Polycarbonate resin composition

Abstract

The present invention relates to a polycarbonate resin composition comprising a polycarbonate resin and an esterification reaction product of a phthalate-based compound and polyalkylene glycol.

Description

Polycarbonate resin composition

[0001] Cross-citation with related applications

[0002] This application claims the benefit of priority based on Korean Patent Application No. 10-2025-0006519 filed January 16, 2025, and all contents disclosed in the document of said Korean patent application are incorporated herein as part of this specification.

[0003] Technology field

[0004] The present invention relates to a polycarbonate resin composition that has excellent light transmittance characteristics and a low YI, and can be used in fields requiring optical properties.

[0005] Polycarbonate resin possesses excellent impact strength, dimensional stability, heat resistance, and transparency. Due to these properties, it is used in a wide variety of fields, including exterior materials for electrical and electronic products, automotive parts, construction materials, and optical components.

[0006] Recently, the applications of polycarbonate resins have been expanding, and their use is increasing, particularly in fields requiring excellent optical properties such as light guide plates, automotive lamps, automotive DRLs, general lamps, and lenses. However, polycarbonate resins used in these fields requiring superior optical properties need to have higher transmittance and a lower YI (Yellow Index) compared to general polycarbonate resins, and thus the development of polycarbonate resin compositions capable of satisfying these characteristics is required.

[0007]

[0008] Prior art literature

[0009] (Patent Document 1) KR 10-2016-0146517 A

[0010]

[0011] The present invention is intended to provide a polycarbonate resin composition having excellent light transmittance characteristics and a low YI.

[0012] To solve the above problem, the present invention provides a polycarbonate resin composition.

[0013] More specifically, (1) the present invention provides a polycarbonate resin composition comprising a polycarbonate resin and an esterification reaction product of a phthalate-based compound and a polyalkylene glycol.

[0014] (2) The present invention provides a polycarbonate resin composition according to (1), wherein the polycarbonate resin has a weight average molecular weight of 10,000 g / mol or more and 60,000 g / mol or less.

[0015] (3) The present invention provides a polycarbonate resin composition in which, in (1) or (2), the esterification reaction product is represented by the following chemical formula 1 or 2:

[0016] [Chemical Formula 1]

[0017]

[0018] [Chemical Formula 2]

[0019]

[0020] In the above chemical formulas 1 and 2, R1 and R2 are each independently an alkylene group having 1 to 5 carbon atoms, and

[0021] The above m and n are each independently integers greater than or equal to 1.

[0022] (4) The present invention provides a polycarbonate resin composition in which, in any one of (1) to (3), the phthalate compound is one or more selected from the group consisting of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dimethyl terephthalate, diethyl terephthalate and dipropyl terephthalate.

[0023] (5) The present invention provides a polycarbonate resin composition in which, in any one of (1) to (4), the polyalkylene glycol is one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polybutylene glycol and polytetramethylene glycol.

[0024] (6) The present invention provides a polycarbonate resin composition in which, in any one of (1) to (5), the weight average molecular weight of the polyalkylene glycol is 500 g / mol or more and 5000 g / mol or less.

[0025] (7) The present invention provides a polycarbonate resin composition in which, in any one of (1) to (6), the molar ratio between the phthalate compound and the polyalkylene glycol is 1:1.5 to 1:3.

[0026] (8) The present invention provides a polycarbonate resin composition in which, in any one of (1) to (7), the esterification reaction product is included in an amount of 0.005 parts by weight or more and 5 parts by weight or less per 100 parts by weight of polycarbonate resin.

[0027] (9) The present invention provides a polycarbonate resin composition characterized by further including a phosphorus-based antioxidant in any one of (1) to (8).

[0028] (10) The present invention provides a polycarbonate resin composition in which, in any one of (1) to (9), the phosphorus-based antioxidant is included in an amount of 0.005 parts by weight or more and 5 parts by weight or less per 100 parts by weight of polycarbonate resin.

[0029] (11) The present invention provides a polycarbonate resin composition characterized by further including a hindered phenolic antioxidant in any one of (1) to (10).

[0030] (12) The present invention provides a polycarbonate resin composition in which, in any one of (1) to (11), the hindered phenolic antioxidant is included in an amount of 0.005 parts by weight or more and 5 parts by weight or less per 100 parts by weight of polycarbonate resin.

