TRANSPARENT RESIN COMPOSITION AND TRANSPARENT RESIN MOLDED ARTICLE

Abstract

To provide a transparent resin composition having excellent optical characteristics, particularly, excellent optical characteristics under high temperature and high humidity.

There is provided a transparent resin composition, including: an aromatic polycarbonate resin; and a water-insoluble organic sulfonic acid and/or a metal salt thereof, in which a content of the water-insoluble organic sulfonic acid and/or the metal salt thereof is 0.01 to 3.0 pts.Math.mass to 100 pts.Math.mass of the aromatic polycarbonate resin, and a dissolved amount of the water-insoluble organic sulfonic acid and/or the metal salt thereof is not more than 0.5 g to 100 g of pure water.

Claims

1. A transparent resin composition, comprising: an aromatic polycarbonate resin; and a water-insoluble organic sulfonic acid and/or a metal salt thereof; wherein a content of the water-insoluble organic sulfonic acid and/or the metal salt thereof is 0.01 to 3.0 pts.Math.mass to 100 pts.Math.mass of the aromatic polycarbonate resin, solubility of the water-insoluble organic sulfonic acid and/or the metal salt thereof is 0.5 g or less in 100 g of pure water, and a total light transmittance of the transparent resin composition is at least 75% at a wavelength of 380 to 730 nm in the JIS K7136 standard.

2. The transparent resin composition according to claim 1, wherein a weight-average molecular weight of the aromatic polycarbonate resin in terms of polystyrene is between 36,000 and 63,000.

3. The transparent resin composition according to claim 1, wherein the aromatic polycarbonate resin includes a recovered polycarbonate resin, and a content of the recovered polycarbonate resin is from 1 to less than 100 mass % to the total mass of the aromatic polycarbonate resin.

4. The transparent resin composition according to claim 1, wherein the aromatic polycarbonate resin includes a recovered polycarbonate resin.

5. The transparent resin composition according to claim 1, wherein the aromatic polycarbonate resin includes an aromatic polycarbonate compound having 0.01 to 3.0 mol % branch structure.

6. The transparent resin composition according to claim 1, wherein the aromatic polycarbonate resin includes an aromatic polycarbonate-polyorganosiloxane copolymer.

7. The transparent resin composition according to claim 1, wherein the water-insoluble organic sulfonic acid is a metal salt of the water-insoluble organic sulfonic acid that includes an aromatic sulfonic acid metal salt compound.

8. The transparent resin composition according to claim 7, wherein a weight-average molecular weight of the aromatic sulfonic acid metal salt compound in terms of polystyrene is at least 30,000.

9. The transparent resin composition according to claim 7, wherein the aromatic sulfonic acid metal salt compound comprises a sulfonic acid metal base, and wherein a content of the sulfonic acid metal base is 0.1 to 10 mol %.

10. The transparent resin composition according to claim 7, wherein the aromatic sulfonic acid metal salt compound is a potassium salt of polystyrene sulfonic acid.

11. The transparent resin composition according to claim 1, further comprising a light diffusing agent.

12. The transparent resin composition according to claim 11, wherein the light diffusing agent is an inorganic particle or an organic particle, and an average particle diameter of the inorganic particle or the organic particle is 0.1 to 50 μm.

13. The transparent resin composition according to claim 11, wherein a content of the light diffusing agent is 0.0005 to 6.0 pts.Math.mass to 100 pts.Math.mass of the aromatic polycarbonate resin.

14. The transparent resin composition according to claim 1, further comprising a drip preventing agent, wherein a content of the drip preventing agent is not more than 0.03 pts.Math.mass to 100 pts.Math.mass of the aromatic polycarbonate resin.

15. The transparent resin composition according to claim 1, wherein the total light transmittance of the transparent resin composition is not less than 85% at a wavelength of 380 to 730 nm in the JIS K7136 standard.

