WO2017003123A1 - Copolycarbonate resin and preparation method therefor - Google Patents

Abstract

The present invention relates to a polycarbonate resin and a preparation method therefor, and has an effect of providing a polycarbonate resin, which has excellent chemical resistance and abrasion resistance by applying a predetermined comonomer, and a preparation method therefor.

Description

Copolycarbonate resin and preparation method thereof

[Reciprocal citation with application (s)]

This application claims the benefit of priority based on Korean Patent Application No. 10-2015-0094030 dated July 01, 2015, and all content disclosed in the literature of that Korean patent application is incorporated as part of this specification.

The present disclosure relates to a copolycarbonate resin and a method for producing the same, and more particularly, to a copolycarbonate resin having a superior chemical resistance and abrasion resistance by applying a predetermined comonomer and a method for producing the same.

Polycarbonate resins are prepared by condensation polymerization of aromatic diols such as bisphenol A and carbonate precursors such as phosgene. It is applied to a wide range of fields.

In order to apply such polycarbonate resins in recent years, many studies have been attempted to obtain desired physical properties by copolymerizing two or more different types of aromatic diols and introducing units having different structures into the main chain of polycarbonate.

However, the polycarbonate resin has a problem that it is difficult to apply to a product that requires high chemical resistance and wear resistance because of poor chemical resistance and wear resistance.

[Prior art document]

[Patent Documents]

Korean Unexamined Patent Publication No. 2002-0016922 (2002.03.06)

In order to solve the problems of the prior art, it is an object of the present invention to provide a copolycarbonate resin containing a predetermined modified poly (alkylene dicarboxylate) as a comonomer and a method for producing the same.

Moreover, an object of this invention is to provide the molded article manufactured from the said copolycarbonate resin.

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

In order to achieve the above object, the present disclosure provides a polymerized copolycarbonate resin including a bisphenol-based monomer, a comonomer represented by the following formula (1), and a carbonate precursor.

[Formula 1]

(The R ₁ and R ₂ are independently alkylene having 1 to 10 carbon atoms, n is an integer of 1 to 50)

In addition, the present disclosure provides a method for producing a copolycarbonate resin, comprising the step of interfacial polymerization including a bisphenol-based monomer, a comonomer represented by Formula 1, and a carbonate precursor.

The present invention also provides a molded article prepared from the copolycarbonate resin.

According to the present disclosure there is an effect of providing a copolycarbonate resin having a good chemical resistance and abrasion resistance by applying a predetermined comonomer and a method for producing the same.

Hereinafter, the present description will be described in detail.

The present inventors have found that when a modified poly (alkylene dicarboxylate) in which both ends of a poly (alkylene dicarboxylate) are modified with 4-hydroxybenzoic acid is used as a comonomer of a polycarbonate resin, It was confirmed that the chemical resistance and the wear resistance of the carbonate resin were greatly improved, and based on this, the present disclosure was completed.

The copolycarbonate resin of the present disclosure is characterized by including a bisphenol-based monomer, a comonomer represented by the following formula (1) and a carbonate precursor.

[Formula 1]

(The R ₁ and R ₂ are independently alkylene having 1 to 10 carbon atoms, n is an integer of 1 to 50)

For example, R ₁ and R ₂ are independently alkylene having 2 to 6 carbon atoms or alkylene group having 3 to 5 carbon atoms, and have excellent effects of chemical resistance and wear resistance within this range.

N is an integer of 5-40 or an integer of 10-30, for example, and there exists an effect excellent in chemical resistance and abrasion resistance within this range.

The comonomer represented by Chemical Formula 1 is, for example, as shown in Scheme 1 below, 1) polycondensation reaction of alkanediol and dicarboxylic acid to synthesize poly (alkylene dicarboxylate), 2) thus synthesized It can be prepared by esterifying poly (alkylene dicarboxylate) and 4-hydroxybenzoic acid.