[0031] The polycarbonate resin composition according to the present invention has excellent light transmission characteristics, particularly long-light transmittance, and has a low YI, making it particularly suitable for use as a material in various fields where excellent optical properties are required.

[0032] Hereinafter, the present invention will be described in more detail to aid in understanding the invention.

[0033]

[0034] Terms and words used in the description and claims of the present invention should not be interpreted as being limited to their ordinary or dictionary meanings, and should be interpreted in a meaning and concept consistent with the technical spirit of the present invention, based on the principle that the inventor can appropriately define the concept of the terms to best describe his invention.

[0035]

[0036] In the present invention, the polycarbonate resin composition may refer to a resin composition comprising polycarbonate as an essential component.

[0037]

[0038] Polycarbonate resin composition

[0039] The present invention provides a polycarbonate resin composition comprising a polycarbonate resin and an esterification reaction product of a phthalate-based compound and a polyalkylene glycol.

[0040]

[0041] The polycarbonate resin composition of the present invention can exhibit improved optical properties while maintaining the excellent mechanical properties of the polycarbonate resin itself by including an esterification reaction product of a phthalate-based compound and a polyalkylene glycol together with the polycarbonate resin.

[0042]

[0043] Hereinafter, the polycarbonate resin composition of the present invention will be described in more detail.

[0044]

[0045] Polycarbonate resin

[0046] The polycarbonate resin included in the polycarbonate resin composition of the present invention is intended to provide basic characteristics of the resin composition and has excellent heat resistance, impact resistance, mechanical strength, and transparency.

[0047] The above polycarbonate resin may be a polymer prepared by reacting a diphenol compound, phosgene, a carbonate ester, or a combination thereof, and the above diphenol compound may include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane (also called 'Bisphenol-A'), 2,4-bis(4-hydroxyphenyl)-2-methylbutane, bis(4-hydroxyphenyl)methane, 1,1-bis(4-hydroxyphenyl)cyclohexane, 2,2-bis(3-chloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dimethyl-4-hydroxyphenyl)propane, 2,2-bis(3,5-dichloro-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane, 2,2-bis(3,5-dibromo-4-hydroxyphenyl)propane. Examples include bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, bis(4-hydroxyphenyl)ether, etc. Preferably, 4,4'-dihydroxydiphenyl and 2,2-bis(4-hydroxyphenyl)propane may be used.

[0048] The above polycarbonate may be a mixture of copolymers prepared from two or more types of diphenols. In addition, the above polycarbonate may be linear polycarbonate, branched polycarbonate, polyester carbonate copolymer resin, etc.

[0049] Examples of the above linear polycarbonate include polycarbonates prepared from bisphenol-A. Examples of the above branched polycarbonate include those prepared by reacting a polyfunctional aromatic compound, such as trimellitic anhydride or trimellitic acid, with diphenols and carbonates. The above polyfunctional aromatic compound may be included in an amount of 0.05 to 2 mol% relative to the total amount of branched polycarbonate. Examples of the above polyester carbonate copolymer resin include those prepared by reacting a difunctional carboxylic acid with diphenols and carbonates. Examples of the above carbonates include diaryl carbonates such as diphenyl carbonate, ethylene carbonate, etc.

[0050]

[0051] The above polycarbonate may have a weight-average molecular weight of 10,000 g / mol or more, 12,000 g / mol or more, or 14,000 g / mol or more, and 60,000 g / mol or less, 55,000 g / mol or less, or 50,000 g / mol or less. When using a polycarbonate having a weight-average molecular weight within the above-described range, the overall physical properties of the polycarbonate resin composition may be excellent, and the balance between them may also be excellent. Meanwhile, although examples of methods for measuring the weight-average molecular weight are not significantly limited, for example, the weight-average molecular weight equivalent to polystyrene (PS) measured by the GPC method may be used. In the process of measuring the weight-average molecular weight of polycarbonate equivalent measured by the above GPC method, commonly known analytical devices (e.g., GPC measuring equipment: Agilent 1200 series), detectors such as a refractive index detector, and analytical columns may be used, and commonly applied temperature conditions, solvents, and flow rates may be applied. Specific examples of the above measurement conditions include a temperature of 25°C, a tetrahydrofuran solvent, and a flow rate of 1 mL / min, and the measurement may be performed using a PS standard.

