Polycarbonate composite composition and its preparation method

Abstract

A polycarbonate composite composition is provided that exhibits improved surface hardness while maintaining impact strength. The polycarbonate composite composition comprising polycarbonate and specific ester repeating units according to the invention is characterized by excellent surface hardness while retaining the inherent basic physical properties of polycarbonate.

Description

Technical Field

[0001] Cross-reference to related applications

[0002] This application is based on and claims priority to Korean Patent Applications No. 10-2021-0075030 and No. 10-2022-0069251, filed on June 9, 2021 and June 8, 2022, respectively, the disclosures of which are incorporated herein by reference in their entirety.

[0003] This invention provides a polycarbonate composite composition with excellent impact strength and surface hardness. Background Technology

[0004] Polycarbonate resin is prepared by polycondensation of aromatic glycols such as bisphenol A and carbonate precursors such as phosgene. It possesses excellent impact strength, dimensional stability, heat resistance, and transparency. Therefore, polycarbonate resin has a wide range of applications, including exterior materials for electrical and electronic products, automotive parts, building materials, and optical components.

[0005] Recently, numerous studies have been conducted to apply these polycarbonate resins to a wider range of fields by copolymerizing two or more aromatic glycol compounds with different structures and introducing monomers with different structures into the polycarbonate backbone to obtain the desired physical properties. In particular, with the recent increase in demand for glass alternative plastics, it is necessary to study polycarbonates with suitable physical properties for use in internal / external materials.

[0006] On the other hand, although existing scratch-resistant polycarbonates possess excellent surface hardness, their low impact strength limits their application as internal / external materials. Therefore, it is necessary to develop polycarbonates that exhibit improved impact resistance at room temperature while maintaining improved surface hardness properties by compensating for the reduced impact strength of scratch-resistant polycarbonates.

[0007] Therefore, the inventors have discovered a polycarbonate composite composition that satisfies the above conditions, which is prepared by compounding an existing polycarbonate with a polymer containing ester repeating units from an aromatic diol, as described below, thereby completing the present invention. Summary of the Invention

[0008] Technical issues

[0009] A polycarbonate composite composition is provided that exhibits excellent impact resistance at room temperature while maintaining the physical properties of existing scratch-resistant polycarbonates, as well as a method for preparing the composition.

[0010] Technical solution

[0011] To address the above problems, a polycarbonate composite composition is provided comprising a polycarbonate containing repeating units represented by Formula 1 below; and a polymer containing repeating units represented by Formula 2 below, wherein the polycarbonate containing repeating units represented by Formula 1 has a weight-average molecular weight of 10,000 g / mol to 100,000 g / mol, and the polymer containing repeating units represented by Formula 2 has an content of 10 parts by weight to 40 parts by weight.

[0012] [Formula 1]

[0013]

[0014] In Equation 1,

[0015] R1 to R4 are each independently hydrogen and C. 1-10 Alkyl, C 1-10 Alkoxy or halogen, and

[0016] Z is an unsubstituted or phenyl-substituted C. 1-10 Alkylene, unsubstituted or C 1-10 Alkyl-substituted C 3-15 Cycloalkylene, O, S, SO, SO2, or CO,

[0017] [Equation 2]

[0018]

[0019] In Equation 2,

[0020] Y is a divalent organic group represented by formula 2-1 or formula 2-2 below.

[0021] [Equation 2-1]

[0022]

[0023] [Equation 2-2]

[0024]

[0025] A method for preparing the polycarbonate composite composition is also provided, the method comprising the steps of: preparing a polycarbonate comprising repeating units represented by Formula 1 (step 1); preparing a polymer comprising repeating units represented by Formula 2 (step 2); and blending the polycarbonate with the polymer comprising repeating units represented by Formula 2 (step 3), wherein the polycarbonate comprising repeating units represented by Formula 1 has a weight-average molecular weight of 10,000 g / mol to 100,000 g / mol, and the polymer comprising repeating units represented by Formula 2 has an content of 10 parts by weight to 40 parts by weight.

[0026] The polycarbonate in question is prepared by polycondensation of aromatic glycol compounds such as bisphenol A with carbonate precursors such as phosgene. It possesses excellent impact strength, dimensional stability, heat resistance, and transparency. Therefore, polycarbonate resins have a wide range of applications, including exterior materials for electrical and electronic products, automotive parts, building materials, and optical components. In particular, scratch-resistant polycarbonates with improved surface hardness are considered to have high application potential; however, their typically lower impact strength limits their market application.

[0027] Therefore, in this invention, the impact strength of scratch-resistant polycarbonate can be improved by compounding existing polycarbonate with a polymer containing ester repeating units from aromatic glycols.

[0028] The present invention will be described in detail below, and for ease of classification and explanation of the components, polycarbonate will be referred to as the “first polymer”, and polymers containing repeating units represented by Formula 2 will be referred to as the “second polymer”.

[0029] Polycarbonate (first polymer)

[0030] The polycarbonate (first polymer) according to the present invention refers to a repeating unit produced by the reaction of an aromatic diol with a carbonate precursor.

