KR20200080471A - Polycarbonate resin composition having excellent heat resistance and fluidity and molded article comprising the same - Google Patents

Abstract

The present invention relates to a polycarbonate resin composition having excellent heat resistance and fluidity, and a molded article comprising the same. More particularly, the present invention relates to: a polycarbonate resin composition which includes a polyester compound having a specific structure, a polyester-polycarbonate block copolymer having a specific structure, and a polyarylate resin in a specific weight ratio, and thus exhibits remarkably excellent heat resistance compared to a conventional high heat-resistant polycarbonate resin while having excellent balance of physical properties such as fluidity and impact resistance; and a molded article comprising the same.

Description

A polycarbonate resin composition having excellent heat resistance and fluidity and molded article comprising the same}

The present invention relates to a polycarbonate resin composition excellent in heat resistance and fluidity and a molded article comprising the same, and more specifically, a specific structure of a polyester compound, a specific structure of a polyester-polycarbonate block copolymer and a polyarylate resin By including in a specific weight ratio, the present invention relates to a polycarbonate resin composition and a molded article comprising the same, which exhibits remarkably excellent heat resistance as compared with a conventional high heat-resistant polycarbonate resin, and also has excellent physical properties such as fluidity and impact resistance.

Polycarbonate resins are widely used as electrical parts, mechanical parts and industrial resins due to their excellent heat resistance, mechanical properties (especially impact strength) and transparency. In particular, when polycarbonate resin is used as a TV housing, a computer monitor housing, a copier, a printer, a notebook battery, a lithium battery case material, etc., which are highly dissipated among electric and electronic fields, excellent heat resistance is required as well as mechanical properties.

However, a general polycarbonate resin is selectively invaded by a specific solvent, has no resistance, has good creep resistance against static loads, but is relatively easily destroyed when the temperature and various environmental conditions are paired, and the resistance to dynamic loads is complicated. There was.

Accordingly, research has been continuously conducted to increase the heat resistance of the polycarbonate resin, and as a result, a high heat resistance polycarbonate resin has been developed (eg, US Patent 5,070,177, US Patent 4,918,149, Domestic Patent No. 10-2016-0007194) ). In general, such a high heat-resistant polycarbonate resin is modified bisphenol A to introduce a three-dimensional substituent at the ortho (ortho) position to increase the hydrolysability, and increase the heat deformation temperature. However, such a conventional high heat-resistant polycarbonate resin has a problem in that impact resistance and fluidity are inferior to that of a general polycarbonate resin.

Therefore, there is a need to develop a polycarbonate resin composition that maintains excellent impact resistance and fluidity while significantly improving heat resistance.

The present invention is to solve the problems of the prior art as described above, and provides a polycarbonate resin composition and a molded article comprising the same excellent in the balance of physical properties such as fluidity and impact resistance while significantly improving the heat resistance compared to the conventional high heat resistance polycarbonate resin Doing so is a technical task.

In order to solve the above technical problem, the present invention, based on a total of 100 parts by weight of a polycarbonate resin composition, (1) 24 to 34 parts by weight of a polyester oligomer having a structure represented by Formula 1; (2) 41 to 67 parts by weight of a polyester-polycarbonate block copolymer obtained by reacting a polyester oligomer having a structure represented by Formula 1 and a polycarbonate oligomer; And (3) 5 to 34 parts by weight of a polyarylate resin containing a bisphenol component and an aromatic dicarboxylic acid component comprising a compound represented by the following formula (4) as a monomer component:

[Formula 1]

In Chemical Formula 1,

R ₁ independently represents a hydrogen atom, an alkyl, cycloalkyl, cycloalkylalkyl or aryl group,

X independently represents oxygen or NR ₂ , wherein R ₂ independently represents a hydrogen atom, an alkyl, cycloalkyl, cycloalkylalkyl or aryl group,

R ₃ independently represents an alkylene, cycloalkylene, cycloalkylenealkylene or arylene group,

m is an integer from 2 to 50 independently;

[Formula 4]

In Chemical Formula 4,

R ₈ and R ₉ each independently represent an alkyl group.

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

The polycarbonate resin composition according to the present invention is excellent in heat resistance, and at the same time, excellent in the balance of physical properties such as fluidity, impact resistance and transparency, and is useful for products requiring heat resistance, such as housings for office equipment and electrical and electronic products, and interior and exterior parts of automobiles. It can be used, and in particular, a molded article having excellent moldability can be produced due to high fluidity.

Hereinafter, the present invention will be described in more detail.

The polycarbonate resin composition of the present invention includes (1) a polyester oligomer, (2) a polyester-polycarbonate block copolymer, and (3) a polyarylate resin.

(1) Polyester oligomer

The polyester oligomer included in the polycarbonate resin composition of the present invention has a structure represented by Formula 1 below:

[Formula 1]

In Chemical Formula 1,

R ₁ independently represents a hydrogen atom, an alkyl, cycloalkyl, cycloalkylalkyl or aryl group, more specifically, 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, and more specifically a hydrogen atom; An alkyl group having 1 to 3 carbon atoms, a cycloalkyl group having 5 to 6 carbon atoms, a cycloalkyl alkyl group having 6 to 9 carbon atoms; Or represents an aryl group having 6 carbon atoms,

