Polycarbonate resin composition

Abstract

The present invention is characterized in that the optical properties of a polycarbonate resin, specifically, long-wavelength light transmittance and a long-wavelength light yellowness index can be improved by using additives having a special structure in the polycarbonate resin.

Description

polycarbonate resin composition

[0001] Cross-citation with related application(s)

[0002] This application claims the benefit of priority to Korean Patent Application No. 10-2023-0077613, filed June 16, 2023, the entire disclosure of which is incorporated herein by reference.

[0003]

[0004] The present invention relates to a polycarbonate resin composition having excellent optical properties, particularly light transmittance and light yellowness.

[0005] Polycarbonate resin is known to have excellent impact resistance, transparency, strength, flame retardancy, electrical properties, and heat resistance, and is widely used in the manufacture of molded parts for automobiles and electrical / electronic products, and its demand is increasing day by day.

[0006]

[0007] As the application areas of polycarbonate resins have expanded, demand is increasing in areas requiring high optical properties, such as light guide plates, automotive lamps, DRLs, general lamps, and lenses. Consequently, there is a growing need to develop resins with higher transmittance and lower YI than conventional polycarbonate resins.

[0008]

[0009] In the past, the use of phenolic compounds or phosphorus compounds has been proposed to secure thermal stability, etc., so that the physical properties can be maintained even during high-temperature processing of polycarbonate resins. However, the use of these compounds alone has limitations in improving the transmittance, especially the long-wave transmittance and long-wave yellowness.

[0010]

[0011] Meanwhile, various additives are being studied to further improve the above, but in general, in order to improve the optical properties of polycarbonate resin, compatibility with polycarbonate resin must also be considered as important for the optical properties to be improved according to the use of additives.

[0012]

[0013] Accordingly, in the present invention, the optical properties of polycarbonate resin, particularly light transmittance and light yellowness, were studied extensively through various additives, and as a result, it was confirmed that the above-mentioned purpose was achieved when an additive having a special structure, as described below, was used, thereby completing the present invention.

[0014] The present invention provides a polycarbonate resin composition having excellent light transmittance and light yellowness.

[0015] In addition, the present invention provides a method for producing the polycarbonate resin composition.

[0016] To solve the above problem, the present invention provides the following polycarbonate resin composition:

[0017] polycarbonate resin; and

[0018] Containing a polycarbonate diol represented by the following chemical formula 1,

[0019] Polycarbonate resin composition:

[0020] [Chemical Formula 1]

[0021]

[0022] In the above chemical formula 1,

[0023] R1 and R2 are each independently C5~C 10 Straight-chain alkylene, or C5~C 10 It is cycloalkylene,

[0024] n and m are each independently integers greater than or equal to 1.

[0025]

[0026] The term "polycarbonate resin" used in the present invention refers to a polymer manufactured by reacting a diphenol compound, phosgene, a carbonic ester, or a combination thereof. Polycarbonate has excellent heat resistance, impact resistance, mechanical strength, transparency, etc., and is widely used in the manufacture of transparent sheets, packaging materials, automobile bumpers, UV-blocking films, etc., and is particularly used as an optical material in the present invention.

[0027]

[0028] The above diphenol compounds include hydroquinone, resorcinol, 4,4'-dihydroxydiphenyl, 2,2-bis(4-hydroxyphenyl)propane ('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, bis(4-hydroxyphenyl)sulfoxide, bis(4-hydroxyphenyl)ketone, Bis(4-hydroxyphenyl)ether, etc. can be mentioned. Preferably, 4,4'-dihydroxydiphenyl and 2,2-bis(4-hydroxyphenyl)propane can be used, and in this case, the structure of the polycarbonate is as shown in the following chemical formula 2:

[0029] [Chemical Formula 2]

[0030]

[0031]

[0032] The above polycarbonate may be a mixture of copolymers prepared from two or more diphenols. In addition, the above polycarbonate may be a linear polycarbonate, a branched polycarbonate, a polyester carbonate copolymer resin, or the like.

[0033]

[0034] Examples of the linear polycarbonate include polycarbonates manufactured from bisphenol-A. Examples of the branched polycarbonate include those manufactured by reacting polyfunctional aromatic compounds such as trimellitic anhydride and trimellitic acid with diphenols and carbonates. The polyfunctional aromatic compounds may be included in an amount of 0.05 to 2 mol% based on the total amount of the branched polycarbonate. Examples of the polyester carbonate copolymer resin include those manufactured by reacting difunctional carboxylic acids with diphenols and carbonates. Examples of the carbonate include diaryl carbonates such as diphenyl carbonate, ethylene carbonate, and the like.