[0031] Preferably, the polycarbonate (first polymer) comprises repeating units represented by Formula 1 below:

[0032] [Formula 1]

[0033]

[0034] In Equation 1,

[0035] R1 to R4 are each independently hydrogen and C. 1-10 Alkyl, C 1-10 Alkoxy or halogen, and

[0036] Z is an unsubstituted or phenyl-substituted C. 1-10 Alkylene, unsubstituted or C 1-10 Alkyl-substituted C 3-15 Cycloalkylene, O, S, SO, SO2, or CO,

[0037] Preferably, R1 to R4 are each independently hydrogen and C. 1-4 Alkyl or halogen. More preferably, R1 to R4 are each independently hydrogen, methyl, chlorine, or bromine.

[0038] Additionally, preferably, Z is an unsubstituted or phenyl-substituted straight-chain or branched C 1-10Alkylene, more preferably methylene, ethane-1,1-diyl, propane-2,2-diyl, butane-2,2-diyl, 1-phenylethane-1,1-diyl, or diphenylmethylene. Additionally, Z is preferably cyclohexane-1,1-diyl, O, S, SO, SO2, or CO.

[0039] Preferably, the compound represented by Formula 1 may be derived from 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- The first or second aromatic diol compound selected from 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 (bisphenol C), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane.

[0040] The phrase “from aromatic diol compounds” refers to the repeating unit represented by Formula 1 formed by the reaction of the hydroxyl group of an aromatic diol compound with a carbonate precursor.

[0041] For example, when the aromatic diol compound bisphenol A is polymerized with the carbonate precursor triphosgene, the repeating unit represented by Formula 1 can be represented by the following Formula 1-1:

[0042] [Equation 1-1]

[0043]

[0044] As a carbonate precursor, one or more selected from dimethyl carbonate, diethyl carbonate, dibutyl carbonate, dicyclohexyl carbonate, diphenyl carbonate, dimethyl carbonate, bis(chlorophenyl) carbonate, di-m-toluene carbonate, dinaphthalene carbonate, bis(diphenyl) carbonate, phosgene, triphosgene, diphosgene, bromophosgene, and dihalocarbamates can be used. Preferably, triphosgene or phosgene can be used.

[0045] Based on conversion values ​​relative to standard polycarbonate (PC standard), the weight-average molecular weight (Mw) of polycarbonate (first polymer), measured by gel permeation chromatography (GPC), can range from 10,000 g / mol to 100,000 g / mol. When the weight-average molecular weight of polycarbonate is less than 10,000 g / mol, the mechanical properties of the composite composition may deteriorate; when it is greater than 100,000 g / mol, there may be issues with the uniformity of the composite composition preparation. More preferably, the weight-average molecular weight can be 12,000 g / mol or more, 15,000 g / mol or more, 20,000 g / mol or more, 25,000 g / mol or more, 30,000 g / mol or more, 35,000 g / mol or more, 40,000 g / mol or more, or 45,000 g / mol or more, and is 70,000 g / mol or less, 65,000 g / mol or less, 60,000 g / mol or less, 55,000 g / mol or less, or 53,000 g / mol or less. Furthermore, composite compositions in which the molecular weight of the first polymer is greater than the molecular weight of the second polymer (described later) can exhibit excellent impact strength and improved surface hardness properties at room temperature.

[0046] Second polymer

[0047] Furthermore, the polycarbonate composite composition according to the invention comprises a polymer (second polymer) containing repeating units represented by Formula 2.

[0048] The repeating unit represented by Formula 2 is an ester repeating unit comprising an aromatic diol compound and a phthalate compound, and has a structure in which the phthalate compound bound to the aromatic diol repeats randomly.

[0049] Existing polycarbonates have attracted attention as internal and external materials for automotive or electrical and electronic products, or as a glass alternative, due to their excellent impact strength, heat resistance, and transparency. However, as the surface hardness of polycarbonates increases, there is a problem of decreased impact strength. Therefore, the inventors have discovered that when a polymer containing repeating units represented by Formula 2 is compounded with polycarbonate, the composite can exhibit improved impact resistance at room temperature while exhibiting the excellent inherent properties of existing polycarbonates.

[0050] Preferably, the polymer comprising the repeating unit represented by Formula 2 has a weight-average molecular weight of 8,000 g / mol to 50,000 g / mol. More preferably, the polymer comprising the repeating unit represented by Formula 2 has a weight-average molecular weight of 8,500 g / mol or more, 9,000 g / mol or more, or 10,000 g / mol or more, and is 45,000 g / mol or less, 40,000 g / mol or less, or 37,000 g / mol or less. When the weight-average molecular weight of the polymer comprising the repeating unit represented by Formula 2 is less than 8,000 g / mol, there is a problem of potentially low impact resistance at room temperature; when it is greater than 50,000 g / mol, there is a problem of excessively low flowability, which may result in poor injection molding.

[0051] Preferably, based on 100 parts by weight of the polycarbonate composite composition, the polycarbonate composite composition according to the invention comprises a polymer containing repeating units represented by Formula 2 in an amount of 10 to 40 parts by weight. More preferably, based on 100 parts by weight of the polycarbonate composite composition, the content of the polymer containing repeating units represented by Formula 2 is 11 parts by weight or more, 12 parts by weight or more, 13 parts by weight or more, 14 parts by weight or more, or 15 parts by weight or more, and is 39 parts by weight or less, 38 parts by weight or less, 37 parts by weight or less, 36 parts by weight or less, or 35 parts by weight or less.

