KR20220088578A - Copolymer having balanced good scratch resistance and impact resistance and preparation method thereof, and molded article comprising the same - Google Patents

Abstract

The present invention relates to a copolymer, a method for preparing the same, and a molded article including the same, and more particularly, to a repeating unit derived from an aromatic diol having a fused aromatic ring structure; repeating units derived from diallyl bisphenol; and polycarbonate repeating units; by including in a specific content ratio, while maintaining excellent impact strength, the surface hardness is improved compared to conventional linear polycarbonate and polycarbonate copolymers, resulting in a well-balanced copolymer with excellent scratch resistance and impact resistance and It relates to a manufacturing method thereof, and a molded article including the same.

Description

A copolymer with excellent scratch resistance and impact resistance, and a method for manufacturing the same, and a molded article comprising the same

The present invention relates to a copolymer, a method for preparing the same, and a molded article including the same, and more particularly, to a repeating unit derived from an aromatic diol having a fused aromatic ring structure; repeating units derived from diallyl bisphenol; and polycarbonate repeating units; by including in a specific content ratio, while maintaining excellent impact strength, the surface hardness is improved compared to conventional linear polycarbonate and polycarbonate copolymers, resulting in a well-balanced copolymer with excellent scratch resistance and impact resistance and It relates to a manufacturing method thereof, and a molded article including the same.

Polycarbonate has excellent mechanical properties such as tensile strength and impact resistance, and has excellent dimensional stability, heat resistance, and optical transparency, so it is widely used for industrial purposes. Research on various copolymers is continued in order to improve the physical properties of polycarbonate, for example, a polysiloxane-polycarbonate copolymer has been proposed to improve low-temperature impact resistance (US Patent Publication No. 2003-0105226).

The chemical structure of polycarbonate prepared using bisphenol A and phosgene basically has a hydroxyl group at the terminal group, and a new type of polymer can be prepared by using a method of activating hydroxyl groups of both terminal groups. In this case, polymerization may be performed in an aqueous solution, at an interface, or in a non-aqueous solution.

However, especially polycarbonates made from bisphenol A have limited scratch resistance. Therefore, in order to prevent or minimize the scratch damage, it is necessary to apply a hard coat as a surface modification, which is accompanied by an additional process and cost, and has disadvantages of poor durability.

Korean Patent Registration No. 10-1815930 discloses a polycarbonate copolymer having improved scratch resistance and antifogging properties, and the polycarbonate copolymer disclosed herein exhibits excellent antifogging properties, but scratch resistance. needs further improvement.

Accordingly, there is a demand for the development of a polycarbonate copolymer with improved scratch resistance while maintaining excellent transparency and impact resistance, which are inherent properties of polycarbonate.

The present invention is to solve the problems of the prior art as described above, and while maintaining excellent impact strength, the surface hardness is improved compared to the existing linear polycarbonate and polycarbonate copolymer, so that scratch resistance and impact resistance are excellently balanced. It is a technical task to provide a copolymer, a method for manufacturing the same, and a molded article comprising the same.

The present invention in order to solve the above technical problem, (A) a substituted or unsubstituted, repeating unit derived from an aromatic diol having a fused aromatic ring; (B) repeating units derived from substituted or unsubstituted diallyl bisphenol; and (C) a polycarbonate repeating unit; wherein, with respect to 1 mole of the total of the repeating units (A) and (B), the molar ratio of the repeating unit (A) is greater than 0.2 to less than 0.8, and the repeating unit ( and wherein the molar ratio of B) is greater than 0.2 and less than 0.8.

According to another aspect of the present invention, there is provided a diol component comprising (a) a substituted or unsubstituted aromatic diol having a fused aromatic ring and (b) a substituted or unsubstituted diallyl bisphenol; and (c) copolymerizing a carbonic acid diester compound or a carbonate precursor, wherein the molar ratio of the diol compound (a) to 1 mol in total of the diol compounds (a) and (b) exceeds 0.2 to 0.8 Less than, the molar ratio of the diol compound (b) is more than 0.2 to less than 0.8, a method for producing a copolymer is provided.

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

Since the copolymer according to the present invention exhibits improved scratch resistance while maintaining excellent impact resistance and transparency, molded articles (eg, films, sheets, lenses, cover glasses, interior and exterior materials, etc.) including them are used for optical applications in various industries. And it can be used very suitably for the use of a material lightweight substitute.