X independently represents oxygen or NR ₂ , wherein R ₂ independently represents a hydrogen atom, an alkyl, cycloalkyl, cycloalkylalkyl or aryl group, more specifically, R ₂ is independently a hydrogen atom; An alkyl group having 1 to 4 carbon atoms (for example, it may be methyl, ethyl, propyl or butyl); A cycloalkyl group having 3 to 10 carbon atoms 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 (for example, cyclopropane, cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane) , Chlorocyclohexane, methylcyclopentane, 1-bromo-2-methyl-cyclopentane or 1-chloro-1-ethyl-cyclohexane); Or an aryl group having 6 to 10 carbon atoms 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 (for example, it may be phenyl, benzyl, tolyl or chlorophenyl),

R ₃ independently represents an alkylene, cycloalkylene, cycloalkylenealkylene or arylene group, more specifically, R ₃ is independently an alkylene group having 1 to 10 carbon atoms, a cycloalkylene group having 3 to 6 carbon atoms, a carbon number It represents a cycloalkylene-alkylene group of 4 to 10 or an arylene group of 6 to 10 carbon atoms, and more specifically, an alkylene group of 1 to 6 carbon atoms, a cycloalkylene group of 5 to 6 carbon atoms, a cycloalkyl of 6 to 9 carbon atoms. Represents an alkylene-alkylene group or an arylene group having 6 carbon atoms,

m is an integer of 2 to 50 independently, more specifically an integer of 3 to 30, and more specifically represents an integer of 5 to 20.

According to an embodiment of the present invention, the polyester oligomer having the structure of Chemical Formula 1 may be prepared by condensation reaction of a compound represented by Chemical Formula 1-1 with a compound represented by Chemical Formula 1-2:

[Formula 1-1]

[Formula 1-2]

In Chemical Formulas 1-1 and 1-2,

R ₁ , X and R ₃ are as defined in Formula 1 above,

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

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

In one embodiment, the number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of the polyester oligomer prepared by condensation reaction of the compound of Formula 1-1 and the compound of Formula 1-2 is 500 to 30,000 g/mol However, it is not limited thereto.

In 100 parts by weight of the polycarbonate resin composition of the present invention, the polyester oligomer having the structure represented by Formula 1 is included in an amount of 24 to 34 parts by weight. If the content of the polyester oligomer in 100 parts by weight of the polycarbonate resin composition is less than 24 parts by weight, the heat resistance is lowered, whereas, if it exceeds 34 parts by weight, the impact resistance is reduced.

In one embodiment, the amount of the polyester oligomer having the structure represented by Formula 1, based on 100 parts by weight of the polycarbonate resin composition, may be 24 parts by weight or more, 25 parts by weight or more, 26 parts by weight or more, or 27 parts by weight or more It may also be 34 parts by weight or less, 33 parts by weight or less, 32 parts by weight or less, 31 parts by weight or less, or 30 parts by weight or less.

(2) Polyester-polycarbonate block copolymer

The polyester-polycarbonate block copolymer contained in the polycarbonate resin composition of the present invention is obtained by reacting a polyester oligomer having a structure represented by Formula 1 and a polycarbonate oligomer.

The polyester oligomer having a structure represented by Chemical Formula 1 used in the preparation of the polyester-polycarbonate block copolymer is as described above.

There is no particular limitation in the method for producing a polycarbonate oligomer used in the production of the polyester-polycarbonate block copolymer. For example, a phosgene method in which a divalent phenol compound and phosgene are mixed together may be prepared, but is not limited thereto.

The divalent phenol compounds used in the production of polycarbonate oligomer may be, for example, the following Formula 2 compound.

[Formula 2]

In Chemical Formula 2,

A is a straight, branched or cyclic alkylene group having no functional group; Or a linear, branched or cyclic alkylene group comprising at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, phenyl, isobutylphenyl or naphthyl, preferably A having 1 to 1 carbon atoms. A straight alkylene group of 10, a branched alkylene group of 3 to 10 carbon atoms, or a cyclic alkylene group of 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, and preferably 0 or 1.

The compound of Formula 2 is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4-hydroxy Phenyl)-(4-isobutylphenyl)methane, 1,1-bis(4-hydroxyphenyl)ethane, 1-ethyl-1,1-bis(4-hydroxyphenyl)propane, 1-phenyl-1, 1-bis(4-hydroxyphenyl)ethane, 1-naphthyl-1,1-bis(4-hydroxyphenyl)ethane, 1,2-bis(4-hydroxyphenyl)ethane, 1,10-bis (4-hydroxyphenyl)decane, 2-methyl-1,1-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxyphenyl)propane, 2,2-bis(4-hydroxy Hydroxyphenyl)butane, 2,2-bis(4-hydroxyphenyl)pentane, 2,2-bis(4-hydroxyphenyl)hexane, 2,2-bis(4-hydroxyphenyl)nonane, 2,2 -Bis(3-methyl-4-hydroxyphenyl)propane, 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)methane, resorcinol, hydroquinone, 4,4'-dihydroxy Phenyl ether [bis(4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dichlorodi Phenyl ether, bis(3,5-dimethyl-4-hydroxyphenyl) ether, bis(3,5-dichloro-4-hydroxyphenyl) ether, 1,4-dihydroxy-2,5-dichlorobenzene, 1,4-dihydroxy-3-methylbenzene, 4,4'-dihydroxydiphenol [p,p'-dihydroxyphenyl], 3,3'-dichloro-4,4'-dihydroxy Phenyl, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dichloro- 4-hydroxyphenyl)cyclohexane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)cyclododecane, 1,1-bis(4-hydroxyphenyl)cyclododecane, 1,1 -Bis(4-hydroxyphenyl)butane, 1,1-bis(4-hydroxyphenyl)decane, 1,4-bis(4-hydroxyphenyl)propane, 1,4-bis(4-hydroxyphenyl) )Butane, 1,4-bis(4- Hydroxyphenyl)isobutane, 2,2-bis(4-hydroxyphenyl)butane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, bis(3,5-dimethyl-4-hydroxy Hydroxyphenyl)methane, bis(3,5-dichloro-4-hydroxyphenyl)methane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5 -Dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,4-bis(4-hydroxyphenyl)-2-methyl- Butane, 4,4'-thiodiphenol [bis(4-hydroxyphenyl)sulfone], bis(3,5-dimethyl-4-hydroxyphenyl)sulfone, bis(3-chloro-4-hydroxyphenyl) Sulfone, bis(4-hydroxyphenyl)sulfide, bis(4-hydroxyphenyl)sulfoxide, bis(3-methyl-4-hydroxyphenyl)sulfide, bis(3,5-dimethyl-4-hydroxyphenyl) )Sulfide, bis(3,5-dibromo-4-hydroxyphenyl)sulfoxide, 4,4'-dihydroxybenzophenone, 3,3',5,5'-tetramethyl-4,4' -Dihydroxybenzophenone, 4,4'-dihydroxy diphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene, or 2,6-dihydroxynaphthalene. Representative of these is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other dihydric phenol compounds (dihydric phenol) may refer to U.S. Pat. They can be used in combination with each other.