[0052] Polycarbonate composite composition

[0053] The polycarbonate composite composition according to the invention is a composition in which polycarbonate (first polymer) and a polymer (second polymer) comprising repeating units represented by Formula 2 are blended.

[0054] As described, polycarbonate composite compositions prepared by blending heterogeneous polymers can exhibit a variety of physical properties beyond the inherent physical properties of the individual unit polymers, or the physical properties of the individual polymers can be supplemented by blending heterogeneous polymers. In this invention, the polycarbonate (first polymer) has a weight-average molecular weight of 10,000 g / mol to 100,000 g / mol, and the content of the second polymer according to the invention is 10 parts by weight to 40 parts by weight, thereby improving surface hardness while maintaining impact strength.

[0055] Preferably, the weight-average molecular weight of the polycarbonate composite composition is from 10,000 g / mol to 100,000 g / mol. More preferably, it is 15,000 g / mol or more, 20,000 g / mol or more, 25,000 g / mol or more, 30,000 g / mol or more, 35,000 g / mol or more, 40,000 g / mol or more, or 45,000 g / mol or more, and is 85,000 g / mol or less, 80,000 g / mol or less, 75,000 g / mol or less, or 70,000 g / mol or less.

[0056] Preferably, the impact strength of the polycarbonate composite composition according to the invention, measured at 23°C according to ASTM D256 (1 / 8-inch, notched cantilever beam), is from 500 J / m to 1,000 J / m at room temperature. More preferably, the impact strength at room temperature is above 550 J / m, above 575 J / m, or above 6000 J / m. Furthermore, the higher the value, the better the impact strength at room temperature, and therefore there is no upper limit. For example, it can be below 990 J / m, below 980 J / m, or below 970 J / m.

[0057] Preferably, the pencil hardness of the polycarbonate composite composition according to the present invention, as determined according to ASTM D3363, is HB or higher.

[0058] Preparation method of polycarbonate composite composition

[0059] The method for preparing the polycarbonate composite composition according to the present invention may include the following steps: preparing a polycarbonate comprising repeating units represented by Formula 1 (step 1); preparing a polymer comprising repeating units represented by Formula 2 (step 2); and blending the polycarbonate with the polymer comprising repeating units represented by Formula 2 (step 3), wherein the polycarbonate comprising repeating units represented by Formula 1 has a weight-average molecular weight of 10,000 g / mol to 100,000 g / mol, and the polymer comprising repeating units represented by Formula 2 has an content of 10 parts by weight to 40 parts by weight.

[0060] Step 1 is the step of preparing a first polymer, which is a polycarbonate containing repeating units represented by Formula 1, and can be prepared by a general method of preparing polycarbonate by reacting an aromatic diol compound with a carbonate precursor.

[0061] For example, the reaction of carbonate precursors with aromatic diol compounds can be carried out via interfacial polymerization. This interfacial polymerization involves mixing an organic solvent containing the carbonate precursor with an aqueous solution containing the aromatic diol compound, and allowing polymerization to occur at their phase interface.

[0062] In this configuration, polymerization can be carried out at atmospheric pressure and low temperatures, and the molecular weight is easily controlled. Interfacial polymerization can be conducted in the presence of acidic binders and organic solvents. Furthermore, interfacial polymerization may include, for example, a step of adding a coupling agent after prepolymerization and then polymerizing again. In this case, polycarbonates with high molecular weights can be obtained.

[0063] There are no particular restrictions on the materials used in the interfacial polymerization, as long as they are materials applicable to polycarbonate polymerization, and the amount used can be adjusted as needed.

[0064] The acidic binder is an ester exchange catalyst and may include basic compounds such as group I or group II metal compounds, basic boron compounds, basic phosphorus compounds, basic ammonium compounds, amine compounds, etc.

[0065] Group 1 metal compounds can include, for example, sodium hydroxide, potassium hydroxide, lithium hydroxide, cesium hydroxide, sodium bicarbonate, potassium bicarbonate, lithium bicarbonate, cesium bicarbonate, sodium carbonate, potassium carbonate, lithium carbonate, cesium carbonate, sodium acetate, potassium acetate, lithium acetate, cesium acetate, sodium stearate, potassium stearate, lithium stearate, cesium stearate, sodium borohydride, potassium borohydride, lithium borohydride, cesium borohydride, and phenylated sodium borohydride. (boron), potassium boron phenylide, lithium boron phenylide, cesium boron phenylide, sodium benzoate, potassium benzoate, lithium benzoate, cesium benzoate, disodium hydrogen phosphate, dipotassium hydrogen phosphate, dilithium hydrogen phosphate, dicesium hydrogen phosphate, disodium phenyl phosphate, dipotassium phenyl phosphate, dilithium phenyl phosphate, dicesium phenyl phosphate, sodium, potassium, lithium or cesium phosphate, alkoxides or phenolic salts of sodium, potassium, lithium or cesium, or disodium salt, dipotassium salt, dilithium salt or dicesium salt of bisphenol A, etc.