[0035]

[0036] Preferably, the polycarbonate has a weight average molecular weight of 14,000 g / mol to 50,000 g / mol. More preferably, the polycarbonate has a weight average molecular weight of 15,000 g / mol or more, 16,000 g / mol or more, 17,000 g / mol or more, 18,000 g / mol or more, 19,000 g / mol or more, 20,000 g / mol or more; 45,000 g / mol or less, 40,000 g / mol or less, 35,000 g / mol or less, 30,000 g / mol or less, or 25,000 g / mol or less.

[0037]

[0038] Meanwhile, the polycarbonate diol represented by the chemical formula 1 included in the composition of the present invention is a substance added to improve the optical properties of the polycarbonate resin.

[0039]

[0040] In particular, the polycarbonate diol according to the present invention has excellent compatibility with polycarbonate resin due to the presence of a carbonate structure in its molecular structure, and thus can more effectively improve the optical properties of the polycarbonate resin.

[0041]

[0042] Meanwhile, the polycarbonate diol according to the present invention contains two types of repeating units and is a random copolymer. Preferably, the molar ratio of the repeating units in the polycarbonate diol is 1:9 to 9:1. That is, n:m in the chemical formula 1 is preferably 1:9 to 9:1. More preferably, n:m in the chemical formula 1 is 1:8 to 8:1, 1:7 to 7:1, 1:6 to 6:1, 1:5 to 5:1, 1:4 to 4:1, 1:3 to 3:1, or 1:2 to 2:1.

[0043]

[0044] Preferably, R1 and R2 are different from each other. Preferably, one of R1 and R2 is straight-chain hexanediyl and the other is straight-chain pentanediyl.

[0045]

[0046] Preferably, the polycarbonate diol is included in an amount of 0.005 to 5.0 parts by weight relative to 100 parts by weight of the polycarbonate resin. When the content is less than 0.005 parts by weight, the effect of adding the polycarbonate diol is minimal, and when the content is more than 5.0 parts by weight, there is a concern that the original physical properties of the polycarbonate resin may be impaired. More preferably, the polycarbonate diol is included in an amount of 0.01 parts by weight or more, 0.02 parts by weight or more, 0.03 parts by weight or more, 0.04 parts by weight or more, 0.05 parts by weight or more, 0.06 parts by weight or more, 0.07 parts by weight or more, 0.08 parts by weight or more, 0.09 parts by weight or more, or 0.1 parts by weight or more relative to 100 parts by weight of the polycarbonate resin; Contained in amounts of 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, or 1.0 parts by weight or less.

[0047]

[0048] Preferably, the polycarbonate diol has a weight average molecular weight of 300 g / mol to 3,000 g / mol. More preferably, the polycarbonate diol has a weight average molecular weight of 400 g / mol or more, or 500 g / mol or more; 2,900 g / mol or less, 2,800 g / mol or less, 2,700 g / mol or less, 2,600 g / mol or less, 2,500 g / mol or less, 2,400 g / mol or less, 2,300 g / mol or less, 2,200 g / mol or less, 2,100 g / mol or less, or 2,000 g / mol or less.

[0049]

[0050] Meanwhile, the polycarbonate resin composition according to the present invention may additionally include an antioxidant as needed. The antioxidant may play a role in maintaining the physical properties of the polycarbonate resin, particularly during high-temperature processing.

[0051]

[0052] The antioxidant described above is not limited to those used in polycarbonate resins, and for example, a phosphorus compound or a phenolic compound may be used. Representative examples thereof include at least one selected from the group consisting of PEP-36 (Bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritoldiphosphite) and DP9228 (bis(2,4-dicumylphenyl)pentaerythritol diphosphate). In addition, an example of the hindered phenolic antioxidant may include IR1010 ([3-[3-(4-hydroxy3,5-ditert-butyl-phenyl)propanoyloxy]-2,2-bis[3-(4-hydroxy-3,5-ditert-butylphenyl)propanoyloxymethyl]propyl] 3-(4-hydroxy-3,5-ditert-butyl-phenyl)propanoate). In addition, the antioxidant may be used alone or in combination of two or more. When two or more antioxidants are used, the weight ratio between the antioxidants is 1:15 to 15:1.