Scheme 1

The esterification reaction of 2) is another reaction of poly (alkylene dicarboxylate) and 4-acetoxybenzoyl chloride and then hydrolyzing the product under a base catalyst to convert acetoxy groups to hydroxy groups. Can be.

The 4-acetoxybenzoyl chloride can be prepared by, for example, chlorination of 4-acetoxybenzoic acid, and the cloning is not particularly limited in the case of the method of normally cloning carboxylic acid. .

Catalysts, solvents and other reaction conditions used in the polycondensation reaction and esterification reaction are generally limited in the case of catalysts, solvents and other reaction conditions used in the condensation polymerization reaction or esterification reaction of diol compounds and dicarboxylic acids. Instead, it can select and use suitably as needed.

For example, the comonomer may be included in an amount of 0.1 to 19% by weight, 0.1 to 15% by weight, 0.5 to 10% by weight, or 0.5 to 5% by weight based on the total weight of the bisphenol-based monomer and the comonomer. It is effective in chemical resistance and wear resistance.

For example, the comonomer represented by Chemical Formula 1 has a tin content of 10 mass ppm or less (as an element) or 5 mass ppm (as an element), and in this case, the thermal stability of the copolycarbonate resin produced, particularly at high temperatures Stability is excellent effect.

The tin content may be achieved by, for example, treating a reaction mixture including the compound represented by Chemical Formula 1 with an aqueous solution of phosphoric acid or a solid adsorbent, but is not limited thereto.

For example, an organic solvent such as methylene chloride may be used as the organic phase or the diluent when treating the aqueous phosphoric acid solution or the solid adsorbent.

The aqueous solution of phosphoric acid may be, for example, 0.5 to 40% by mass, 1.0 to 10% by mass, or 2 to 5% by mass. Within this range, the extraction efficiency and economic efficiency of the tin compound are excellent, and the effect of minimizing environmental damage is excellent. have.

The solid adsorbent is not particularly limited in the case of a solid adsorbent capable of adsorbing tin compounds, for example, activated clay; Acidic clay; Ion exchange resins; Chelate resins; Activated carbon; Composite adsorbents composed of silica, magnesia, alumina and the like; And the like.

As another example, the comonomer represented by Formula 1 has a hydroxybenzoic acid content of 500 mass ppm or less, or 100 mass ppm or less, and in this case, the thermal stability of the manufactured copolycarbonate resin is excellent, particularly at high temperature. In addition, there is an effect that separation of the aqueous phase and the organic phase in the washing step during the interfacial polymerization of the copolycarbonate resin.

As another example, the comonomer represented by Formula 1 has a hydroxybenzoic acid alkyl ester content of 1.0% by mass or less, or 0.5% by mass or less, in which case the thermal stability of the copolycarbonate resin prepared, in particular, the thermal stability at high temperature This is excellent, and there is an effect of minimizing the molecular weight fluctuation by the hydroxybenzoic acid alkyl ester that can act as an end terminator during interfacial polymerization of the copolycarbonate resin.

The tin content may be measured using, for example, an inductively coupled plasma optical emission spectrometry (ICP-OES) device, and may be measured according to JIS K0116 using ICP-OES SPS-5100 manufactured by SII NanoTechnology.

The hydroxybenzoic acid and the hydroxybenzoic acid alkyl ester content may be measured using, for example, a high-performance liquid chromatography (HPLC) apparatus. As a specific example, a GL science ODS-3 column may be used, and the column temperature is 40 ° C. : Mixed solution of 0.5 mass% phosphoric acid aqueous solution and acetonitrile (1: 2 to capacity), flow rate: 1.0 ml / min, based on a calibration curve of hydroxybenzoic acid and hydroxybenzoic acid alkyl ester standard. .