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

As used herein, that any group or structure is “substituted” means that the group or structure is a halogen atom (eg, F, Cl or Br), a hydroxy group, an alkyl group (eg, having 1 to 10 carbon atoms, or 1 to 6 carbon atoms). alkyl group), an alkoxy group (eg, an alkoxy group having 1 to 10 carbon atoms, or an alkoxy group having 1 to 6 carbon atoms), a cycloalkyl group (eg, a cycloalkyl group having 3 to 10 carbon atoms or 3 to 6 carbon atoms), an aryl group (eg, 6 carbon atoms) to 12, or an aryl group having 6 carbon atoms) or a combination thereof means substituted by one or more functional groups selected from the group consisting of.

The copolymer of the present invention comprises (A) repeating units derived from aromatic diols having fused aromatic rings, substituted or unsubstituted; (B) repeating units derived from substituted or unsubstituted diallyl bisphenol; and (C) polycarbonate repeating units.

In one embodiment, the repeating unit (A) may be derived from an aromatic diol having a substituted or unsubstituted structure in which 2 to 4 C6-aromatic rings are fused, and more specifically, a substituted or unsubstituted It may be derived from a substituted naphthalene diol, a substituted or unsubstituted phenanthrene diol, or a combination thereof, and more specifically, may be derived from a compound represented by the following formula (1):

[Formula 1]

HO-Z-OH

In Formula 1,

또는

또는 이들의 조합이며,Z is

or

or a combination thereof,

A hydroxyl group (OH) is attached to any carbon that can be bonded while maintaining the aromaticity of Z.

In one embodiment, the repeating unit (B) may be derived from substituted or unsubstituted diallyl bisphenol A, and more specifically, may be derived from a compound of the following structure:

In the copolymer of the present invention, the molar ratio of the repeating unit (A) to 1 mole in total of the repeating units (A) and (B) is more than 0.2 to less than 0.8, and the molar ratio of the repeating unit (B) is greater than 0.2 and less than 0.8. If the molar ratio of the repeating unit (A) is 0.2 or less or the molar ratio of the repeating unit (B) is 0.8 or more with respect to 1 mole of the total of the repeating units (A) and (B) contained in the copolymer of the present invention, the resulting copolymer of the surface hardness (scratch resistance) deteriorates, and conversely, when the molar ratio of the repeating unit (A) is 0.8 or more or the molar ratio of the repeating unit (B) is 0.2 or less, the impact strength (impact resistance) of the resulting copolymer is poor .

More specifically, the molar ratio of the repeating unit (A) to 1 mole in total of the repeating units (A) and (B) included in the copolymer of the present invention is, for example, greater than 0.2, 0.21 or more, 0.23 or more, 0.25 or more, 0.27 or more, 0.29 or more, or 0.3 or more, and may be less than 0.8, 0.79 or less, 0.77 or less, 0.75 or less, 0.73 or less, 0.71 or less, or 0.7 or less, but is not limited thereto.

In addition, more specifically, the molar ratio of the repeating unit (B) to 1 mole in total of the repeating units (A) and (B) contained in the copolymer of the present invention is, for example, more than 0.2, 0.21 or more, 0.23 or more. , 0.25 or more, 0.27 or more, 0.29 or more, or 0.3 or more, and may be less than 0.8, 0.79 or less, 0.77 or less, 0.75 or less, 0.73 or less, 0.71 or less, or 0.7 or less, but is not limited thereto.

According to one embodiment of the present invention, the copolymer of the present invention, the substituted or unsubstituted, aromatic diol having a fused aromatic ring and a diol compound other than the substituted or unsubstituted diallyl bisphenol (hereinafter, “addition It may further include a repeating unit derived from a diol compound of”).

In one embodiment, the additional diol compound may be a dihydric phenol compound.

More specifically, the dihydric phenol compound may be a compound having a structure represented by the following Chemical Formula 2:

[Formula 2]

In Formula 2,

A is a straight, branched or cyclic alkylene group having no functional group; or a straight, branched or cyclic alkylene group (eg, having 1 carbon atom a linear alkylene group having 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 ₁ and R ₂ are each independently a halogen atom (eg, Cl or Br, etc.); or a straight, branched or cyclic alkyl group (eg, a linear alkyl group having 1 to 10 carbon atoms, a branched alkyl group having 3 to 10 carbon atoms, or a cyclic alkyl group having 3 to 10 carbon atoms);

m and n each independently represent the integer of 0-4.