16. The transparent resin composition according to claim 1, wherein a rate of decrease of a total light transmittance of the transparent resin composition after an acceleration test under a condition of 120° C., 100% relative humidity, and 24 hours is within 8% of a total light transmittance of the transparent resin composition before the acceleration test.

17. A transparent resin molded article that is obtained by molding the transparent resin composition according to claim 1.

18. The transparent resin molded article according to claim 17 that is a cover for lighting apparatus or a diffusing cover for lighting apparatus for display.

19. A transparent resin composition, comprising: an aromatic polycarbonate resin; and a water-insoluble organic sulfonic acid and/or a metal salt thereof; wherein a content of the water-insoluble organic sulfonic acid and/or the metal salt thereof is 0.01 to 3.0 pts.Math.mass to 100 pts.Math.mass of the aromatic polycarbonate resin, solubility of the water-insoluble organic sulfonic acid and/or the metal salt thereof is 0.5 g or less in 100 g of pure water, and a total light transmittance of the transparent resin composition is at least 75% at a wavelength of 380 to 730 nm in the JIS K7136 standard, and a rate of decrease of a total light transmittance of the transparent resin composition after an acceleration test under a condition of 120° C., 100% relative humidity, and 24 hours is within 8% of a total light transmittance of the transparent resin composition before the acceleration test.

20. A transparent resin composition, comprising: an aromatic polycarbonate resin; and a water-insoluble organic sulfonic acid and/or a metal salt thereof; wherein a content of the water-insoluble organic sulfonic acid and/or the metal salt thereof is 0.01 to 3.0 pts.Math.mass to 100 pts.Math.mass of the aromatic polycarbonate resin, solubility of the water-insoluble organic sulfonic acid and/or the metal salt thereof is 0.5 g or less in 100 g of pure water, and a total light transmittance of the transparent resin composition is at least 85% at a wavelength of 380 to 730 nm in the JIS K7136 standard, and a rate of decrease of a total light transmittance of the transparent resin composition after an acceleration test under a condition of 120° C., 100% relative humidity, and 24 hours is within 8% of a total light transmittance of the transparent resin composition before the acceleration test.

Description

EXAMPLES

[0142] Hereinafter, the effects of the present technology will be specifically described with Examples. Note that the scope of the present technology is not limited to Examples.

[0143] Transparent resin compositions according to Examples 1-1 to 1-8 and Examples 2-1 to 2-11 and resin compositions according to Comparative Examples 1-1 to 1-6 and Comparative Examples 2-1 to 2-6 were prepared, and each of the transparent resin compositions and each of the resin compositions were evaluated. The composition (pts.Math.mass) of each of the transparent resin compositions according to Examples 1-1 to 1-8 and evaluation results of total light transmittance (%), haze (%), flame retardancy, and durability thereof are shown in the following Table 1. The composition (pts.Math.mass) of each of the resin composition according to Comparative Examples 1-1 to 1-6 and evaluation results of total light transmittance (%), haze (%), flame retardancy, and durability thereof are shown in the following Table 2. The composition (pts.Math.mass) of each of the transparent resin compositions according to Examples 2-1 to 2-11 and evaluation results of total light transmittance (%), haze (%), flame retardancy, and durability thereof are shown in the following Table 3. The composition (pts.Math.mass) of each of the resin compositions according to Comparative Examples 2-1 to 2-6 and evaluation results of total light transmittance (%), haze (%), flame retardancy, and durability are shown in the following Table 4.

[Transparent Resin Compositions According to Examples 1-1 to 1-8 and Examples 2-1 to 2-11, and Resin Compositions According to Comparative Examples 1-1 to 1-6 and 2-1 to 2-6]

[0144] Each component contained in the transparent resin compositions according to Examples 1-1 to 1-8 and Examples 2-1 to 2-11 and resin compositions according to Comparative Examples 1-1 to 1-6 and 2-1 to 2-6 will be described. Note that the components (A component, B component, C component, and D component) respectively correspond to the aromatic polycarbonate resin, the water-insoluble organic sulfonic acid and/or the metal salt thereof, the light diffusing agent, and the drip preventing agent described in the above-mentioned first embodiment.