Examples of the bisphenol monomers include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide and bis ( 4-hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2,2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 2,2-bis (4-hydroxy-3,5-dibro Mophenyl) propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis ( 4-hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1 With 1-bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, α, ω-bis [3- (ο-hydroxyphenyl) propyl] polydimethylsiloxaneIt may be at least one member selected from the group true luer, preferably from bisphenol A, in which case the effect of increasing the fluidity of the resin.

The bisphenol-based monomer is, for example, 81 to 99.9% by weight, 85 to 99.9% by weight, 90 to 99.5% by weight, or 95 to 99.5% by weight relative to the total weight of the bisphenol-based monomers and comonomers, within this range Intrinsic properties of the carbonate resin has an excellent effect.

The carbonate precursor may be, for example, a compound represented by the following Chemical Formula 2, and has an effect of imparting essential properties of the polycarbonate resin within this range.

[Formula 2]

(X ₁ , X ₂ are independently halogen, haloalkyl group, halocycloalkyl group, haloaryl group, alkoxy group or haloalkoxy group.)

In another example, the carbonate precursor is dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, ditoryl carbonate, bis (chlorophenyl) carbonate, di-m-cresyl carbonate, dinaphthyl Carbonate, bis (diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene and bishaloformate, and may be at least one selected from the group consisting of triphosgene or phosgene, in which case polycarbonate There is an effect of imparting essential properties of the resin.

The carbonate precursor may be, for example, 10 to 150 parts by weight, 30 to 100 parts by weight, or 40 to 70 parts by weight based on 100 parts by weight of the total weight of the bisphenol-based monomer and comonomer, and within this range, a polycarbonate resin The intrinsic properties of have excellent effects.

The copolycarbonate may be polymerized by further including, for example, a molecular weight regulator.

The molecular weight modifier may be, for example, mono-alkylphenol.

The mono-alkylphenols are, for example, p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, ecosylphenol, docosylphenol and triacontyl. It is 1 or more types chosen from the group which consists of phenols, Preferably it is para-tert- butylphenol, In this case, a molecular weight control effect is large.

The molecular weight modifier may be, for example, 0.1 to 10 parts by weight, 0.1 to 6 parts by weight, or 1 to 5 parts by weight based on 100 parts by weight of the total weight of the bisphenol-based monomer and the comonomer, and may be a target within this range. ) Molecular weight can be obtained.

For example, the copolycarbonate resin may have a weight average molecular weight of 10,000 to 50,000 g / mol, 25,000 to 45,000 g / mol, or 20,000 to 40,000 g / mol, and has excellent chemical resistance and wear resistance within this range. .

The copolycarbonate resin, for example, has a weight loss amount of 10% by weight after contact with an aqueous 20 wt% HCl solution according to ASTM D543 method for 168 hours, and has excellent chemical resistance within this range.

The copolycarbonate resin is, for example, 10% by weight, preferably 3% by weight or less, after contact with methanol for 168 hours based on ASTM D543 method, and has excellent chemical resistance within this range.

% Weight reduction of the present description means ((weight before contact-weight after contact) / weight before contact) X 100.

The copolycarbonate resin is, for example, wear resistance according to the ASTM D3363 method is 1B or more, preferably HB or more, there is an effect that can be applied to products that require high wear resistance within this range.

The copolycarbonate resin composition of the present disclosure is characterized in that it comprises 100 parts by weight of the copolycarbonate resin, 0.005 to 0.5 parts by weight of the diphosphite compound, 0.001 to 0.5 parts by weight of alicyclic epoxy compound and 0.01 to 1 part by weight of modified silicone. .

The diphosphite compound is, for example, bis (2,4-dicumylphenyl) pentaerythritol diphosphite, and, for example, may be Doverphos S-9228PC manufactured by Dover Chemical, having a residual sodium component of 1 mass ppm or less, in this case, high temperature. It has an excellent thermal stability during molding and excellent light transmittance, brightness and weather resistance.