Specifically, the compound of Formula 2 is, for example, bis(4-hydroxyphenyl)methane, bis(4-hydroxyphenyl)phenylmethane, bis(4-hydroxyphenyl)naphthylmethane, bis(4 -Hydroxyphenyl)-(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-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-hydroxy Roxyphenyl)pentane, 4,4-bis(4-hydroxyphenyl)heptane, diphenyl-bis(4-hydroxyphenyl)methane, resorcinol, hydroquinone, 4,4'- Dihydroxyphenyl ether [bis (4-hydroxyphenyl) ether], 4,4'-dihydroxy-2,5-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3' -dichlorodiphenyl 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'- Dihydroxyphenyl, 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-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-hydroxy Phenyl)-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'-dihydroxydiphenyl, methylhydroquinone, 1,5-dihydroxynaphthalene or 2,6-dihydroxynaphthalene may be selected from , but is not necessarily limited thereto. A typical example is 2,2-bis(4-hydroxyphenyl)propane (bisphenol A). Other functional dihydric phenols (dihydric phenol) may refer to US Pat. Nos. 2,999,835, US 3,028,365, US 3,153,008, and US 3,334,154, and the like, and the dihydric phenols are singly or in combination of two or more. can be used

According to one embodiment, in the copolymer of the present invention, the total molar ratio of the repeating units (A) and (B) per mole of the repeating units derived from the total diol component may be greater than 0.7. In the copolymer of the present invention, when the relative content of the sum of the repeating units (A) and (B) is less than the above level, compared to the total repeating units derived from the diol component, the surface hardness (scratch resistance) of the resulting copolymer is can be bad

More specifically, the total molar ratio of the repeating units (A) and (B) per mole of repeating units derived from all the diol components included in the copolymer of the present invention is, for example, 0.71 or more, 0.72 or more, 0.73 or more, 0.74 or more, or 0.75 or more, and may be 1.0 or less, 0.95 or less, 0.9 or less, 0.85 or less, or 0.8 or less, but is not limited thereto.

In one embodiment, when the copolymer of the present invention further includes the repeating unit derived from the additional diol compound, the additional repeating unit derived from the diol compound is included in an amount of less than 0.3 moles per mole of the total repeating unit derived from the diol component. can do.

The polycarbonate repeating unit included in the copolymer of the present invention may be derived from a carbonic acid diester compound or a carbonate precursor.

In one embodiment, the carbonic acid diester compound may be selected from dialkyl carbonate, diaryl carbonate, alkylene carbonate, or a combination thereof.

In one embodiment, examples of the dialkyl carbonate include dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diisobutyl carbonate, ethyl normal butyl carbonate and ethyl isobutyl carbonate, and the dia Examples of the lyl carbonate include diphenyl carbonate, ditolyl carbonate, bis(chlorophenyl) carbonate and di(m-cresyl) carbonate, and examples of the alkylene carbonate include ethylene carbonate, trimethylene carbonate, tetramethylene carbonate, 1,2-propylene carbonate, 1,2-butylene carbonate, 1,3-butylene carbonate, 2,3-butylene carbonate, 1,2-pentylene carbonate, 1,3-pentylene carbonate, 1 ,4-pentylene carbonate, 1,5-pentylene carbonate, 2,3-pentylene carbonate, 2,4-pentylene carbonate and neopentylene carbonate.

In one embodiment, the carbonic acid diester compound may be selected from dimethyl carbonate, diethyl carbonate, diphenyl carbonate, ethylene carbonate, or a combination thereof, more preferably diphenyl carbonate.

In one embodiment, the carbonic acid diester compound may be selected from compounds represented by the following formula (3).

[Formula 3]

In Formula 3, Y and Y' are each independently selected from an unsubstituted or halogen-substituted alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or an aralkyl group having 7 to 25 carbon atoms, Y and Y' may be the same as or different from each other.

In one embodiment, the carbonic acid diester compound represented by Formula 3 is selected from diphenyl carbonate, ditolyl carbonate, bischlorophenyl carbonate, dimethyl carbonate, diethyl carbonate, di-t-butyl carbonate, or mixtures thereof. may be used, but preferably diphenyl carbonate or dimethyl carbonate may be used.