According to an embodiment of the present invention, the divalent phenol compounds (eg, bisphenol A) are added to an aqueous alkali solution, and then the mixture is reacted by mixing the mixture with an organic solvent (eg dichloromethane) injected with phosgene gas. If desired, an oligomeric polycarbonate can be prepared, wherein the molar ratio of the phosgene:divalent phenolic 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 prepared oligomeric polycarbonate may be 1,000 to 2,000.

According to another embodiment of the present invention, the divalent phenol compound (eg, bisphenol A) is added to an aqueous alkali solution, and then the mixture is reacted by mixing the mixture with an organic solvent (eg, dichloromethane) injected with phosgene gas. (At this time, the molar ratio of the phosgene:divalent phenolic compound may be maintained in the range of about 1:1 to 1.5:1, preferably about 1:1 to 1.2:1). Polycarbonate oligomer may be formed by adding.

The polycarbonate oligomer forming reaction can be carried out generally at a temperature in the range of about 15°C to 60°C. Alkali metal hydroxide can be introduced into the reaction mixture to adjust the pH of the reaction mixture. The alkali metal hydroxide may be, for example, sodium hydroxide. As the molecular weight modifier, a monofunctional compound similar to a monomer used in polycarbonate production may be used. The monofunctional substance is, for example, phenol or a derivative thereof (eg, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumyl phenol, p- Isooctylphenol, and p-isononylphenol, etc.), or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) can 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 Formula 3 below.

[Formula 3]

^{_{(R 6) 4 Q + Z}} -

In Chemical Formula 3,

R ₆ may independently represent an alkyl group having 1 to 10 carbon atoms,

Q can represent nitrogen or phosphorus,

Z may represent a halogen atom or -OR ₇ , where 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 transition catalyst is, 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, CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NZ. Here, 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 change catalyst is preferably about 0.1 to 10% by weight of the reaction mixture. If the content of the phase change catalyst is less than 0.1% by weight, the reactivity may deteriorate, and if it exceeds 10% by weight, precipitation may occur, and as a result, transparency of the copolymer may deteriorate.

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

When the washing is completed, the concentration of the organic phase dispersed in methylene chloride is constantly adjusted to granulate using a predetermined amount of secondary distilled water in the range of 40°C to 80°C. If the temperature of the secondary distilled water is less than 40°C, the granulation time may be slow, and the granulation time may be excessive. If it exceeds 80°C, it is difficult to obtain a polycarbonate having a constant particle size. When the assembly is completed, it is preferably dried at 100°C to 110°C for 5 hours to 10 hours, and secondly dried at 110°C to 120°C for 5 hours to 10 hours.

The prepared polycarbonate oligomer may have a viscosity average molecular weight of 1,000 to 30,000, more specifically 1,000 to 20,000, and more specifically 1,000 to 15,000. If the viscosity average molecular weight is less than 1,000, mechanical properties may be remarkably deteriorated, and if it exceeds 30,000, copolymerization reactivity may be deteriorated. The polyester-polycarbonate block copolymer included in the polycarbonate resin composition of the present invention can be obtained by copolymerizing a polyester oligomer having the structure of Formula 1 and the above-described polycarbonate oligomer, and the polyester-polycarbonate The block copolymer includes a polyester block and a polycarbonate block as repeating units.

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

In one embodiment, the amount of the polyester block having the structure of Formula 1 in the polyester-polycarbonate block copolymer is based on 100 wt% of the total weight of the monomer compounds constituting the polyester-polycarbonate block copolymer. When done, 0.5% to 55% by weight (specifically 0.5% to 50% by weight, more specifically 1% to 50% by weight, even more specifically 10% to 50% by weight, even more specifically Is 10% by weight to 40% by weight). If the relative content of the polyester block having the structure of Formula 1 in the polyester-polycarbonate block copolymer is less than this, heat resistance may be deteriorated. Conversely, when it is more than this, physical properties such as transparency, fluidity, and impact strength are lowered, and manufacturing cost This can increase.