[0066] In addition, Group 2 metal compounds may include, for example, calcium hydroxide, barium hydroxide, magnesium hydroxide, strontium hydroxide, calcium bicarbonate, barium bicarbonate, magnesium bicarbonate, strontium bicarbonate, calcium carbonate, barium carbonate, magnesium carbonate, strontium carbonate, calcium acetate, barium acetate, magnesium acetate, strontium acetate, calcium stearate, barium stearate, magnesium stearate, strontium stearate, etc.

[0067] There are no particular limitations on the organic solvent, as long as it is a solvent commonly used for polycarbonate polymerization. For example, halogenated hydrocarbons such as dichloromethane and chlorobenzene can be used.

[0068] Furthermore, in order to control the molecular weight of the polycarbonate during polymerization, polymerization is preferably carried out in the presence of a molecular weight regulator. In particular, the weight-average molecular weight of the polycarbonate according to the invention can be controlled to be from 10,000 g / mol to 100,000 g / mol. As a molecular weight regulator, C0.05 can be used. 1-20Alkylphenols. Specific examples may include p-tert-butylphenol, p-cumylphenol, decylphenol, dodecylphenol, tetradecylphenol, hexadecylphenol, octadecylphenol, eicosylphenol, dodecylphenol, triacontylphenol, etc. The molecular weight regulator may be added before, during, or after polymerization initiation. Based on 100 parts by weight of the aromatic glycol compound, the content of the molecular weight regulator may be, for example, 0.01 parts by weight or more, 0.1 parts by weight or more, or 1 part by weight or more, and 10 parts by weight or less, 6 parts by weight or less, or 5 parts by weight or less. Within the above range, the desired molecular weight can be obtained.

[0069] In addition, reaction promoters can be used to accelerate the reaction during interfacial polymerization, such as tertiary amine compounds, quaternary ammonium compounds, or quaternary phosphine compounds such as triethylamine, tetra-n-butylammonium bromide, and tetra-n-butylphosphine bromide.

[0070] In interfacial polymerization, the reaction temperature can range from 0°C to 40°C, and the reaction time can range from 10 minutes to 5 hours. Furthermore, during the reaction, the pH can preferably be maintained above 9 or above 11.

[0071] After polycarbonate is prepared by polymerization, further steps such as filtration or drying can be performed to provide polycarbonate.

[0072] In the method for preparing the polycarbonate composite composition of the present invention, step 2 is the step of preparing a second polymer containing an ester repeating unit, which is a repeating unit represented by formula 2.

[0073] According to one embodiment of the present invention, step 2 comprises the polymerization of bisphenol C and compounds represented by the following formulas 3-1 and 3-2:

[0074] [Equation 3-1]

[0075]

[0076] [Equation 3-2]

[0077]

[0078] In equations 3-1 and 3-2,

[0079] X is a halogen.

[0080] More preferably, X is bromine or chlorine.

[0081] The method for preparing the repeating unit represented by Equation 2 is the same as that for reaction scheme 1 below:

[0082] [Reaction Scheme 1]

[0083]

[0084] In reaction scheme 1, X and Y are the same as defined above.

[0085] The repeating unit represented by Formula 2 in this invention is prepared by reacting an aromatic diol compound with two or more polyfunctional acyl halide compounds, as shown in reaction scheme 1. Specifically, the repeating unit can be prepared by esterification of an aromatic diol with a polyfunctional acyl halide. Because two or more acyl halides are used, it has a random repeating structure derived from the terephthalic acid ester unit of the acyl halide.

[0086] Preferably, the amount of the compounds represented by Formulas 3-1 and 3-2 relative to the equivalent of bisphenol C can be from 0.1 equivalents to 1 equivalent, more preferably 0.15 equivalents or more, 0.2 equivalents or more, 0.3 equivalents or more, and less than 0.95 equivalents, less than 0.9 equivalents, or less than 0.85 equivalents. When the amount of the compounds represented by Formulas 3-1 and 3-2 relative to the equivalent of bisphenol C is less than 0.1 equivalents, there is a problem that oligomers are not formed, while when the amount is greater than 1 equivalent, there is a problem that unreacted substances may be generated.

[0087] For example, the aromatic diol used to prepare the repeating unit represented by Formula 2 can be bisphenol C (BPC), and the polyfunctional acyl halide can be isophthaloyl chloride (IPCl), terephthaloyl chloride (TPCl), or a mixture thereof.

[0088] Furthermore, in the method for preparing the polycarbonate composite composition of the present invention, step 3 is a step of blending the polycarbonate prepared in step 1 with the polymer containing ester repeating units prepared in step 2.

[0089] As described above, the polycarbonate composite composition of the present invention is prepared by blending heterogeneous polymers and may include 10 to 40 parts by weight of a polymer containing repeating units represented by Formula 2, thereby increasing surface hardness while maintaining the impact strength of existing polycarbonates.

[0090] Regarding the blending in step 3 of the present invention, the method of blending the polymer can be carried out using techniques generally known in the art, such as melt kneading, but there are no particular limitations.