In one embodiment, the carbonate precursor may be selected from the group consisting of phosgene (carbonyl chloride), carbonyl bromide, bishalo formate, diphenyl carbonate, dimethyl carbonate, or a combination thereof.

According to one embodiment, in the copolymer of the present invention, the molar ratio of polycarbonate repeating units per mole of repeating units derived from the total diol component may be 0.9 or more, 0.95 or more, or 0.98 or more, and 1.1 or less, 1.05 or less, or 1.02 or less. can

In the copolymer of the present invention, when the relative content of the polycarbonate repeating unit compared to the total diol component-derived repeating unit is excessively less than the above level, the thermal stability of the copolymer may deteriorate or it may not be possible to obtain a desired level of molecular weight, Conversely, if it is excessively higher than the above level, toxic gas may be generated during copolymer molding, or it may cause decomposition.

In one embodiment, the viscosity average molecular weight of the copolymer of the present invention may be 10,000 to 80,000, but is not limited thereto. If the viscosity average molecular weight of the copolymer is excessively less than the above level, mechanical properties such as impact strength and tensile strength may be reduced, and if it is excessively greater than the above level, moldability may decrease.

The copolymer of the present invention is a random copolymer, and may be prepared using a polymerization method widely known to those of ordinary skill in the art. For example, it can manufacture using the melt polymerization method by transesterification or the phosgene polymerization method.

Accordingly, according to another aspect of the present invention, there is provided a diol component comprising (a) a substituted or unsubstituted aromatic diol having a fused aromatic ring and (b) a substituted or unsubstituted diallyl bisphenol; and (c) copolymerizing a carbonic acid diester compound or a carbonate precursor, wherein the molar ratio of the diol compound (a) to 1 mol in total of the diol compounds (a) and (b) exceeds 0.2 to 0.8 Less than, the molar ratio of the diol compound (b) is more than 0.2 to less than 0.8, a method for producing a copolymer is provided.

According to an embodiment of the present invention, the diol component may further include a diol compound (“additional diol compound”) other than the diol compounds (a) and (b).

Specific types and usage of the diol compounds (a) and (b), additional diol compounds, diester carbonate compounds, and carbonate precursors usable in the method for preparing the copolymer according to the present invention are as described above.

There is no particular limitation on the conditions of the copolymerization reaction, and for example, it may be carried out at room temperature (eg, 20-30°C) or elevated temperature (eg, 150-250°C), but is not limited thereto.

In one embodiment, the method for preparing the copolymer may be carried out in the presence of a catalyst.

A polymerization catalyst and/or a phase transfer catalyst may be used as the catalyst. As the polymerization catalyst, for example, a base catalyst, more specifically, an organic amine catalyst such as triethylamine (TEA) may be used, and as the phase transfer catalyst, for example, a compound of Formula 4 may be used. .

[Formula 4]

(R ₃ ) ₄ Q ⁺ Z ^-

In Formula 4, R ₃ represents an alkyl group having 1 to 10 carbon atoms, Q represents nitrogen or phosphorus, and Z represents a halogen atom or —OR ₄ . Here, R ₄ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms.

Specifically, the phase transfer 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 or CH ₃ [CH ₃ (CH ₂ ) ₂ ] ₃ NZ have. In the above formulas, Z represents Cl, Br or -OR ₄ , wherein R ₄ represents a hydrogen atom, an alkyl group having 1 to 18 carbon atoms, or an aryl group having 6 to 18 carbon atoms. When the phase transfer catalyst is used, the content thereof is preferably 0.01 wt% or more in terms of transparency of the resulting copolymer, but is not limited thereto.

In one embodiment, a molecular weight modifier may be used in the method for preparing the copolymer.

As the molecular weight control agent, a monofunctional compound similar to a monomer used for preparing polycarbonate may be used. The monofunctional substances include, for example, p-isopropylphenol, p-tert-butylphenol (PTBP), p-cumylphenol, p-isooctylphenol and p-isononyl. phenol-based derivatives such as phenol, or aliphatic alcohols. Preferably, p-tert-butylphenol (PTBP) can be used.

In one embodiment, the method for preparing the copolymer may further include extracting the organic phase from the resulting mixture after the copolymerization reaction is completed.