More specifically, the amount of the polyester block having the structure of Formula 1 in the polyester-polycarbonate block copolymer, based on the total weight of the monomer compound constituting the polyester-polycarbonate block copolymer 100% by weight When, 2 wt% or more, 3 wt% or more, 4 wt% or more, 5 wt% or more, 9 wt% or more, or 10 wt% or more, and also, 54 wt% or less, 53 wt% or less, 52 wt% or less , 51% by weight or less, 50% by weight or less, or 40% by weight or less.

The polyester-polycarbonate block copolymer, as measured in a methylene chloride solution, preferably has a viscosity average molecular weight (Mv) of 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 polyester-polycarbonate block copolymer is less than 10,000, mechanical properties may be remarkably deteriorated, and if it exceeds 200,000, problems may arise in the processing of the resin due to an increase in melt viscosity.

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

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

As the polymerization catalyst, for example, a basic catalyst such as alkali metal hydroxide, alkyl ammonium salt, or alkyl amine can be used.

According to another embodiment of the present invention, by adding the polyester oligomer having the structure represented by the formula (1) to the organic phase-aqueous mixture containing the polycarbonate oligomer prepared above, step by step molecular weight regulator and polymerization catalyst to the poly Ester-polycarbonate block copolymers can be prepared. The molecular weight modifier and polymerization catalyst are as described above.

In addition, according to an embodiment, the prepared polyester-polycarbonate block copolymer is separated after alkali washing the organic phase dispersed in methylene chloride, and then the organic phase is washed with 0.1N hydrochloric acid solution and then distilled water Washing is repeated 2 to 3 times, and when the washing is completed, the concentration of the organic phase dispersed in methylene chloride is constantly adjusted to granulate using a certain amount of pure water in the range of 40°C to 80°C. If the temperature of the pure water is less than 40°C, the assembly speed may be slow and the assembly time may be very long. If the temperature of the pure water exceeds 80°C, it may be difficult to obtain a copolymer shape with a constant size. When the assembly is completed, it is preferably dried at 100°C to 110°C for 5 hours to 10 hours, and secondly dried at 110°C to 120°C for 5 to 10 hours.

In 100 parts by weight of the polycarbonate resin composition of the present invention, the polyester-polycarbonate block copolymer is contained in an amount of 41 to 67 parts by weight. When the content of the polyester-polycarbonate block copolymer in 100 parts by weight of the polycarbonate resin composition is less than 41 parts by weight, impact resistance may be deteriorated. Conversely, when it exceeds 67 parts by weight, fluidity is reduced.

In one embodiment, the amount of the polyester-polycarbonate block copolymer, based on 100 parts by weight of the polycarbonate resin composition, 41 parts by weight or more, 43 parts by weight or more, 45 parts by weight or more, 48 parts by weight or more, 50 parts by weight Or more, 52 parts by weight or more, or 55 parts by weight or more, and 67 parts by weight or less, 65 parts by weight or less, 62 parts by weight or less, 60 parts by weight or less, 58 parts by weight or less, 55 parts by weight or less or 50 parts by weight or less Can.

(3) Polyarylate Suzy

The polyarylate resin contained in the polycarbonate resin composition of the present invention contains a bisphenol component and an aromatic dicarboxylic acid component comprising a compound represented by the following formula (4) as a monomer component:

[Formula 4]

In Chemical Formula 4,

R ₈ and R ₉ each independently represent an alkyl group, and more specifically, an alkyl group having 1 to 10 carbon atoms. Examples of the alkyl group include a hydrocarbon group having 1 to 6 carbon atoms, particularly a saturated hydrocarbon group, and preferably a saturated hydrocarbon group having 1 to 4 carbon atoms. Preferably, R ₈ and R ₉ may be a methyl group, ethyl group, propyl group or butyl group at the same time.

The polyarylate resin contained in the polycarbonate resin composition of the present invention includes a bisphenol component and an aromatic dicarboxylic acid component as monomer components.

As a bisphenol component, it is necessary to contain the compound represented by the said general formula (4) which has an alkyl group only in the 3rd position of the benzene ring of bisphenol.

As the compound represented by the formula (4), for example, 2,2-bis(3-methyl-4-hydroxyphenyl)propane (hereinafter sometimes referred to as BisC), 2,2-bis(3-ethyl- 4-hydroxyphenyl)propane and 2,2-bis(3-tert-butyl-4-hydroxyphenyl)propane.

In the bisphenol component, it is preferable to contain the compound represented by the formula (4) in an amount of 90 mol% or more based on the total amount of the bisphenol component, and it is more preferable to contain 95 mol% or more. When the compound represented by the formula (4) is not contained in the bisphenol component, solution stability in a polar organic solvent having high hygroscopicity (hereinafter sometimes referred to simply as solution stability) and solubility in an organic solvent (hereinafter simply referred to as solubility) It is not preferred because it decreases, or because the ultraviolet absorbing properties and adhesion to various materials are lowered.

As a bisphenol component, you may contain other bisphenols other than the compound represented by Formula (4) in the range which does not impair the effect of this invention. Examples of other bisphenols include 2,2-bis(4-hydroxyphenyl)propane (hereinafter sometimes referred to as BisA) and 2,2-bis(3,5-dimethyl-4-hydroxy) Phenyl)propane (hereinafter sometimes referred to as TMBPA), 9,9-bis(3-methyl-4-hydroxyphenyl)fluorene, 1,1-bis(4-hydroxyphenyl)-1-phenyl Ethane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 1,1-bis(4-hydroxyphenyl)ethane, 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)ethane , 1,1-bis(3-methyl-4-hydroxyphenyl)ethane, bis(4-hydroxyphenyl)methane, bis(3,5-dimethyl-4-hydroxyphenyl)methane, bis(3-methyl -4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)hexane or 1,1-bis(3,5-dimethyl-4-hydroxyphenyl)hexane. The content of other bisphenols is preferably 10 mol% or less, more preferably 5 mol% or less, and substantially not included in the bisphenol component from the viewpoint of further improvement in ultraviolet absorption properties, solubility and solution stability. It is more preferable not to.