[0053]

[0054] Preferably, the antioxidant is included in an amount of 0.005 to 5.0 parts by weight relative to 100 parts by weight of the polycarbonate resin. When the content is less than 0.005 parts by weight, the effect of adding the antioxidant is minimal, and when the content is more than 5.0 parts by weight, there is a concern that the original physical properties of the antioxidant resin may be impaired. More preferably, the antioxidant is included in an amount of 0.01 parts by weight or more, 0.02 parts by weight or more, 0.03 parts by weight or more, 0.04 parts by weight or more, 0.05 parts by weight or more, 0.06 parts by weight or more, 0.07 parts by weight or more, 0.08 parts by weight or more, 0.09 parts by weight or more, or 0.1 parts by weight or more relative to 100 parts by weight of the polycarbonate resin; or 4.0 parts by weight or less, 3.0 parts by weight or less, 2.0 parts by weight or less, or 1.0 parts by weight or less.

[0055]

[0056] In addition, the polycarbonate resin composition according to the present invention may additionally include, if necessary, at least one selected from the group consisting of a heat stabilizer, a light stabilizer, a plasticizer, an antistatic agent, a nucleating agent, a flame retardant, an activator, an impact modifier, a fluorescent whitening agent, an ultraviolet absorber, a pigment, and a dye.

[0057]

[0058] Preferably, the polycarbonate resin composition according to the present invention has a long-wavelength transmittance of 85.0% or more. The method for measuring the long-wavelength transmittance is specified in the examples described below. More preferably, the polycarbonate resin composition according to the present invention has a long-wavelength transmittance of 85.1% or more, 85.2% or more, 85.3% or more, 85.4% or more, or 85.5% or more. Meanwhile, the theoretical upper limit of the long-wavelength transmittance is 100%, but for example, the polycarbonate resin composition according to the present invention has a long-wavelength transmittance of 95% or less, 94% or less, 93% or less, 92% or less, 91% or less, or 90% or less.

[0059]

[0060] Preferably, the polycarbonate resin composition according to the present invention has a long-wavelength YI of 5.30 or less. The method for measuring the long-wavelength YI is specified in the examples described below. More preferably, the polycarbonate resin composition according to the present invention has a long-wavelength YI of 5.25 or less, 5.20 or less, 5.19 or less, 5.18 or less, 5.17 or less, 5.16 or less, 5.15 or less, 5.14 or less, 5.13 or less, 5.12 or less, 5.11 or less, or 5.10 or less. In addition, the polycarbonate resin composition according to the present invention has a long-wavelength YI of 5.00 or more, 5.01 or more, 5.02 or more, 5.03 or more, 5.04 or more, or 5.05 or more.

[0061]

[0062] The present invention also provides an article comprising the polycarbonate resin composition. Preferably, the article is an extrusion-molded article or an injection-molded article.

[0063]

[0064] The method for manufacturing the above product may include the steps of mixing the polycarbonate resin composition according to the present invention and the additives described above, if necessary, using a mixer, then extruding the mixture using an extruder to manufacture pellets, drying the pellets, and then injecting them using an injection molding machine.

[0065] As described above, the polycarbonate resin composition according to the present invention has excellent optical properties, particularly light transmittance and light yellowness.

[0066] Hereinafter, embodiments of the present invention will be described in more detail in the following examples. However, the following examples are merely illustrative of embodiments of the present invention, and the content of the present invention is not limited by the following examples.

[0067]

[0068] In the following examples and comparative examples, the following materials were used.

[0069]

[0070] (A): Polycarbonate resin

[0071] LUPOY PC 1300-30-NP (bisphenol A-based polycarbonate resin, manufacturer: LG chemical, weight average molecular weight (Mw): 21,100 g / mol (measured by GPC using PC Standard using Agilent 1200 series)) was used.