According to one embodiment, after preparing the copolymer, the organic phase dispersed in methylene chloride is separated after washing with alkali. Subsequently, the organic phase is washed with a 0.1N hydrochloric acid solution, and then washed with distilled water 2 to 3 times. When washing is complete, the concentration of the organic phase dispersed in methylene chloride is constantly adjusted, and granulation is performed using a certain amount of pure water in the range of 30 to 100°C, preferably in the range of 60 to 80°C. If the temperature of the pure water is less than 30 ℃, the assembly speed is slow, the assembly time may be very long, and if the temperature of the pure water exceeds 100 ℃, it may be difficult to obtain the shape of the polycarbonate in a certain size. When the assembly is completed, it is preferable to dry at 100 to 120° C. for 5 to 10 hours, more preferably firstly at 100 to 110° C. for 5 to 10 hours, and secondly at 110 to 120° C. for 5 to 10 hours. It can be dried while

Since the copolymer of the present invention exhibits improved scratch resistance while maintaining excellent impact resistance and transparency, molded articles (eg, films, sheets, lenses, cover glasses, interior and exterior materials, etc.) including them are used in various industries for optical applications and It can be used very well for the use of material lightweight substitutes.

Accordingly, according to another aspect of the present invention, there is provided a molded article comprising the copolymer of the present invention. In the present invention, 'molded article' means a molded article by extrusion, injection, or other known processing.

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 thereby.

[Example]

<Preparation of copolymer>

Example 1: Terpolymer prepared by phosgene polymerization using 2,6-naphthalene diol and diallyl bisphenol A

In a 3L three-necked reactor, 125.71 g of 2,6-naphthalene diol (0.7 moles based on 1 mole of total diols) and 103.74 g of diallyl bisphenol A (0.3 moles based on 1 mole of total diols) were mixed with 900 ml of 5.6 wt% aqueous sodium hydroxide solution After dissolving in , 121.14 g of phosgene was collected in methylene chloride and reacted while slowly introducing it through a Teflon tube (5 mm). The external temperature was maintained at 0°C. The reactants passing through the tubular reactor were interfacially reacted for about 10 minutes under a nitrogen atmosphere. After the reaction was completed, 1 L of the reaction product was mixed with 2.98 g of p-tert-butylphenol (PTBP) and 0.24 ml of a trimethylamine catalyst, followed by an interfacial reaction for 1 hour. After separating the layers, the organic phase was taken, sodium hydroxide aqueous solution prepared by dissolving 14 g of sodium hydroxide in 140 g of distilled water and 255 g of methylene chloride were mixed, and 250 μl of triethylamine was added and reacted for 1 hour and 30 minutes. After the reaction was completed, distilled water was added to perform alkali washing, and only the organic phase was separated. The organic phase was washed with 0.1N hydrochloric acid solution, followed by repeated washing with distilled water 3 times. After washing was completed, the concentration of the organic phase was made constant, and then granulated at 80° C. using a certain amount of distilled water. After the assembly was completed, the terpolymer was obtained by drying at 105° C. for 12 hours.

Example 2: Terpolymer prepared by phosgene polymerization using 2,6-naphthalene diol and diallyl bisphenol A

The content of 2,6-naphthalene diol was changed from 125.71 g (0.7 moles based on 1 mole of total diols) to 82.9 g (0.5 moles based on 1 mole of total diols), and the content of diallyl bisphenol A was changed to 103.74 g ( A terpolymer was obtained in the same manner as in Example 1, except for changing from 0.3 mol based on 1 mol of total diols) to 159.6 g (0.5 mol based on 1 mol of total diols).

Example 3: Terpolymer prepared by melt polymerization using 2,6-naphthalene diol and diallyl bisphenol A

In a 2L three-necked condensation reactor, 268.27 g of diphenyl carbonate, 58 g of 2,6-naphthalene diol (0.3 mol based on 1 mol of the total diol), 260.6 g of diallyl bisphenol A (0.7 mol based on 1 mol of the total diol), and 0.0001 g of cesium carbonate was added, and the mixture was stirred while slowly raising the temperature to 180° C. under a nitrogen gas atmosphere. Thereafter, the pressure was gradually lowered to 50 torr over 1 hour, and the temperature of the reactor was raised to 260° C. to continue the reaction while removing phenol, a by-product. A terpolymer was obtained by removing the residual amount of phenol and terminating the reaction while lowering the pressure to 0.1 torr for an additional 1 hour.