Examples of the aromatic dicarboxylic acid component include phthalic acids such as terephthalic acid, isophthalic acid and orthophthalic acid; Terephthalic acid and iso substituted with 1 to 2 alkyl groups selected from the group consisting of methyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, sec-butyl and tert-butyl groups Phthalic acid derivatives such as phthalic acid; Biphenyl dicarboxylic acids such as 4,4'-biphenyldicarboxylic acid [BPDC] and 2,2'-biphenyldicarboxylic acid; Naphthalene dicarboxylic acids such as 1,5-naphthalenedicarboxylic acid and 2,6-naphthalenedicarboxylic acid; Or diphenyl ether-2,2'-dicarboxylic acid, diphenyl ether-2,3'-dicarboxylic acid, diphenyl ether-2,4'-dicarboxylic acid, diphenyl ether-3,3'-dicarboxylic acid, di And diphenyl ether dicarboxylic acids such as phenyl ether-3,4'-dicarboxylic acid and diphenyl ether-4,4'-dicarboxylic acid. From the viewpoint of mechanical strength, it is preferable to contain an aromatic dicarboxylic acid component selected from phthalic acids and biphenyl dicarboxylic acids, particularly terephthalic acid and isophthalic acid. In the aromatic dicarboxylic acid component, phthalic acid and biphenyl dicarboxylic acid, particularly terephthalic acid and isophthalic acid, are preferably contained in an amount of 90 mol% or more based on the total amount of the aromatic dicarboxylic acid component, more preferably 95 mol% or more. desirable.

From the viewpoint of solution stability and solubility, the molar ratio of terephthalic acid to isophthalic acid is preferably terephthalic acid/isophthalic acid=7/3 to 3/7, and more preferably 6/4 to 4/6.

In the present invention, to the extent that the effects of the present invention are not impaired, the polyarylate resin includes other components such as an aliphatic diol, an alicyclic diol, an aliphatic dicarboxylic acid, or an alicyclic dicarboxylic acid in addition to the bisphenol component and aromatic dicarboxylic acid component. May be contained as a monomer component. As an aliphatic diol, ethylene glycol and propylene glycol are mentioned, for example. Examples of the alicyclic diol include 1,4-cyclohexanediol, 1,3-cyclohexane diol, and 1,2-cyclohexanediol. As an aliphatic dicarboxylic acid, adipic acid and sebacic acid are mentioned, for example. Examples of the alicyclic dicarboxylic acid include 1,4-cyclohexanedicarboxylic acid, 1,3-cyclohexane dicarboxylic acid, and 1,2-cyclohexanedicarboxylic acid. It is preferable to make content of another additional monomer component less than 10 mol% with respect to the total number of moles of a raw material monomer, and it is more preferable not to contain substantially.

In one embodiment of the present invention, the polyarylate resin may have a structure represented by Formula 5 below.

[Formula 5]

In Chemical Formula 5,

R ₈ and R ₉ are as defined in Chemical Formula 4, n is an integer of 2 to 100, preferably 2 to 80, more preferably 30 to 80.

The polyarylate resin having a structure represented by Chemical Formula 5 may have a number average molecular weight (Mn) measured by gel permeation chromatography (GPC) of 500 to 30,000 g/mol, but is not limited thereto.

In 100 parts by weight of the polycarbonate resin composition of the present invention, the polyarylate resin is contained in an amount of 5 to 34 parts by weight. When the content of the polyarylate resin in 100 parts by weight of the polycarbonate resin composition is less than 5 parts by weight, heat resistance may deteriorate, whereas when it exceeds 34 parts by weight, fluidity decreases.

In one embodiment, the amount of the polyarylate resin, based on 100 parts by weight of the polycarbonate resin composition, 5 parts by weight or more, 7 parts by weight or more, 10 parts by weight or more, 15 parts by weight or more, 20 parts by weight or more, 25 parts by weight It may be at least 30 parts by weight or more, and may be 34 parts by weight or less, 30 parts by weight or less, 28 parts by weight or less, 25 parts by weight or less, 22 parts by weight or less, or 20 parts by weight or less.

The method for producing the polyarylate resin contained in the polycarbonate resin composition of the present invention is not particularly limited as long as the hydroxy group concentration can be within a predetermined range, but since the control of the hydroxy group concentration is easy, hydroxycarboxylic acid is used during melt polymerization. A method of controlling using ingredients is preferred.

As a method of increasing the hydroxy group concentration of the polyester, a method of performing a depolymerization reaction by adding a polyvalent glycol component after the polycondensation reaction is completed is widely known. However, in the case of a polyarylate resin, the progress of the depolymerization reaction by a polyhydric glycol component, a divalent phenol component, or a hydroxycarboxylic acid component is slow, and the reaction time of the entire reaction is lengthened. In addition, a portion of the monomer components added during the depolymerization reaction remain unreacted, and a portion of the monomer components constituting the polyarylate resin is produced as a monomer by the depolymerization reaction. For this reason, the method of performing a depolymerization reaction is not preferable.