The alicyclic epoxy compound is, for example, 1,2 of 3,4-epoxycyclohexenylmethyl-3 ', 4'-epoxycyclohexenecarboxylate and 2,2-bis (idoxymethyl) -1-butanol. -Epoxy-4- (2-oxyranyl) cyclohexane adducts and mixtures thereof, specifically 2021P, EHPE3150 or EHPE3150CE from Daicel Chemical Industries, Ltd.

The modified silicone is, for example, a functional group-containing modified silicone compound in which at least one group of methoxy group, vinyl group and phenyl group is introduced into the silicone compound, preferably organopolysiloxane having a phenyl group, methoxy group and vinyl group. It may be KR511 of Shin-Etsu Chemical Co., Ltd., in which case there is an effect of improving the thermal stability during molding.

Method for producing a copolycarbonate resin of the present substrate is characterized in that it comprises a step of interfacial polymerization including a bisphenol-based monomer, a comonomer represented by the formula (1) and a carbonate precursor.

[Formula 1]

(The R ₁ and R ₂ are independently alkylene having 1 to 10 carbon atoms, n is an integer of 1 to 50)

For example, R ₁ and R ₂ are independently an alkylene having 2 to 6 carbon atoms or an alkylene group having 3 to 5 carbon atoms, and have excellent effects of chemical resistance and wear resistance within this range.

N is an integer of 5-40 or an integer of 10-30, for example, and there exists an effect excellent in chemical resistance and abrasion resistance within this range.

The interfacial polymerization can be polymerized at atmospheric pressure and low temperature, for example, and has an effect of easily controlling the molecular weight.

The interfacial polymerization may be carried out by further including at least one of an acid binder, an organic solvent and a reaction accelerator.

For example, the interfacial polymerization may include a step of prepolymerization, a coupling agent, and then polymerization again. In this case, a high molecular weight copolycarbonate resin may be obtained.

The other materials used for the interfacial polymerization are not particularly limited when the materials can be used for the polymerization of polycarbonate, and the amount of the materials used may be adjusted as necessary.

The acid binder may be, for example, an alkali metal hydroxide such as sodium hydroxide or potassium hydroxide, or an amine compound such as pyridine.

The organic solvent is not particularly limited in the case of a solvent usually used for polymerization of polycarbonate, and may be, for example, a halogenated hydrocarbon such as methylene chloride and chlorobenzene.

The interfacial polymerization is, for example, reactions such as tertiary amine compounds such as triethylamine, tetra-n-butylammonium bromide, tetra-n-butylphosphonium bromide, quaternary ammonium compounds, and quaternary phosphonium compounds to promote reaction. Accelerators may be used further.

The reaction temperature of the interfacial polymerization is, for example, 0 to 40 ℃, the reaction time is for example 10 minutes to 5 hours, the pH of the reaction may be preferably maintained at 9 or more or 11 or more, for example.

The interfacial polymerization may be carried out by further including, for example, a molecular weight regulator, which may be added before the start of the polymerization, during the start of the polymerization or after the start of the polymerization.

The molded article of the present disclosure is characterized by containing the copolycarbonate resin of the present disclosure.

The molded article may be, for example, an injection molded article.

The molded article may further include one or more selected from the group consisting of, for example, antioxidants, heat stabilizers, light stabilizers, plasticizers, antistatic agents, nucleating agents, flame retardants, lubricants, impact modifiers, fluorescent brighteners, ultraviolet absorbers, pigments and dyes. Can be.

The method for producing the molded article is, for example, after mixing the copolycarbonate resin and the additives, such as antioxidants of the present invention well using a mixer, the mixture is extruded into an extruder to produce a pellet, and then dried It may include the step of injection into an injection molding machine.

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

EXAMPLE

Example 1

<Preparation of modified poly (alkylene dicarboxylate) comonomer>

4-hydroxybenzoic acid modified poly (butylene adipate) was prepared by esterifying poly (1,4-butylene adipate) having an average Mn of 2,000 (n = 10) with 4-hydroxybenzoic acid.