Example 4: Quaternary copolymer prepared by melt polymerization using 2,6-naphthalene diol, diallyl bisphenol A and bisphenol A

Diphenyl carbonate is changed from 268.27 g to 312.1 g, and the content of 2,6-naphthalene diol is changed from 58 g (0.3 mol based on 1 mol of the total diol) to 116.6 g (0.5 mol based on 1 mol of the total diol) , the content of diallyl bisphenol A was changed from 260.6 g (0.7 mol based on 1 mol of the total of the total diols) to 112.3 g (0.25 mol based on the total of 1 mol of the total diol), and 83.14 g of bisphenol A (total of the total diols) as a diol compound A quaternary copolymer was obtained in the same manner as in Example 3, except that 0.25 mol based on 1 mol in total) was additionally used.

Example 5: Terpolymer prepared by phosgene polymerization using 2,7-phenanthrene diol and diallyl bisphenol A

A terpolymer was obtained in the same manner as in Example 1, except that 175.9 g of 2,7-phenanthrene diol (0.7 mol based on 1 mol of total diol in total) was used instead of 2,6-naphthalene diol. did

Example 6: Terpolymer prepared by melt polymerization using 2,7-phenanthrene diol and diallyl bisphenol A

A terpolymer was obtained in the same manner as in Example 3, except that 81.2 g of 2,7-phenanthrene diol (0.3 mol based on 1 mol of the total diol in total) was used instead of 2,6-naphthalene diol. did

Comparative Example 1: Preparation of a thermoplastic aromatic polycarbonate (linear polycarbonate) resin

A linear polycarbonate having a viscosity average molecular weight of 21,000 was prepared by a conventional interfacial polymerization method.

Comparative Example 2: Copolymer prepared by phosgene polymerization using 2,6-naphthalene diol

The copolymer was carried out in the same manner as in Example 1, except that only 207.9 g of 2,6-naphthalene diol (1 mol relative to 1 mol of the total diol in total) was used as the diol compound, and diallyl bisphenol A was not used. was obtained.

Comparative Example 3: Copolymer prepared by phosgene polymerization using diallyl bisphenol A

As the diol compound, only 332.63 g of diallyl bisphenol A (1 mol relative to the total of 1 mol of the total diol) was used, 2,6-naphthalene diol was not used, and the content of phosgene was changed from 121.14 g to 106.69 g. was carried out in the same manner as in Example 1 to obtain a copolymer.

Comparative Example 4: Terpolymer prepared by phosgene polymerization using 2,6-naphthalene diol and bisphenol A

The content of 2,6-naphthalene diol was changed from 125.71 g (0.7 moles based on 1 mole of total diols) to 124.79 g (0.5 moles based on 1 mole of total diols), and bisphenol A 177.88 instead of diallyl bisphenol A g (0.5 mol based on 1 mol of the total diol in total) was used, and the same method as in Example 1 was followed to obtain a terpolymer.

Comparative Example 5: Terpolymer prepared by phosgene polymerization using diallyl bisphenol A and bisphenol A

Bisphenol A 138.02 g (0.5 moles based on 1 mole of total diols) was used instead of 2,6-naphthalene diol, and the content of diallyl bisphenol A was changed from 103.74 g (0.3 moles based on 1 mole of total diols) to 186.46 A terpolymer was obtained in the same manner as in Example 1, except that it was changed to g (0.5 mol based on 1 mol of the total diol in total).

Comparative Example 6: Terpolymer prepared by phosgene polymerization using 2,6-naphthalene diol and diallyl bisphenol A

The content of 2,6-naphthalene diol was changed from 125.71 g (0.7 moles based on 1 mole of total diols) to 35.91 g (0.2 moles based on 1 mole of total diols), and the content of diallyl bisphenol A was changed to 103.74 g ( A terpolymer was obtained in the same manner as in Example 1, except for changing from 0.3 mol based on 1 mol of the total diol) to 276.64 g (0.8 mol based on the total 1 mol of the total diol).

Comparative Example 7: Terpolymer prepared by melt polymerization using 2,6-naphthalene diol and diallyl bisphenol A

The content of 2,6-naphthalene diol was changed from 58 g (0.3 mol based on 1 mol of the total diol in total) to 143.66 g (0.8 mol based on 1 mol of the total diol in the total), and the content of diallyl bisphenol A was changed to 260.6 g (total of 1 mol) A terpolymer was obtained in the same manner as in Example 3 except for changing from 0.7 mol based on 1 mol of the total diol) to 69.16 g (0.2 mol based on the total 1 mol of the total diol).