[0091] According to one embodiment of the present invention, a molded article formed from a polycarbonate composite composition is provided.

[0092] The molded articles can be applied to a wide range of fields, such as internal and external materials for electrical and electronic products, automotive parts, building materials, optical components, and clothing materials.

[0093] Since the molded article is manufactured using the aforementioned polycarbonate composite composition, it exhibits high scratch resistance while displaying the excellent properties of polycarbonate. Therefore, this molded article is expected to be applicable in fields where its use is limited by the low surface hardness of existing polycarbonate molded articles.

[0094] There are no particular limitations on the method of providing molded articles from polycarbonate composite compositions. For non-limiting examples, molded articles can be provided by adding additives commonly used in the art to which this invention pertains to the polycarbonate composition as needed, then mixing it, extruding the mixture using an extruder to produce granules, drying the granules, and then injecting the granules using an injection molding machine.

[0095] The mixing of polycarbonate composite compositions can be carried out by melt kneading, for example using a ribbon mixer, Henschel mixer, Banbury mixer, drum tumbler, single-screw extruder, twin-screw extruder, co-kneader, or multi-screw extruder. The temperature during melt kneading can be appropriately controlled as needed.

[0096] Next, the melt-kneaded product or granules are used as raw materials, and molding methods such as injection molding, injection compression molding, extrusion molding, vacuum molding, blow molding, stamping, pneumatic molding, foam molding, hot bending molding, compression molding, calendering, and rotational molding can be applied.

[0097] When using injection molding, the polycarbonate composition is placed at a high temperature of 200°C to 400°C. Preferably, due to the excellent heat resistance of the polycarbonate composition, polymer modification or yellowing rarely occurs during the above-mentioned melt kneading or injection process.

[0098] The size and thickness of the molded part can be adjusted appropriately according to its intended use, and its shape can also be flat or curved, depending on the intended use.

[0099] As described above, the molded article according to another embodiment can exhibit high scratch resistance while maintaining excellent properties, such as the excellent impact resistance characteristic of polycarbonate, thus enabling its application in a variety of fields.

[0100] Beneficial effects

[0101] As described above, the polycarbonate composite composition comprising polycarbonate and specific ester repeating units according to the present invention is characterized by having excellent surface hardness while maintaining the basic physical properties of polycarbonate. Detailed Implementation

[0102] In the following sections, preferred exemplary embodiments will be provided to better understand the invention. However, the following exemplary embodiments are provided for illustrative purposes only, and the invention is not limited thereto.

[0103] <Example>

[0104] Preparation Example 1-1: Preparation of polycarbonate (50,000 g / mol)

[0105] 620g of water, 116.47g of bisphenol A (BPA), 102.5g of 40% NaOH aqueous solution and 200ml of MeCl2 were added to a 2L main reactor equipped with a nitrogen purging device and a condenser, and kept at room temperature by a circulator, and then stirred for several minutes.

[0106] Stop nitrogen purging. Place 62g of triphosgene and 120g of MeCl2 in a 1L round-bottom flask, dissolve the triphosgene in it, and slowly add the dissolved triphosgene solution to the main reactor. After the addition is complete, add 2.66g of p-tert-butylphenol (PTBP) and stir for 10 minutes. Then, add 97g of 40% by weight NaOH aqueous solution and 1.16g of TEA as a coupling agent. At this point, maintain the reaction pH between 11 and 13.

[0107] After allowing the solution to stand for a period of time to allow sufficient reaction, the reaction is terminated by adding HCl to lower the pH to 3 or 4. Then, stirring is stopped, the organic and aqueous layers are separated, the aqueous layer is removed, and pure H2O is added again. The washing process is repeated 3 to 5 times.

[0108] After complete washing, only the organic layer was extracted, and polymer crystals were obtained by reprecipitation using non-solvents such as methanol and H2O. In this respect, the prepared polycarbonate had a weight-average molecular weight of 50,000 g / mol.

[0109] Preparation Examples 1-2: Preparation of Polycarbonate (51,000 g / mol)

[0110] Polycarbonate was prepared using the same method as in Preparation Example 1-1, except that 2.6 g of p-tert-butylphenol (PTBP) was used. The resulting polycarbonate had a weight-average molecular weight of 51,000 g / mol.

[0111] Preparation Examples 1-3: Preparation of Polycarbonate (49,000 g / mol)

[0112] Polycarbonate was prepared using the same method as in Preparation Example 1-1, except that 2.7 g of p-tert-butylphenol (PTBP) was used. The resulting polycarbonate had a weight-average molecular weight of 49,000 g / mol.

[0113] Preparation Examples 1-4: Preparation of Polycarbonate (46,000 g / mol)

[0114] Polycarbonate was prepared using the same method as in Preparation Example 1-1, except that 2.9 g of p-tert-butylphenol (PTBP) was used. The resulting polycarbonate had a weight-average molecular weight of 46,000 g / mol.

[0115] Preparation Examples 1-5: Preparation of Polycarbonate (36,000 g / mol)

[0116] Polycarbonate was prepared using the same method as in Preparation Example 1-1, except that 3.7 g of p-tert-butylphenol (PTBP) was used. The resulting polycarbonate had a weight-average molecular weight of 36,000 g / mol.