In the present invention, the method of controlling the concentration of a hydroxy group using a hydroxycarboxylic acid component during melt polymerization is a method for performing an acetylation reaction and a deacetic acid polymerization reaction, after the acetylation reaction and before the deacetic acid polymerization reaction, It is a method of adding a hydroxycarboxylic acid component. That is, after the acetylation reaction is performed, the hydroxycarboxylic acid component is added until the deacetic acid polymerization reaction is performed. Such a method is also preferable from the viewpoint of solubility of the polyarylate resin in a general-purpose solvent. On the other hand, as long as the effects of the present invention are not impaired, a portion of the hydroxycarboxylic acid component may be added to carry out an acetylation reaction, and after the acetylation reaction, before the deacetic acid polymerization reaction, the remaining hydroxycarboxylic acid component may be added.

The acetylation reaction is a reaction of acetylating a divalent phenol component or a divalent phenol component and a hydroxycarboxylic acid component. In the acetylation reaction, an aromatic dicarboxylic acid component, a divalent phenol component, and acetic anhydride are added to the reaction vessel, or an aromatic dicarboxylic acid component, a divalent phenol component, hydroxycarboxylic acid, and acetic anhydride are added. Thereafter, nitrogen substitution is performed, and the mixture is stirred under an inert atmosphere at a temperature of 100 to 240°C, preferably 120 to 180°C, for 5 minutes to 8 hours, preferably 30 minutes to 5 hours, under normal pressure or under pressure. The molar ratio of acetic anhydride to the hydroxyl group of the divalent phenol component is preferably 1.00 to 1.20.

The deacetic acid polymerization reaction is a reaction of polycondensation by reacting acetylated divalent phenol with aromatic dicarboxylic acid. In the deacetic acid polymerization reaction, at a temperature of 240° C. or higher, preferably 260° C. or higher, more preferably 280° C. or higher, 500 Pa or lower, preferably 260 Pa or lower, more preferably 130 Pa or lower, at least 30 minutes Hold and stir. When the temperature is less than 240° C., when the pressure reduction degree exceeds 500 Pa, or when the holding time is less than 30 minutes, the amount of acetic acid in the polyarylate resin obtained by insufficient deacetic acid reaction becomes high, or the whole polymerization time becomes longer, The polymer color tone may deteriorate.

There is usually a preliminary step of adjusting the temperature and pressure of the reaction system to the temperature and pressure for the deacetic acid polymerization reaction between the acetylation reaction and the deacetic acid polymerization reaction. In the production method of the present invention, a hydroxycarboxylic acid component may be added in this preliminary step. Specifically, in the preliminary step, after the temperature of the reaction system is raised and the pressure is reduced, a hydroxycarboxylic acid component may be added before the temperature rise, or a hydroxycarboxylic acid component may be added after the temperature rise and before the pressure reduction. The hydroxycarboxylic acid component may be added before and after the temperature increase and at both the time before and after the pressure reduction.

In the present invention, after reacting acetic anhydride with a divalent phenol component or with a divalent phenol component and a hydroxycarboxylic acid component, a hydroxycarboxylic acid component is added. For this reason, the hydroxy group of the hydroxycarboxylic acid component added after the acetylation reaction is not acetylated. As a result, among the terminal groups of the hydroxycarboxylic acid component, the carboxyl group having excellent reactivity proceeds with the reaction of the polyarylate resin in the deacetic acid polymerization reaction step, but the reaction of the non-acetylated hydroxy group with the polyarylate resin It does not proceed. For this reason, it is estimated that the hydroxy group concentration of the polyarylate resin obtained can be made into a predetermined range.

In the acetylation reaction and the deacetic acid polymerization reaction, it is preferable to use a catalyst if necessary. Examples of the catalyst include organic titanium acid compounds such as tetrabutyl titanate; Zinc acetate; Alkali metal salts such as potassium acetate; Alkaline earth metal salts such as magnesium acetate; Antimony trioxide; Organotin compounds such as hydroxybutyltin oxide and tin octylate; And heterocyclic compounds such as N-methylimidazole. The amount of the catalyst added is usually 1.0 mol% or less, more preferably 0.5 mol% or less, and more preferably 0.2 mol% or less, based on the total monomer components of the polyarylate resin obtained.

The polycarbonate resin composition of the present invention is excellent in heat resistance, and at the same time, excellent in the balance of physical properties such as fluidity, impact resistance and transparency, so it can be usefully used in products requiring heat resistance, such as housings for office equipment and electrical and electronic products, automobile interior and exterior parts, etc. It is possible to manufacture a molded article having excellent moldability, especially due to its high fluidity.

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

The method of processing the polycarbonate resin composition of the present invention to produce a molded article is not particularly limited, and a molded article can be manufactured using a method commonly used in the field of plastic molding. For example, the polycarbonate resin composition may be melt-extruded in an extruder and manufactured in pellet form, or a molded article may be manufactured by various processes such as injection molding, blow molding, extrusion molding, and thermoforming.

Hereinafter, the present invention will be described in more detail through Examples and Comparative Examples. However, the scope of the present invention is not limited to these.