[0052]

[0053] Esterification reaction product of phthalate compounds and polyalkylene glycols

[0054] The polycarbonate resin composition of the present invention can provide excellent optical properties by including the esterification reaction product of a phthalate-based compound and a polyalkylene glycol.

[0055] The above phthalate-based compound may include all of a phthalate compound, an isophthalate compound, and a terephthalate compound, and preferably may be a terephthalate compound or an isophthalate compound. More specifically, the above phthalate-based compound may be a dialkyl phthalate, a dialkyl isophthalate, or a dialkyl terephthalate having 1 to 5 carbon atoms in the alkyl group, and more specifically, may be one or more selected from the group consisting of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dimethyl terephthalate, diethyl terephthalate, and dipropyl terephthalate.

[0056] In addition, the polyalkylene glycol may be one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol, and preferably may be polypropylene glycol. The weight average molecular weight of the polyalkylene glycol may be 500 g / mol or more and 5,000 g / mol or less, and preferably 500 g / mol or more, 700 g / mol or more, or 1,000 g / mol or more, and 5,000 g / mol or less, 4,000 g / mol or less, or 3,000 g / mol or less. When the weight average molecular weight of the polyalkylene glycol satisfies the above conditions, the optical properties of the polycarbonate resin may be further improved.

[0057]

[0058] The molar ratio between the above phthalate-based compound and the polyalkylene glycol may be 1:1.5 to 1:3, preferably 1:1.8 to 1:2.5 or 1:1.8 to 1:2.4, and particularly specifically 1:2.3. Since one phthalate-based compound has two ester groups, unnecessary components in the esterification reaction product can be minimized when the molar ratio within the above-described range is satisfied.

[0059]

[0060] More specifically, the esterification reaction product may be represented by the following chemical formula 1 or 2.

[0061] [Chemical Formula 1]

[0062]

[0063] [Chemical Formula 2]

[0064]

[0065]

[0066] In the above chemical formulas 1 and 2, R1 and R2 are each independently an alkylene group having 1 to 5 carbon atoms, and m and n are each independently an integer of 1 or more.

[0067]

[0068] In the above chemical formula 1, R1 and R2 are preferably alkylene groups having 2 to 4 carbon atoms, and more specifically, may be ethylene, 1-methylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, or tetramethylene. The above n and m are preferably 1 to 120, and more specifically, may be 1 or more, 3 or more, 5 or more, 7 or more, or 10 or more, and 120 or less, 110 or less, 100 or less, 90 or less, 80 or less, 70 or less, or 60 or less.

[0069]

[0070] The above esterification reaction product may be included in an amount of 0.005 parts by weight or more and 5 parts by weight or less per 100 parts by weight of polycarbonate resin, preferably 0.005 parts by weight or more, 0.01 parts by weight or more, 0.02 parts by weight or more, or 0.03 parts by weight or more, and may be included in an amount of 5 parts by weight or less, 3 parts by weight or less, 1 part by weight or less, or 0.5 parts by weight or less. When the content of the esterification reaction product is within an appropriate range, optical properties can be improved without deterioration of other physical properties.

[0071]

[0072] The polycarbonate resin composition of the present invention may further include a phosphorus-based antioxidant and / or a hindered phenolic antioxidant. The phosphorus-based antioxidant and the hindered phenolic antioxidant can prevent oxidation of the polycarbonate resin composition and maintain its physical properties. The phosphorus-based antioxidant may be PEP-36 (Bis(2,6-di-ter-butyl-4-methylphenyl)pentaerythritol-diphosphite) and / or DP9228 (bis(2,4-dicumylphenyl)pentaerythritol diphosphate). The hindered phenolic antioxidant mentioned above may be IR1010 ([3-[3-(4-hydroxy-3,5-ditert-butyl-phenyl)propanoyloxy]-2,2-bis[3-(4-hydroxy-3,5-ditert-butyl-phenyl)propanoyloxymethyl]propyl] 3-(4-hydroxy-3,5-ditert-butyl-phenyl)propanoate).

[0073] The above phosphorus-based antioxidant may be included in an amount of 0.005 parts by weight or more and 5 parts by weight or less per 100 parts by weight of polycarbonate resin, preferably in an amount of 0.01 parts by weight or more and 0.5 parts by weight or less. The above hindered phenolic antioxidant may be included in an amount of 0.005 parts by weight or more and 5 parts by weight or less per 100 parts by weight of polycarbonate resin, preferably in an amount of 0.01 parts by weight or more and 0.5 parts by weight or less. When the content of the above antioxidants is appropriate, the antioxidant effect can be maximized without deterioration of physical properties.