[0117] Preparation Examples 1-6: Preparation of Polycarbonate (8,000 g / mol)

[0118] Polycarbonate was prepared using the same method as in Preparation Example 1-1, except that 22.8 g of p-tert-butylphenol (PTBP) was used. The resulting polycarbonate had a weight-average molecular weight of 8,000 g / mol.

[0119] Preparation Example 2-1: Preparation of Ester Polymer (BPCIPTP, 10,000 g / mol)

[0120] Bisphenol C (BPC, 23.86 g, 0.093 mol), terephthaloyl chloride (TPCl, 10.5 g, 0.052 mol), and isophthaloyl chloride (IPCl, 10.5 g, 0.052 mol) were dispersed / dissolved in dichloromethane. Triethylamine (TEA, 36.66 mL) was then slowly added dropwise while stirring at room temperature for 4 hours or longer. The reaction was then terminated with 1 N HCl, and the stirred reaction product was washed several times with distilled water using a separatory funnel. The solvent was then removed using a rotary vacuum evaporator, and the product was dried overnight at 120 °C to obtain a solid. The resulting polymer (BPCIPTP) had a molecular weight of 10,000 g / mol.

[0121] Preparation Example 2-2: Preparation of Ester Polymer (BPCIPTP, 20,000 g / mol)

[0122] The polymer was prepared using the same method as in Preparation Example 2-1, except that 26 g of BPC, 11 g of TPCl, and 11 g of IPCl were used. The resulting polymer (BPCIPTP) had a molecular weight of 20,000 g / mol.

[0123] Preparation Examples 2-3: Preparation of Ester Polymer (BPCIPTP, 30,000 g / mol)

[0124] The polymer was prepared using the same method as in Preparation Example 2-1, except that 26 g of BPC, 10 g of TPCl, and 10 g of IPCl were used. The resulting polymer (BPCIPTP) had a molecular weight of 30,000 g / mol.

[0125] Preparation Examples 2-4: Preparation of Ester Polymer (BPCIPTP, 35,000 g / mol)

[0126] The polymer was prepared using the same method as in Preparation Example 2-1, except that 26 g of BPC, 10.5 g of TPCl, and 10.5 g of IPCl were used. The resulting polymer (BPCIPTP) had a molecular weight of 35,000 g / mol.

[0127] Comparative Preparation Example 2-1: Preparation of Ester Polymer (BPAIPTP, 20,000 g / mol)

[0128] The polymer was prepared using the same method as in Preparation Example 2-1, except that BPA was used instead of BPC. The resulting polymer (BPAIPTP) had a molecular weight of 20,000 g / mol.

[0129] Comparative Preparation Example 2-2: Preparation of Ester Polymer (Resorcinol IPTP, 20,000 g / mol)

[0130] The polymer was prepared using the same method as in Preparation Example 2-1, except that resorcinol was used instead of BPC. The resulting polymer (resorcinol IPTP) had a molecular weight of 20,000 g / mol.

[0131] Example 1

[0132] The polycarbonate (50,000 g / mol) prepared in Preparation Example 1-1 and the BPCIPTP (10,000 g / mol) prepared in Preparation Example 2-1 were blended in a weight ratio of 85:15, and 500 ppm of Irgafos 168 (BASF Corp.) was added as an antioxidant to prepare a polycarbonate composite composition.

[0133] Subsequently, the polycarbonate composite composition was fed into an extruder (HAAKE Rheomex OS single-screw extruder), melt-kneaded at a barrel temperature of 250°C, and then granulated. Injection molding was then performed continuously using an injection molding machine (BABYPLAST 6 / 10P) at a cylinder temperature of 270°C and a die temperature of 80°C to prepare 3 mm thick specimens for measuring surface hardness and 3.175 mm (1 / 8 inch) thick specimens for measuring impact strength.

[0134] Example 2

[0135] Except that the polycarbonate (51,000 g / mol) prepared in Preparation Examples 1-2 and the BPCIPTP (35,000 g / mol) prepared in Preparation Examples 2-4 were blended at a weight ratio of 65:35, the polycarbonate composite composition was prepared in the same manner as in Example 1.

[0136] Example 3

[0137] Except that the polycarbonate (50,000 g / mol) prepared in Preparation Example 1-1 and the BPCIPTP (20,000 g / mol) prepared in Preparation Example 2-2 were blended at a weight ratio of 85:15, the polycarbonate composite composition was prepared in the same manner as in Example 1.

[0138] Example 4

[0139] Except that the polycarbonate (51,000 g / mol) prepared in Preparation Examples 1-2 and the BPCIPTP (30,000 g / mol) prepared in Preparation Examples 2-3 were blended at a weight ratio of 65:35, the polycarbonate composite composition was prepared in the same manner as in Example 1.

[0140] Example 5

[0141] Except that the polycarbonate (51,000 g / mol) prepared in Preparation Examples 1-2 and the BPCIPTP (20,000 g / mol) prepared in Preparation Examples 2-2 were blended at a weight ratio of 75:25, the polycarbonate composite composition was prepared in the same manner as in Example 1.