The structure of the prepared 4-hydroxybenzoic acid modified poly (butylene adipate) was confirmed by ¹ H NMR and ¹³ C NMR.

<Production of Copolycarbonate Resin>

2044 g of water, 140 g of NaOH, and 225.04 g (corresponding to 97 wt%) of BPA (bisphenol A) were added to the polymerization reactor, and the mixture was dissolved under N ₂ atmosphere. Here, 4.6 g of PTBP (para-tert butylphenol) and 6.96 g (corresponding to 3% by weight) of 4-hydroxybenzoic acid-modified poly (butylene adipate) prepared above were dissolved and dissolved in MC (methylene chloride). Then, 128 g of TPG (triphosgene) was dissolved in MC, and the pH was maintained at 11 or more. The reaction was carried out for 1 hour, and after 10 minutes, 46 g of TEA (triethylamine) was added for a coupling reaction. After 1 hour and 20 minutes of total reaction time, the pH was lowered to 4 to remove TEA, and the resulting polymer was washed three times with distilled water to adjust the pH of the produced polymer to 6-7 neutral. The polymer thus obtained was obtained by reprecipitation in a mixed solution of methanol and hexane and then dried at 120 ° C. to obtain a final copolycarbonate resin.

The obtained copolycarbonate resin measured molecular weight by GPC using PC standard (Standard) to confirm that the weight average molecular weight is 29,700 g / mol.

Preparation of Injection Specimen

0.050 parts by weight of tris (2,4-di-tert-butylphenyl) phosphite and octadecyl-3- (3,5-di-tert-butyl-4-hydroxyphenyl) in 100 parts by weight of the prepared copolycarbonate resin After adding 0.010 parts by weight of propionate and 0.030 parts by weight of pentaerythritol tetrastearate, pelletizing it with a vented HAAK Mini CTW, and using a HAAK Minijet injection molding machine, a cylinder temperature of 300 ° C. and a mold temperature of 120 ° C. Haze specimens were prepared by injection molding with Izod specimens and Disk (1.5 mm height, 40 mm diameter).

Example 2

Except for using comonomer 11.6 g (corresponding to 5% by weight) and bisphenol A in 220.4 g (corresponding to 95% by weight) in Example 1, copolycarbonate and its Injection specimens were prepared.

The obtained copolycarbonate resin measured molecular weight by GPC using PC standard (Standard) to confirm that the weight average molecular weight is 29,800 g / mol.

Example 3

Copolycarbonate and its injection in the same manner as in Example 1, except that 23.2 g (corresponding to 10% by weight) of comonomer and 208.8 g (corresponding to 90% by weight) of bisphenol was used in Example 1. Specimen was prepared.

The obtained copolycarbonate resin was measured by GPC using PC standard (Standard) to determine the weight average molecular weight of 29,600 g / mol.

Comparative Example 1

Except not using a comonomer in Example 1, polycarbonate and an injection specimen thereof was prepared in the same manner as in Example 1.

The obtained copolycarbonate resin measured molecular weight by GPC using PC standard (Standard) to confirm that the weight average molecular weight is 29,700 g / mol.

Comparative Example 2

In Example 1, except that 46.4g (corresponding to 20% by weight) of the comonomer and 185.6g (corresponding to 80% by weight) of bisphenol A, the copolycarbonate and the same method as in Example 1 Injection specimens were prepared.

The obtained copolycarbonate resin measured molecular weight by GPC using PC standard (Standard) to confirm that the weight average molecular weight is 29,900 g / mol.

[Test Example]

The properties of the injection specimens prepared in Examples 1 to 3 and Comparative Examples 1 and 2 were measured by the following method, and the results are shown in Table 1 below.

