g of the compound of the formula (8) obtained in Preparation Example 1 (55% by weight based on the total weight of the monomer constituting the copolymer) was added to the polycarbonate oligomer solution obtained in Preparation Example 2, A block copolymer was prepared in the same manner as in Example 3.

Example  1 to 9 and Comparative Example  1 to 5: Preparation of polycarbonate resin composition

The polycarbonate block copolymer obtained in Production Examples 3 to 7, the antioxidant and the fluidizing agent were mixed by the Henschel mixer in the contents shown in the following Table 1, uniformly dispersed, and then the biaxial melt The raw material was melted and kneaded using a mixing extruder. Subsequently, the melt discharged through the extrusion die was cooled to produce molding pellets. The prepared pellets were dried by hot air at a temperature of 90 ° C to 100 ° C for 4 hours or more, and injection molded at a temperature of 280 to 320 ° C to prepare specimens. The properties of the prepared specimens were measured and evaluated, and the results are shown in Table 2 below.

[Component description]

- Production Example 3: The polycarbonate block copolymer obtained in Production Example 3

- Production Example 4: The polycarbonate block copolymer obtained in Production Example 4

- Production Example 5: The polycarbonate block copolymer obtained in Production Example 5

- Production Example 6: The polycarbonate block copolymer obtained in Production Example 6

- Production Example 7: Polycarbonate block copolymer obtained in Production Example 7

- Antioxidant: The compound of Formula 4 (S9228, manufactured by Dover Chemical Co.)

- Fluidizing agent: Compound (7) (CR741, manufactured by DAIHACHI Chemical Co., Ltd.)

[Measurement of physical properties]

(1) Glass transition temperature

The glass transition temperature was measured using a differential scanning calorimeter (Perkin-Elmer DSC-7 & Robotic).

(2) Viscosity average molecular weight

The viscosity of the methylene chloride solution was measured at 20 占 폚 using a Ubbelohde Viscometer, and the intrinsic viscosity [?] Was calculated from the following formula.

^{[η] = 1.23 × 10 -} 5 Mv 0 .83

(3) Fluidity

Measured at 330 캜 and 2.16 kgf according to ASTM D1238.

(4) Impact strength

A notch was applied to the specimen (1/8 ") according to ASTM D256. The final result was calculated as the average of the test results of 10 specimens.

As shown in Table 1, in Examples 1 to 9 according to the present invention, preferable results were obtained in all of the measured and evaluated properties. On the other hand, in Comparative Examples 1 to 3, the impact strength was very poor compared with the Examples. In Comparative Example 4, the heat resistance was very poor (i.e., the glass transition temperature was too low as compared with the Examples) The impact strength was very poor compared to the examples. That is, no comparative example satisfying all of the measured and evaluated physical properties at a desirable level was found.

Claims (8)

(1) a polycarbonate block copolymer; (2) antioxidants; And (3) a fluidizing agent,
Wherein the polycarbonate block copolymer comprises (A) a polyester block having a structure represented by the following formula (1) as a repeating unit; And (B) a polycarbonate block,
The amount of the polyester block in the polycarbonate block copolymer is more than 1 wt% to less than 55 wt% based on 100 wt% of the total weight of the monomer compounds constituting the polycarbonate block copolymer,
Wherein the antioxidant is contained in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the polycarbonate block copolymer,
Wherein the fluidizing agent is contained in an amount of 0.05 part by weight to 1 part by weight based on 100 parts by weight of the polycarbonate block copolymer.
Polycarbonate resin composition:
[Chemical Formula 1]

In Formula 1,
R ₁ is independently a hydrogen atom; An alkyl group having 1 to 4 carbon atoms; A cycloalkyl group having 3 to 6 carbon atoms; A cycloalkylalkyl group having 4 to 10 carbon atoms; Or an aryl group having 6 to 10 carbon atoms,
X independently represents an oxygen atom or NR ₂ , wherein R ₂ is independently a hydrogen atom; An alkyl group having 1 to 4 carbon atoms; A cycloalkyl group having 3 to 10 carbon atoms which is substituted or unsubstituted with a substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms; Or an aryl group having 6 to 10 carbon atoms, which is substituted or unsubstituted with a substituent selected from the group consisting of a halogen atom and an alkyl group having 1 to 4 carbon atoms,
R ₃ independently represents an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, a cycloalkylene-alkylene group having 4 to 10 carbon atoms, or an arylene group having 6 to 10 carbon atoms,
m represents an integer of 2 to 50; The polyester block having the structure represented by the above formula (1) is obtained by condensing an ester oligomer prepared by the condensation reaction between the compound represented by the following formula (1-1) and the compound represented by the following formula (1-2) Phosphoric acid, polycarbonate resin composition:
[Formula 1-1]

[Formula 1-2]

In the above formulas 1-1 and 1-2,
R ₁ , X and R ₃ are as defined in claim 1,
Y independently represents a hydroxy group or a halogen atom. The polycarbonate resin composition according to claim 1, wherein the antioxidant is a phosphite compound. The polycarbonate resin composition according to claim 1, wherein the fluidizing agent is a phosphate ester compound. (1) a step of condensing a compound represented by the following formula (1-1) and a compound represented by the following formula (1-2) to obtain a polyester block oligomer;
(2) copolymerizing the polyester block oligomer obtained in the step (1) with a polycarbonate oligomer to obtain a polycarbonate block copolymer; And
(3) mixing the polycarbonate block copolymer obtained in the step (2) with an antioxidant and a fluidizing agent,
here,
Wherein the amount of the polyester block in the polycarbonate block copolymer obtained in the step (2) ranges from more than 1 wt% to 55 wt% based on 100 wt% of the total weight of the monomer compounds constituting the polycarbonate block copolymer, Lt; / RTI &
In the step (3), the antioxidant is mixed in an amount of 0.01 to 2 parts by weight based on 100 parts by weight of the polycarbonate block copolymer,
Wherein the fluidizing agent is mixed in an amount of 0.05 part by weight to 1 part by weight with respect to 100 parts by weight of the polycarbonate block copolymer in the step (3)
Method of producing polycarbonate resin composition:
[Formula 1-1]

[Formula 1-2]

In the above formulas 1-1 and 1-2,
R ₁ , X and R ₃ are as defined in claim 1,
Y independently represents a hydroxy group or a halogen atom. A molded article comprising the polycarbonate resin composition according to any one of claims 1 to 4. delete delete