[0142] Example 6

[0143] Except that the polycarbonate (36,000 g / mol) prepared in Preparation Examples 1-5 and the BPCIPTP (20,000 g / mol) prepared in Preparation Examples 2-2 were blended at a weight ratio of 65:35, the polycarbonate composite composition was prepared in the same manner as in Example 1.

[0144] Comparative Example 1

[0145] The polycarbonate used in Preparation Examples 1-3 was fed into an extruder (HAAKE Rheomex OS single-screw extruder), melt-kneaded at a barrel temperature of 250°C, and then granulated. Injection molding was performed continuously using an injection molding machine (BABYPLAST 6 / 10P) at a barrel temperature of 270°C and a die temperature of 80°C to prepare 3 mm thick specimens for measuring surface hardness and 3.175 mm (1 / 8 inch) thick specimens for measuring impact strength.

[0146] Comparative Example 2

[0147] Except that the polycarbonate (50,000 g / mol) prepared in Preparation Example 1-1 and the BPAIPTP (20,000 g / mol) prepared in Comparative Preparation Example 2-1 were blended at a weight ratio of 85:15, the polycarbonate composite composition was prepared in the same manner as in Example 1.

[0148] Comparative Example 3

[0149] Except that the polycarbonate (51,000 g / mol) prepared in Preparation Examples 1-2 and the resorcinol IPTP (20,000 g / mol) prepared in Comparative Preparation Examples 2-2 were blended at a weight ratio of 85:15, the polycarbonate composite composition was prepared in the same manner as in Example 1.

[0150] Comparative Example 4

[0151] 620g of water, 98.99g of bisphenol A (BPA), 19.61g of bisphenol C (BPC), 102.5g of 40wt% NaOH aqueous solution and 200ml of MeCl2 were added to a 2L main reactor equipped with a nitrogen purging device and a condenser, and kept at room temperature by a circulator, and then stirred for several minutes.

[0152] Stop nitrogen purging. Place 62g of triphosgene and 120g of MeCl2 in a 1L round-bottom flask, dissolve the triphosgene in it, and slowly add the dissolved triphosgene solution to the main reactor. After the addition is complete, add 2.66g of p-tert-butylphenol (PTBP) and stir for 10 minutes. Then, add 97g of 40% by weight NaOH aqueous solution and 1.16g of TEA as a coupling agent. At this point, the reaction pH is maintained between 11 and 13.

[0153] After allowing the solution to stand for a period of time to allow sufficient reaction, the reaction is terminated by adding HCl to lower the pH to 3 or 4. Then, stirring is stopped, the organic and aqueous layers are separated, the aqueous layer is removed, and pure H2O is added again. The washing process is repeated 3 to 5 times.

[0154] After complete washing, only the organic layer was extracted, and polymer crystals were obtained by reprecipitation using non-solvents such as methanol and H2O. In this respect, the prepared polymer (BPC polycarbonate) had a weight-average molecular weight of 49,000 g / mol.

[0155] Comparative Example 5

[0156] The polymer was prepared in the same manner as in Comparative Example 4, except that 82.53 g of bisphenol A (BPA) and 39.23 g of bisphenol C (BPC) were used. The resulting polymer (BPC polycarbonate) had a weight-average molecular weight of 49,000 g / mol.

[0157] Comparative Example 6

[0158] Except for blending the polycarbonate (46,000 g / mol) prepared in Preparation Examples 1-4 and the BPCIPTP (20,000 g / mol) prepared in Preparation Examples 2-2 at a weight ratio of 55:45, the polycarbonate composite composition was prepared in the same manner as in Example 1.

[0159] Comparative Example 7

[0160] Except for blending the polycarbonate (46,000 g / mol) prepared in Preparation Examples 1-4 and the BPCIPTP (20,000 g / mol) prepared in Preparation Examples 2-2 at a weight ratio of 95:5, the polycarbonate composite composition was prepared in the same manner as in Example 1.

[0161] Comparative Example 8

[0162] Except that the polycarbonate (8,000 g / mol) prepared in Preparation Examples 1-6 and the BPCIPTP (20,000 g / mol) prepared in Preparation Examples 2-2 were blended at a weight ratio of 65:35, the polycarbonate composite composition was prepared in the same manner as in Example 1.

[0163] The polycarbonate composite compositions of the examples and comparative examples are summarized in Table 1 below.

[0164] [Table 1]

[0165]

[0166]

[0167] <Experimental Example>

[0168] Sample preparation

[0169] Relative to 1 part by weight of each polycarbonate composite composition prepared in the Examples and Comparative Examples, 0.050 parts by weight of tris(2,4-di-tert-butylphenyl) phosphite, 0.010 parts by weight of octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, and 0.030 parts by weight of pentaerythritol tetrastearate were added, and granulation was performed using a Φ30 mm twin-screw extruder equipped with a vent. Each specimen was prepared by injection molding using an N-20C injection molding machine (JSW Co., Ltd.) at a barrel temperature of 300°C and a die temperature of 80°C.

[0170] The performance of the samples was determined by the following methods, and the results are shown in Table 2 below.