* Chemical resistance: The weight loss was measured by contacting the solvent for 168 hours according to ASTM D543 method (Evaluation criteria: ◎-Excellent (1 ~ 3wt% reduction), ○-Good (3-10%), △-Poor ( HCl concentration: 20%, NaOH concentration: 1%

* Wear resistance: measured according to ASTM D3363 method.

* Impact strength (J / m): measured at 23 ° C based on ASTM D256 (1/8 inch, Notched Izod).

* Weight average molecular weight (g / mol): Agilent 1200 series was measured using a PC standard calibration.

Example Comparative example One 2 3 One 2 Co-monomer wt% 3 5 10 Ｘ 20 Chemical resistance (solvent) HCI ○ ○ ○ △ ◎ NaOH ○ ○ △ ○ MeOH ○ ○ ◎ △ ◎ Toluene △ ○ ○ △ ○ Wear resistance 1B 1B HB 2B HB Impact strength j / m 870 870 860 880 600

As shown in Table 1, the copolycarbonate resins (Examples 1 to 3) of the present disclosure are conventional copolycarbonate resins (Comparative Example 1) or copolycarbonate resins in which an excessive amount of the comonomer of Formula 1 is used (compared to Compared with Example 2) it was confirmed that the chemical resistance and wear resistance is improved without reducing the impact strength.

Reference Examples 1 to 3

When working up the reaction mixture containing 4-hydroxybenzoic acid-modified poly (butylene adipate) obtained in Example 1, methylene chloride was used as an organic layer solvent or diluent and impurities were extracted with a 3.5 mass% phosphoric acid aqueous solution. 4-hydroxybenzoic acid-modified poly (butylene adipate) comonomers subjected to a process of adsorbing with a silica magnesia-based adsorbent (Mizuka Life, F-2G) and the same as in Examples 1 to 3 When used in the production of copolycarbonate resin by the method it was confirmed that the amount of change (△ YI) of the yellowness (△ Yellow Index) of the final prepared specimens decreased to a significant extent.

Reference Examples 4-6

100 parts by weight of copolycarbonate resin obtained in Example 1, 0.02 parts by weight of bis (2,4-dicumylphenyl) pentaerythritol diphosphite (Doverphos S-9228PC), 3,4-epoxy Organopolysiloxane (Shin-Etsu Chemical Co., Ltd. product) which has 0.02 weight part of cyclohexenyl methyl-3 ', 4'- epoxycyclohexene carboxylate (made by Daicel Chemical Industry Co., Ltd., 2021P) and a phenyl group, a methoxy group, and a vinyl group. KR511) 0.1 part by weight was injected by the method used in <Production of Injection Specimen> of Example 1 to prepare a physical specimen, and the specimen was subjected to retention molding and left for 500 hours under an environment of 95% RH with 85 ° C humidity. As a result of the severe heat and humidity test, it was confirmed that there is little discoloration and cracks do not occur.

Claims (20)

It is polymerized including a bisphenol-based monomer, a comonomer represented by the following formula (1) and a carbonate precursor, characterized in that the comonomer is 0.1 to 19% by weight based on the total weight of the bisphenol-based monomer and comonomer Copolycarbonate resin. [Formula 1]