[ Example ]

Manufacturing example One: Phthalimidine Preparation of polyester oligomer

N-phenyl 3,3-bis-(4-hydroxyphenyl)phthalimidine (PBHPP) (0.6 mol) of the following formula 6-1 is distilled water 1,657 After dissolving in g, the mixture was introduced into a 4-L reactor of 20 L, and terephthaloyl chloride (0.5 mol) of the following Formula 6-2 was dissolved in 6,000 g of Methylene Chloride and then charged into the 4-neck reactor. . Then, caustic soda (Sodium hydroxide) (1.23 mol) was dissolved in distilled water to prepare a caustic soda aqueous solution (10%), which was added to the four-neck reactor by dropping it for 240 minutes. After dropping, the mixture was stirred for 60 minutes, phase separated, and the heavy liquid layer was separated. After separating the separated heavy liquid layer in ethanol, washing with distilled water and drying in an oven for 24 hours to obtain a phthalimidine-based polyester oligomer of Formula 6 (number average molecular weight = 6,000). At this time, the n value of Formula 6 was 11.

[Formula 6-1]

[Formula 6-2]

[Formula 6]

Manufacturing example 2: Preparation of polycarbonate oligomer

In a 10 L 4-neck flask, 600 g (2.63 mol) of bisphenol A was dissolved in 3,300 ml (184.6 g, 4.62 mol) of an aqueous solution of 5.6 wt% sodium hydroxide, and then 260 g (2.63 mol) of phosgene was collected in methylene chloride to prepare a Teflon tube (20 mm). ) And reacted slowly. The external temperature was maintained at 0°C. The reactant that passed through the tubular reactor was subjected to an 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 from the 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), tetrabutylammonium Chloride (tetrabutyl ammonium chloride, TBACl) 7.31 g (26.3 mmol, 1 mol% with respect to bisphenol A), triethylamine (tri-ethylamine, TEA) aqueous solution (15% by weight) 1 mL and then reacted for 30 minutes, poly A carbonate oligomer solution was prepared.

Manufacturing example 3: Preparation of polycarbonate block copolymer

To the polycarbonate oligomer solution obtained in Preparation Example 2, 800 g (40% by weight based on the total amount of the monomer compound constituting the copolymer) of Formula 6 obtained in Preparation Example 1 was added, and layer separation occurred. Then, only the organic phase was collected and mixed with the same amount of methylene chloride (2,830 g), 1.1N sodium hydroxide aqueous solution 1,100 mL (20% by volume based on the total mixture), and triethylamine aqueous solution (15% by weight) 150 μL 1 After the time reaction, 1,670 μL of an aqueous triethylamine solution (15% by weight) and 1,280 g of methylene chloride were further added to react for 1 hour. After separating the layers, pure water was added to the organic phase having an increased viscosity, followed by alkali washing to separate. Subsequently, the organic phase was washed with 0.1N hydrochloric acid solution, and then washed repeatedly with distilled water 2 to 3 times. After the washing was completed and the concentration of the organic phase was constant, it was assembled using a predetermined amount of secondary distilled water at 76°C. After the assembly was completed, a polycarbonate block copolymer was prepared by first drying at 110°C for 8 hours, and secondly drying at 120°C for 10 hours.

Manufacturing example 4: Polyarylate Preparation of resin

In a reaction vessel equipped with a stirring device, 100 parts by weight of BisC as a bisphenol component, 0.9961 parts by weight of p-tert-butylphenol (PTBP) as a terminal sealant, 40.9 parts by weight of sodium hydroxide (NaOH) as an alkali, and tri- as a polymerization catalyst An aqueous solution of n-butylbenzylammonium chloride (TBBAC) (50% by weight) was added in 1.66 parts by weight, and dissolved in 2,640 parts by weight of water (aqueous phase). Separately, 79.94 parts by weight of MPC (isophthalic acid chloride/terephthalic acid chloride=1/1 (molar ratio) mixture) was dissolved in 2,020 parts by weight of methylene chloride (organic phase) (BisC:PTBP:MPC:TBBAC:NaOH=99.16:1.68 :100.60:0.68:260 (molar ratio). The aqueous phase was previously stirred, and the organic phase was added to the aqueous phase under strong agitation, and polymerization was performed at 15°C for 2 hours by interfacial polymerization. Thereafter, stirring was stopped, and the aqueous phase and the organic phase were separated by decantation. After removing the aqueous phase, 500 parts by weight of methylene chloride, 3,000 parts by weight of pure water and 10 parts by weight of acetic acid were added to stop the reaction, and stirred at 15°C for 30 minutes. Thereafter, the organic phase was washed 10 times with pure water, and the organic phase was added in methanol to precipitate the polymer. The precipitated polymer was filtered and dried under vacuum at 120° C. for 12 hours to obtain a polyarylate resin.

Example 1 to 9: Polycarbonate resin composition and specimen preparation

The polyester oligomer obtained in Preparation Example 1, the polycarbonate block copolymer obtained in Preparation Example 3, and the polyarylate resin obtained in Preparation Example 4 were mixed at the contents shown in Table 1 below to prepare a polycarbonate resin composition. Then, the polycarbonate resin composition prepared above was melted and kneaded using a twin-screw extruder at a temperature of 310 to 360°C. Subsequently, the melt produced through the extrusion die was cooled to prepare pellets for molding. After the hot pellets were dried for 4 hours or more at a temperature of 90 to 100°C, the prepared pellets were injection molded at a temperature of 320 to 350°C to prepare specimens. The properties of the prepared specimens were measured and evaluated, and the results are shown in Table 1 below.