[0074]

[0075] Examples

[0076] The present invention will be explained in more detail below through examples. However, the following examples are intended to illustrate the present invention and do not limit the scope of the present invention solely to these examples.

[0077]

[0078] ingredient

[0079] As the polycarbonate resin, a weight-average molecular weight of 45,000 g / mol was used. The weight-average molecular weight was measured by GPC using a PS standard with an Agilent 1200 series. Meanwhile, DP9228 (bis(2,4-dicumylphenyl)pentaerythritol diphosphate) was used as the phosphorus-based antioxidant, and IR1010 ([3-[3-(4-hydroxy-3,5-ditert-butyl-phenyl)propanoyloxy]-2,2-bis[3-(4-hydroxy-3,5-ditert-butyl-phenyl)propanoyloxymethyl]propyl] 3-(4-hydroxy-3,5-ditert-butyl-phenyl)propanoate) was used as the hindered phenol-based antioxidant. As additives for the comparative example, Polycerin DCB2000 and polypropylene glycol (PPG2000) with a weight-average molecular weight of 2,000 g / mol were used.

[0080]

[0081] Preparation Example 1

[0082] Dimethyl terephthalate and polypropylene glycol were introduced into a 500 mL reactor equipped with a Dean-Stark apparatus, with a molar ratio of 1:2.3, along with a titanium tetrabutoxide catalyst. The reaction was initiated at a temperature of 210°C under a nitrogen atmosphere to carry out the esterification reaction between dimethyl terephthalate and polypropylene glycol for a certain period of time, after which the reaction was terminated when methanol, a byproduct, was no longer discharged. After the reaction was terminated, unreacted reactants were removed through a purification process to produce the esterification reaction products of dimethyl terephthalate and polypropylene glycol. In the above process, a total of three types of esterification reaction products were prepared by varying the molecular weight of the polypropylene glycol.

[0083]

[0084] Preparation Example 2

[0085] A total of three types of esterification reaction products were prepared by carrying out the same procedure as in Preparation Example 1 above, except that dimethyl isophthalate was used instead of dimethyl terephthalate.

[0086]

[0087] Examples and Comparative Examples

[0088] A polycarbonate resin composition was prepared by mixing a polycarbonate resin (PC), an esterification reaction product, and an antioxidant according to the ratios listed in Table 1 below.

[0089] PCDCB2000PPG2000PPT1000PPT2000PPT3000PPI1000PPI2000PPI3000DP9228IR1010 Example 1100--0.35--0.150.05 Example 2100---0.35-0.150.05 Example 3100----0.350.150.05 Example 4100-----0.350.150.05 Example 5100-----0.350.150.05 Example 6100-----0.350.150.05 Comparative Example 1100-----0.150.05 Comparative Example 21000.35----0.150.05 Comparative Example 3100-0.35---0.150.05

[0090] Meanwhile, in Table 1 above, PPT1000 refers to an esterification reaction product synthesized using polypropylene glycol and dimethyl terephthalate with a weight-average molecular weight of 1,000 g / mol, and PPT2000 and PPT3000 likewise refer to polypropylene glycol used with weight-average molecular weights of 2,000 g / mol and 3,000 g / mol, respectively. PPI1000 also refers to an esterification reaction product synthesized using polypropylene glycol and dimethyl isophthalate with a weight-average molecular weight of 1,000 g / mol, and PPI2000 and PPI3000 likewise refer to polypropylene glycol used with weight-average molecular weights of 2,000 g / mol and 3,000 g / mol, respectively.

[0091]

[0092] Experimental Example 1. Confirmation of Optical Properties of Polycarbonate Resin Composition

[0093] Pellet was manufactured using the polycarbonate resin composition prepared in the above examples and comparative examples. More specifically, pellets were manufactured at a rate of 55 kg per hour using a twin-screw extruder (L / D=36, φ=45, barrel temperature 260℃).

[0094] Specimens were prepared by injection molding the manufactured pellets using a JSW Co., Ltd. N-20C injection molding machine at a cylinder temperature of 280°C without residence time, and transmittance and color tone were measured for the prepared specimens using the following method. The specimen for measuring 3T transmittance was prepared as a rectangular specimen (3T injection specimen form) with a thickness of 3 mm and a flat scale of 30 mm * 50 mm, and the specimen for measuring 150T transmittance was prepared as a rectangular specimen (4T injection specimen form) with a thickness of 4 mm and a flat scale of 150 mm * 80 mm.