(The R ₁ and R ₂ are independently alkylene having 1 to 10 carbon atoms, n is an integer of 1 to 50) The method of claim 1, The carbonate precursor is characterized in that it comprises 10 to 150 parts by weight based on 100 parts by weight of the total weight of the bisphenol-based monomers and comonomers Copolycarbonate resin. The method of claim 1, The bisphenol monomers include bis (4-hydroxyphenyl) methane, bis (4-hydroxyphenyl) ether, bis (4-hydroxyphenyl) sulfone, bis (4-hydroxyphenyl) sulfoxide, bis (4- Hydroxyphenyl) sulfide, bis (4-hydroxyphenyl) ketone, 1,1-bis (4-hydroxyphenyl) ethane, 2,2-bis (4-hydroxyphenyl) propane (bisphenol A), 2, 2-bis (4-hydroxyphenyl) butane, 1,1-bis (4-hydroxyphenyl) cyclohexane (bisphenol Z), 2,2-bis (4-hydroxy-3,5-dibromophenyl Propane, 2,2-bis (4-hydroxy-3,5-dichlorophenyl) propane, 2,2-bis (4-hydroxy-3-bromophenyl) propane, 2,2-bis (4- Hydroxy-3-chlorophenyl) propane, 2,2-bis (4-hydroxy-3-methylphenyl) propane, 2,2-bis (4-hydroxy-3,5-dimethylphenyl) propane, 1,1 -Bis (4-hydroxyphenyl) -1-phenylethane, bis (4-hydroxyphenyl) diphenylmethane, α, ω-bis [3- (ο-hydroxyphenyl) propyl] polydimethylsiloxane At least one member selected from the group Copolycarbonate resin. The method of claim 1, The carbonate precursor is represented by the formula [Formula 2]

(X ₁ , X ₂ is independently a compound represented by halogen, haloalkyl group, halocycloalkyl group, haloaryl group, alkoxy group or haloalkoxy group) Copolycarbonate resin. The method of claim 1, The copolycarbonate further comprises a molecular weight modifier Copolycarbonate resin. The method of claim 5, The molecular weight modifier is characterized in that the mono-alkylphenol Copolycarbonate resin. The method of claim 5, The molecular weight regulator is characterized in that it comprises 0.1 to 10 parts by weight based on 100 parts by weight of the total weight of the bisphenol-based monomer and comonomer combined Copolycarbonate resin. The method of claim 1, The copolycarbonate resin is characterized in that 10,000 to 50,000 g / mol Copolycarbonate resin. The method of claim 1, The copolycarbonate resin is characterized in that the weight loss after contact with a 20 wt% HCl aqueous solution for 168 hours according to ASTM D543 method is 10% by weight or less Copolycarbonate resin. The method of claim 1, The copolycarbonate resin has a wear resistance of 1B or more according to ASTM D3363 method Copolycarbonate resin. Interfacial polymerization including a bisphenol-based monomer, a comonomer represented by the following formula (1) and a carbonate precursor Method for producing copolycarbonate resin. [Formula 1]

(The R ₁ and R ₂ are independently alkylene having 1 to 10 carbon atoms, n is an integer of 1 to 50) The method of claim 11, The interfacial polymerization is characterized in that it is carried out further comprising a molecular weight modifier. Method for producing copolycarbonate resin. The method of claim 11, The interfacial polymerization is carried out further comprising at least one of an acid binder, an organic solvent and a reaction accelerator. Method for producing copolycarbonate resin. The method of claim 11, The comonomer represented by Formula 1 is characterized in that the tin content is 10 ppm by mass or less (as an element) Method for producing copolycarbonate resin. The method of claim 11, The comonomer represented by Formula 1 has a hydroxybenzoic acid content of 500 mass ppm or less. Method for producing copolycarbonate resin. The method of claim 11, The comonomer represented by Formula 1 is characterized in that the hydroxybenzoic acid alkyl ester content is 1.0% by mass or less Method for producing copolycarbonate resin. Claim 1 to 10, characterized in that it comprises 100 parts by weight of the copolycarbonate resin of claim 1, 0.005 to 0.5 parts by weight of the diphosphite compound, 0.001 to 0.5 parts by weight of alicyclic epoxy compound and 0.01 to 1 parts by weight of modified silicone doing Copolycarbonate resin composition. The method of claim 17, The diphosphite compound is bis (2,4-dicumylphenyl) pentaerythritol diphosphite, characterized in that Copolycarbonate resin composition. A copolycarbonate resin according to any one of claims 1 to 10, characterized by comprising Molded products. The method of claim 19, The molded article is characterized in that the injection molded article Molded products.