[0171] (1) Pencil hardness

[0172] Pencil hardness is measured according to ASTM D 3363. Specifically, the pencil angle is fixed at 45°, and the sample surface is then scratched approximately 6.5 mm to evaluate whether the scratch is visible to the naked eye. This test is repeated by changing the pencil hardness.

[0173] (2) Weight-average molecular weight

[0174] 200 mg of polymer resin was diluted in 200 ml of tetrahydrofuran (THF) solvent to prepare a sample of approximately 1000 ppm. The molecular weight was measured using an Agilent 1200 series GPC instrument at a flow rate of 1 ml / min via an RI detector. As a standard for calculating the sample molecular weight, calibration curves were obtained using eight PS standards, and the molecular weight of the sample was determined based on these curves.

[0175] (3) Impact strength

[0176] Impact strength was measured at 23°C according to ASTM D256 (1 / 8 inch, notched cantilever beam).

[0177] (4) Transmittance

[0178] Transmittance was measured in the range of approximately 350 nm to approximately 1050 nm using UltraScan PRO (manufactured by Hunter Lab) according to ASTM D1003.

[0179] [Table 2]

[0180]

[0181] As shown in Table 2, it has been confirmed that the polycarbonate composite composition according to the present invention exhibits superior pencil hardness compared to existing polycarbonate compositions, while having similar impact strength and transmittance at room temperature.

Claims

1. A polycarbonate composite composition comprising a polycarbonate containing repeating units represented by Formula 1; and a polymer containing repeating units represented by Formula 2. in, The polycarbonate containing repeating units represented by Formula 1 has a weight-average molecular weight of 45,000 g / mol to 55,000 g / mol, and In this embodiment, based on 100 parts by weight of the polycarbonate composite composition, the content of the polymer comprising repeating units represented by Formula 2 is from 15 parts by weight to 25 parts by weight, and The polycarbonate composite composition has a weight-average molecular weight of 45,000 g / mol to 70,000 g / mol. [Formula 1] In Equation 1, R1 to R4 are each independently hydrogen and C. 1-10 Alkyl, C 1-10 Alkoxy or halogen, and Z is an unsubstituted or phenyl-substituted C. 1-10 Alkylene, unsubstituted or C 1-10 Alkyl-substituted C 3-15 Cycloalkylene, O, S, SO, SO2, or CO, [Equation 2] In Equation 2, Y is a divalent organic group represented by formula 2-1 or formula 2-2: [Equation 2-1] [Equation 2-2] 。 2. The polycarbonate composite composition according to claim 1, wherein, The repeating unit represented by Formula 1 is derived from 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( The aromatic diol compound selected from 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 (bisphenol C), 2,2-bis(4-hydroxy-3,5-dimethylphenyl)propane, and 1,1-bis(4-hydroxyphenyl)-1-phenylethane.

3. The polycarbonate composite composition according to claim 1, wherein, The repeating unit represented by Equation 1 is represented by the following Equation 1-1: [Equation 1-1] 。 4. The polycarbonate composite composition according to claim 1, wherein, The polymer containing the repeating unit represented by Formula 2 has a weight-average molecular weight of 8,000 g / mol to 50,000 g / mol.

5. The polycarbonate composite composition according to claim 1, wherein, According to ASTM D3363, the pencil hardness of the polycarbonate composite composition is HB or higher.

6. The polycarbonate composite composition according to claim 1, wherein, According to ASTM D2561 / 8-inch notched cantilever beams measured at 23°C, the cantilever beam impact strength of the polycarbonate composite composition at room temperature is 500 J / m to 1,000 J / m.

7. A method for preparing the polycarbonate composite composition according to any one of claims 1 to 6, the method comprising the following steps: Step 1: Prepare a polycarbonate comprising repeating units represented by Formula 1; Step 2, prepare a polymer comprising repeating units represented by Formula 2; and Step 3: Blend the polycarbonate with the polymer containing repeating units represented by Formula 2. The polycarbonate comprising the repeating unit represented by Formula 1 has a weight-average molecular weight of 45,000 g / mol to 55,000 g / mol, and the polymer comprising the repeating unit represented by Formula 2 has an content of 15 parts by weight to 25 parts by weight. [Formula 1] In Equation 1, R1 to R4 are each independently hydrogen and C. 1-10 Alkyl, C 1-10 Alkoxy or halogen, and Z is an unsubstituted or phenyl-substituted C. 1-10 Alkylene, unsubstituted or C 1-10 Alkyl-substituted C 3-15 Cycloalkylene, O, S, SO, SO2, or CO, [Equation 2] In Equation 2, Y is a divalent organic group represented by formula 2-1 or formula 2-2: [Equation 2-1] [Equation 2-2] 。 8. The method according to claim 7, wherein, Step 2 includes the polymerization of bisphenol C and compounds represented by formulas 3-1 and 3-2 below: [Equation 3-1] [Equation 3-2] In equations 3-1 and 3-2, X is a halogen.

9. The method according to claim 8, wherein, The amounts of the compounds represented by Formulas 3-1 and 3-2 are 0.1 equivalents to 1 equivalent relative to the equivalent of bisphenol C.

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