[0072]

[0073] (B): Polycarbonate diol

[0074] (B1): Duranol T5650E (Manufacturer: Asahi Kasei, number average molecular weight (Mn): 500 g / mol, polycarbonate diol represented by the above chemical formula 1, wherein one of R1 and R2 is a straight-chain hexanediyl and the other is a straight-chain pentanediyl)

[0075] (B2): Duranol T5651 (Manufacturer: Asahi Kasei, number average molecular weight (Mn): 1,000 g / mol, polycarbonate diol represented by the above chemical formula 1, wherein one of R1 and R2 is straight-chain hexanediyl and the other is straight-chain pentanediyl)

[0076] (B3) Duranol T5652 (Manufacturer: Asahi Kasei, number average molecular weight (Mn): 2,000 g / mol, polycarbonate diol represented by the above chemical formula 1, wherein one of R1 and R2 is straight-chain hexanediyl and the other is straight-chain pentanediyl)

[0077] (B4) Duranol G3452 (Manufacturer: Asahi Kasei, number average molecular weight (Mn): 2,000 g / mol, polycarbonate diol represented by the above chemical formula 1, wherein one of R1 and R2 is a straight-chain propanediyl and the other is a straight-chain butanediyl)

[0078]

[0079] (C): Polyalkylene glycol

[0080] (C1) Polycerin DCB-2000 (Manufacturer: NOF Corporation, number-average molecular weight (Mn): 2,000 g / mol)

[0081] (C2) KONIX PP-2000 (Manufacturer: KPX chemical, number-average molecular weight (Mn): 2,000 g / mol, polypropylene glycol)

[0082]

[0083] (D): Antioxidant

[0084] DP9228 (Manufacturer: Dover Chemical Corporation, Cas No. 154862-43-8)

[0085]

[0086] (E) Antioxidant

[0087] IRGANOX® 1010 (Manufacturer: BASF, Cas No. 6683-19-8)

[0088]

[0089] Example 1

[0090] Based on 100 parts by weight of LUPOY PC 1300-30-NP(A), a polycarbonate resin, 3,500 ppmw of Duranol T5650E(B1), 1,500 ppmw of DP9228(D), and 500 ppmw of IRGANOX® 1010(E) were added to produce a polycarbonate resin composition at a rate of 55 kg per hour in a twin-screw extruder (L / D=36, Φ=45, barrel temperature 260°C).

[0091]

[0092] Examples 2 to 9

[0093] A polycarbonate composition was prepared in the same manner as in Example 1, except that Duranol T5650E (B1) was used with changes as shown in Table 1 below.

[0094]

[0095] Comparative Example 1

[0096] A polycarbonate composition was prepared in the same manner as in Example 1, except that 1,500 ppmw of DP9228(D) and 500 ppmw of IRGANOX® 1010(E) were used based on 100 parts by weight of LUPOY PC 1300-30-NP(A), a polycarbonate resin, as shown in Table 1 below.

[0097]

[0098] Comparative Examples 2, 3, and 4

[0099] A polycarbonate composition was prepared in the same manner as in Example 1, except that the materials listed in Table 1 below were used instead of Duranol T5650E (B1).

[0100] Usage (ppmw) 1) Polycarbonate diol polyalkylene glycol antioxidant (B1) (B2) (B3) (B4) (C1) (C2) (D) (E) Example 11, 500000001, 500500 Example 23, 500000001, 500500 Example 35, 500000001, 500500 Example 401, 50000001, 500500 Example 503, 50000001, 500500 Example 605, 50000001, 500500 Example 7001, 5000001, 500500 Example 8003, 5000001, 500500 Example 9005,5000001,500500Comparative example 10000001,500500Comparative example 20003,500001,500500Comparative example 300003,50001,500500Comparative example 4000003,5001,5005001) ppmw means the weight ratio for LUPOY PC 1300-30-NP(A), a polycarbonate resin.

[0101]

[0102] Experimental example

[0103] The physical properties of the polycarbonate compositions manufactured in the above examples and comparative examples were evaluated as follows.

[0104]

[0105] (1) 3T transmittance, 3T YI (280℃)

[0106] Each of the resin pellets manufactured in the above examples and comparative examples was manufactured into a rectangular specimen shape (3T injection specimen shape) having a thickness of 3 mm and a plane scale of 30*50 mm using an N-20C injection molding machine from JSW Co., Ltd. The measurement specimen was manufactured at a barrel temperature of 280°C. According to ASTM D1003, the transmittance at 420 nm was measured under a transmittance condition of 350 to 850 nm using the equipment UltraScan PRO from Hunter lab. In addition, the yellowing index was measured under a transmittance condition of 350 to 1050 nm using the equipment UltraScan PRO from Hunter lab according to ASTM D1925.