[0095] 1) Transmittance (3T) and hue (3T, YI)

[0096] Transmittance at 420 nm was measured using UltraScan PRO (HunterLab) according to ASTM D1003 with transmission conditions of 350–850 nm. In addition, the yellowing index (YI) was measured using Hunter Lab’s UltraScan PRO according to ASTM D1925 with transmission conditions of 350–1050 nm.

[0097] 2) Long light transmittance (150T) and long light hue (150T, YI)

[0098] Using a Spectrophotometer U-4100 (Hitachi), light of 380 to 780 nm was irradiated along the transverse direction of the specimen to measure the 150T long light transmittance (T%) and 150T long light hue (YI). The long light hue was measured in accordance with JIS Z 8722.

[0099] The measurement results are summarized in Table 2 below.

[0100] Transmittance (3T, Tt%) YI (3t, 280℃) Long Light Transmittance (150T, Tt%) Long Light YI (150T) Example 1 91.50.6985.75.14 Example 2 91.40.7085.65.18 Example 3 91.40.7285.35.24 Example 4 91.40.7085.65.16 Example 5 91.30.7385.25.21 Example 6 91.10.7385.15.24 Comparative Example 190.90.8483.45.53 Comparative Example 291.20.7784.65.32 Comparative Example 391.10.7684.95.48

[0101] As can be seen from Table 2 above, the polycarbonate resin composition of the present invention has excellent transmittance and YI characteristics compared to the polycarbonate resin composition of the comparative example, and through this, it was confirmed that optical properties can be improved by using the esterification reaction product of a phthalate-based compound and a polyalkylene glycol together with polycarbonate.

Claims

1. Polycarbonate resin; and A polycarbonate resin composition comprising an esterification reaction product of a phthalate-based compound and a polyalkylene glycol.

2. In Paragraph 1, The above polycarbonate resin is a polycarbonate resin composition having a weight average molecular weight of 10,000 g / mol or more and 60,000 g / mol or less.

3. In Paragraph 1, A polycarbonate resin composition wherein the esterification reaction product is represented by the following chemical formula 1 or 2: [Chemical Formula 1] [Chemical Formula 2] In the above chemical formulas 1 and 2, R1 and R2 are each independently an alkylene group having 1 to 5 carbon atoms, and The above m and n are each independently integers greater than or equal to 1.

4. In Paragraph 1, A polycarbonate resin composition in which the above phthalate-based compound is one or more selected from the group consisting of dimethyl phthalate, diethyl phthalate, dipropyl phthalate, dimethyl isophthalate, diethyl isophthalate, dipropyl isophthalate, dimethyl terephthalate, diethyl terephthalate, and dipropyl terephthalate.

5. In Paragraph 1, A polycarbonate resin composition in which the above polyalkylene glycol is one or more selected from the group consisting of polyethylene glycol, polypropylene glycol, polybutylene glycol, and polytetramethylene glycol.

6. In Paragraph 1, A polycarbonate resin composition having a weight average molecular weight of the above polyalkylene glycol of 500 g / mol or more and 5000 g / mol or less.

7. In Paragraph 1, A polycarbonate resin composition in which the molar ratio between the above phthalate-based compound and the polyalkylene glycol is 1:1.5 to 1:

3.

8. In Paragraph 1, A polycarbonate resin composition in which the above esterification reaction product is included in an amount of 0.005 parts by weight or more and 5 parts by weight or less per 100 parts by weight of polycarbonate resin.

9. In Paragraph 1, A polycarbonate resin composition characterized by further including a phosphorus-based antioxidant.

10. In Paragraph 9, A polycarbonate resin composition in which the above-mentioned phosphorus-based antioxidant is included in an amount of 0.005 parts by weight or more and 5 parts by weight or less per 100 parts by weight of polycarbonate resin.

11. In Paragraph 1, A polycarbonate resin composition characterized by further including a hindered phenolic antioxidant.

12. In Paragraph 11, A polycarbonate resin composition in which the above hindered phenolic antioxidant is included in an amount of 0.005 parts by weight or more and 5 parts by weight or less per 100 parts by weight of polycarbonate resin.

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