[Method of measuring physical properties]

(1) Pencil hardness (scratch resistance)

Yasuda SEIKI's No. The pencil hardness of each specimen of the polyester-polycarbonate block copolymer of Examples and Comparative Examples was measured using a 553-M1 pencil hardness tester. Specifically, the sharpest pencil concentration symbol just before the drawing was scratched at a 45° angle and the coating film was ruptured and scratched was shown as the pencil hardness value.

Pencil hardness is in the order of 9H (highest)-8H-7H-6H-5H-4H-3H-2H-H-F-HB-B-2B-3B-4B-5B-6B-7B-8B-9B (lowest) to lower the hardness.

(2) Impact strength (impact resistance)

Based on ASTM D256, each specimen of Examples and Comparative Examples was evaluated by cutting a notch, and the final test result was performed 10 times for each specimen, and the average value of the 10 test results was calculated.

The composition and physical property values of the copolymers of Examples 1 to 6 and Comparative Examples 1 to 7 are shown in Table 1 below.

[Table 1]

As shown in Table 1, in the case of the copolymers of Examples 1 to 6 according to the present invention, while maintaining excellent impact strength at 40 kg _f cm / cm or more, it is possible to improve the pencil hardness to H or more, Balanced physical properties of scratch resistance and impact resistance can be secured. On the other hand, in the case of the copolymers of Comparative Examples 1 to 7, the pencil hardness was less than H, or the impact strength was less than 40 kg _f cm/cm, and it was not possible to secure balanced physical properties of scratch resistance and impact resistance.

Claims (10)

(A) substituted or unsubstituted repeat units derived from aromatic diols having fused aromatic rings;
(B) repeating units derived from substituted or unsubstituted diallyl bisphenol; and
(C) polycarbonate repeating unit;
The molar ratio of the repeating unit (A) is greater than 0.2 to less than 0.8, and the molar ratio of the repeating unit (B) is greater than 0.2 to less than 0.8, with respect to a total of 1 mole of the repeating units (A) and (B),
copolymer. The copolymer according to claim 1, wherein the repeating unit (A) is derived from an aromatic diol having a structure in which 2 to 4 C 6 -aromatic rings, substituted or unsubstituted, are fused. The copolymer according to claim 1, wherein the repeating unit (A) is derived from a substituted or unsubstituted naphthalene diol, a substituted or unsubstituted phenanthrene diol, or a combination thereof. The copolymer according to claim 1, wherein the repeating unit (B) is derived from substituted or unsubstituted diallyl bisphenol A. 2. The method of claim 1, further comprising repeating units derived from an additional diol compound which is a diol compound other than the substituted or unsubstituted, aromatic diol having a fused aromatic ring and the substituted or unsubstituted diallyl bisphenol. copolymer. The copolymer according to claim 5, wherein the additional diol compound is a compound having the structure of formula (2):
[Formula 2]

In Formula 1,
A is a straight, branched or cyclic alkylene group having no functional group; or a straight, branched or cyclic alkylene group comprising at least one functional group selected from the group consisting of a sulfide group, an ether group, a sulfoxide group, a sulfone group, a ketone group, a phenyl group, an isobutylphenyl group or a naphthyl group,
R ₁ and R ₂ are each independently a halogen atom; or a straight, branched or cyclic alkyl group,
m and n each independently represent the integer of 0-4. The copolymer according to claim 1, wherein the total molar ratio of the repeating units (A) and (B) per mole of all repeating units derived from the diol component is greater than 0.7. The copolymer of claim 1 , wherein the polycarbonate repeat unit is derived from a carbonic acid diester compound or a carbonate precursor. a diol component comprising (a) a substituted or unsubstituted aromatic diol having a fused aromatic ring and (b) a substituted or unsubstituted diallyl bisphenol; And (c) a carbonic acid diester compound or carbonate precursor; comprising the step of copolymerizing,
With respect to a total of 1 mole of the diol compounds (a) and (b), the molar ratio of the diol compound (a) is more than 0.2 to less than 0.8, and the molar ratio of the diol compound (b) is more than 0.2 to less than 0.8,
A method for preparing a copolymer. A molded article comprising the copolymer according to any one of claims 1 to 8.