[0107]

[0108] (2) 150T optical transmittance, 150T YI

[0109] Each of the resin pellets manufactured in the above examples and comparative examples was manufactured into a rectangular specimen shape (4T injection specimen shape) having a thickness of 4 mm and a plane scale of 150*80 mm using an N-20C injection molding machine from JSW Co., Ltd. At this time, the barrel temperature of the injection molding machine was 280℃. Using a Spectrophotometer U-4100 from Hitachi, light of 380 to 780 nm was irradiated along the transverse direction of the specimen to measure the long-wave transmittance (T%) and long-wave color tone (YI). The long-wave color tone was measured in accordance with JIS Z 8722.

[0110]

[0111] (3) YI (3T, 280℃, 15 min)

[0112] Each of the resin pellets manufactured in the above examples and comparative examples was weighed and kept in the cylinder of the injection molding machine using a JSW (Co.) N-20C injection molding machine for 15 minutes, and then three consecutive injections of 3 mm thick specimens of the same specifications as the previous 3T YI (280°C) were performed to manufacture specimens. At this time, the barrel temperature of the injection machine was 280°C. For the third injection specimen among the injected specimens, the YI value was measured in the same manner as the measurement method of 3T YI (280°C).

[0113]

[0114] The above results are shown in Table 2 below.

[0115] Transmittance 3T YI Transmittance YIYI (3T, Tt%) (3T, 280℃) (150T, Tt%) (150T) (3T, 280℃, 15 min) Example 1 91.3 0.6 2 8 4.5 0 5.2 7 0.90 Example 2 91.5 0.6 2 8 5.10 5.14 0.81 Example 3 91.4 0.6 2 8 4.6 0 5.24 0.84 Example 4 91.2 0.6 0 8 4.7 0 5.25 0.88 Example 5 91.6 0.6 1 8 5.6 0 5.12 0.83 Example 6 91.4 0.6 2 8 5.10 5.21 0.86 Example 791.300.6184.905.190.88 Example 891.600.6085.805.070.82 Example 991.500.6085.105.170.84 Comparative Example 191.200.6183.405.530.94 Comparative Example 291.400.6285.105.230.87 Comparative Example 391.300.6384.605.320.91 Comparative Example 491.200.6284.905.480.90

[0116]

[0117] As shown in Table 1 above, there is no significant difference in the 3T transmittance and 3T YI of the examples and comparative examples according to the present invention. However, the examples according to the present invention showed significantly better results than the comparative examples in terms of long-wavelength transmittance and long-wavelength YI, and it can be confirmed from this that the composition according to the present invention has superior optical properties.

Claims

1. Polycarbonate resin; and Containing a polycarbonate diol represented by the following chemical formula 1, Polycarbonate resin composition: [Chemical Formula 1] In the above chemical formula 1, R1 and R2 are each independently C5~C 10 Straight-chain alkylene, or C5~C 10 It is cycloalkylene, n and m are each independently integers greater than or equal to 1.

2. In paragraph 1, The weight average molecular weight of the above polycarbonate resin is 14,000 g / mol to 50,000 g / mol. Composition.

3. In paragraph 1, The above polycarbonate diol is a random copolymer, Composition.

4. In paragraph 1, n:m is 1:9 to 9:1, Composition.

5. In paragraph 1, R1 and R2 are different from each other, Composition.

6. In paragraph 1, One of R1 and R2 is straight-chain hexanediyl, and the other is straight-chain pentanediyl, Composition.

7. In paragraph 1, The above polycarbonate diol has a weight average molecular weight of 300 g / mol to 3,000 g / mol. Composition.

8. In paragraph 1, The above polycarbonate diol is included in an amount of 0.005 to 5.0 parts by weight based on 100 parts by weight of the polycarbonate resin. Composition.

9. In paragraph 1, The above polycarbonate diol is included in an amount of 0.1 to 1.0 parts by weight based on 100 parts by weight of the polycarbonate resin. Composition.

10. In paragraph 1, The composition further comprises an antioxidant, Composition.

11. In paragraph 10, The above antioxidant is included in an amount of 0.005 to 5.0 parts by weight based on 100 parts by weight of the polycarbonate resin. Composition.

12. An article comprising a composition according to any one of claims 1 to 11.

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