Comparative example 1 to 6: Polycarbonate resin composition and specimen preparation

The polyester oligomer obtained in Preparation Example 1, the polycarbonate block copolymer obtained in Preparation Example 3, and the polyarylate resin obtained in Preparation Example 4 were mixed at the contents shown in Table 2 below to prepare a polycarbonate resin composition. Then, the polycarbonate resin composition prepared above was melted and kneaded using a twin-screw extruder at a temperature of 310 to 360°C. Subsequently, the melt produced through the extrusion die was cooled to prepare pellets for molding. After the hot pellets were dried for 4 hours or more at a temperature of 90 to 100°C, the prepared pellets were injection molded at a temperature of 320 to 350°C to prepare specimens. The properties of the prepared specimens were measured and evaluated, and the results are shown in Table 2 below.

[Method of measuring properties]

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

(2) Melt Index: The fluidity was measured under conditions of 330° C. and 2.16 kgf according to ASTM D1238.

(3) Impact strength: evaluated according to ASTM D256 (1/8 inch thick, notched Izod).

As shown in Table 1, in Examples 1 to 9 according to the present invention, a polyester oligomer having a specific structure; Polyester-polycarbonate block copolymers of specific structures; And by containing a polyarylate resin in a specific content range, the heat resistance is remarkably excellent (glass transition temperature is 236°C or higher), and at the same time, the balance of physical properties such as fluidity and impact resistance is also excellent (melting index is 20 g/10min or more) , And the impact strength is 66 kgf cm/cm or more).

However, as shown in Table 2, when a small amount of the polyester oligomer is used (Comparative Example 1), the heat resistance is poor, and when a polyester oligomer is used in excess (Comparative Example 2), the impact resistance is poor, the polyarylate resin When is used in excess (Comparative Example 3), the fluidity is significantly reduced, when a small amount of polyarylate resin is used (Comparative Example 4), the heat resistance is lowered, and when the polyester-polycarbonate block copolymer is used alone ( Comparative Example 5), when the heat resistance was lowered and the melt index was lowered, and when the polyarylate resin was used alone (Comparative Example 6), the heat resistance, fluidity, and impact resistance were lowered, and when the polyarylate resin was not used (Comparison) Example 7), heat resistance was relatively reduced. That is, in all of the comparative examples, the heat resistance, fluidity, and impact resistance were not simultaneously satisfactorily satisfied.

Claims (11)

Based on 100 parts by weight of the total polycarbonate resin composition,
(1) 24 to 34 parts by weight of a polyester oligomer having a structure represented by Formula 1 below;
(2) 41 to 67 parts by weight of a polyester-polycarbonate block copolymer obtained by reacting a polyester oligomer having a structure represented by Formula 1 and a polycarbonate oligomer; And
(3) 5 to 34 parts by weight of a polyarylate resin containing a bisphenol component and an aromatic dicarboxylic acid component comprising a compound represented by the following formula (4) as a monomer component,
Polycarbonate resin composition.
[Formula 1]

In Chemical Formula 1,
R ₁ independently represents a hydrogen atom, an alkyl, cycloalkyl, cycloalkylalkyl or aryl group,
X independently represents oxygen or NR ₂ , wherein R ₂ independently represents a hydrogen atom, an alkyl, cycloalkyl, cycloalkylalkyl or aryl group,
R ₃ independently represents an alkylene, cycloalkylene, cycloalkylenealkylene or arylene group,
m is an integer from 2 to 50 independently;
[Formula 4]

In Chemical Formula 4,
R ₈ and R ₉ each independently represent an alkyl group. The method of claim 1, wherein the polyester oligomer having a structure represented by Formula 1 is prepared by condensation reaction of a compound represented by Formula 1-1 and a compound represented by Formula 1-2 below, polycarbonate resin composition :
[Formula 1-1]

[Formula 1-2]

In Chemical 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 2, wherein a reaction molar ratio of the compound of Formula 1-1 to the compound of Formula 1-2 is 1:0.5 to 1:2. The polycarbonate resin composition according to claim 1, wherein the number average molecular weight of the polyester oligomer having the structure of Formula 1 is 500 to 30,000. The polycarbonate resin composition according to claim 1, wherein the polycarbonate oligomer is prepared by a phosgene method using a divalent phenolic compound and phosgene. The polycarbonate resin composition according to claim 5, wherein the divalent phenolic compound is a compound having the structure of formula (2):
[Formula 2]

In Chemical Formula 2,
A is a straight, branched or cyclic alkylene group having no functional group; Or a linear, branched or cyclic alkylene group comprising at least one functional group selected from the group consisting of sulfide, ether, sulfoxide, sulfone, ketone, phenyl, isobutylphenyl or naphthyl,
R ₄ and R ₅ each independently represent a halogen atom or an alkyl group,
m and n are each independently an integer from 0 to 4. The polycarbonate resin composition according to claim 1, wherein the polycarbonate oligomer has a viscosity average molecular weight of 1,000 to 30,000. The amount of the polyester block having the structure of Formula 1 included in the polyester-polycarbonate block copolymer is 100% by weight of the total weight of the monomer compound constituting the polyester-polycarbonate block copolymer. Based on, 0.5 to 55% by weight, polycarbonate resin composition. The polycarbonate resin composition according to claim 1, wherein the polyester-polycarbonate block copolymer has a viscosity average molecular weight of 10,000 to 200,000. The polycarbonate resin composition of claim 1, wherein the polyarylate resin has a structure represented by Formula 5 below:
[Formula 5]

In Chemical Formula 5,
R ₈ and R ₉ are as defined in claim 1,
n is an integer from 2 to 100. A molded article comprising the polycarbonate resin composition of claim 1.