[0145] (A Component: Aromatic Polycarbonate Resin)

[0146] As an aromatic polycarbonate resin, which is an A component, the following components A-1 to A-4 were used.

[0147] A-1: commercially available PC resin having a medium molecular weight (L-1225L: chemical manufactured by TEIJIN LIMITED, Mw in terms of PS is 45,000).

[0148] A-2: commercially available PC resin having a low molecular weight (L-1225LLL: chemical manufactured by TEIJIN LIMITED, Mw in terms of PS is 33,000).

[0149] A-3: PC resin (Mw in terms of PS: 46,000) pelletized after pulverizing a used building material sheet coarsely and then melt-kneading it by a twin screw extruder.

[0150] A-4: pelletized PC resin (Mw in terms of PS: 32,000) obtained by treating a used CD, which has been pulverized (2 to 20 mm), with an alkaline hot aqueous solution to remove a coating layer (a recording material layer, a label, an adhesive layer, a hardened layer, a metallic reflective layer, and the like), and then melt-kneading it by a twin screw extruder.

[0151] (B Component: Water-Insoluble Organic Sulfonic Acid and/or Metal Salt thereof)

[0152] As a water-insoluble organic sulfonic acid and/or a metal salt thereof, which is a B component, the following component B-1 was used.

[0153] B-1: water-insoluble polymer-type flame retardant, one obtained by introducing a potassium salt of a sulfonic acid into the surface of polystyrene (manufactured by Sony Corp.: PSS-K). A dissolved amount (solubility): 0.11 g/100 g of pure water.

[0154] The dissolved amount (solubility) was calculated by mixing 3 g of the component B-1 with 100 g of pure water, stirring for 30 minutes, and then filtering it with 0.5 μm filter to measure the insoluble matter.

[0155] (b Component: Water-Soluble Flame Retardant)

[0156] Further, as a water-soluble flame retardant, which is a b component, the following components b-1 to b-2 were used.

[0157] b-2: water-soluble flame retardant, commercially available potassium perfluorobutanesulfonate (manufactured by Tokyo Chemical Industry Co., Ltd.: Potassium Nonafluoro-1-butanesulfonate). A dissolved amount (solubility):4.6 g/100 g of pure water.

[0158] b-3: water-soluble flame retardant, commercially available sodium paratoluenesulfonic acid, (manufactured by FUJIFILM Wako Pure Chemical Corporation: p-Toluenesulfonic Acid Sodium Salt). A dissolved amount (solubility): 24.0 g/100 g of pure water.

[0159] The dissolved amount (solubility) was calculated by mixing 25 g of the component b-1 or b-2 with 100 g of pure water, stirring for 30 minutes, and then filtering it with 0.5 μm filter to measure the insoluble matter.

[0160] (C Component: Light Diffusing Agent)

[0161] As a light diffusing agent, which is a C component, the following component C-1 was used.

[0162] C-1: crosslinked (meth) acrylic polymer particle (manufactured by SEKISUI PLASTICS CO., LTD.: TECHPOLYMER MBX-5).

[0163] (D Component: Drip Preventing Agent)

[0164] As a drip preventing agent, which is a D component, the following component D-1 was used.

[0165] D-1: commercially available PTFE (manufactured by DAIKIN INDUSTRIES, LTD.: POLYFLON FA500H) as polytetrafluoroethylene having fibril-forming ability

[0166] [Molding of Transparent Resin Compositions according to Examples 1-1 to 1-8 and Examples 2-1 to 2-11 and Resin Compositions according to Comparative Examples 1-1 to 1-6 and 2-1 to 2-6]

[0167] The above-mentioned various components (components A-1 to A-4, component B-1, components b-1 to b-2, component C-1, and component D-1) were blended at a formulation ratio shown in the following Table 1 (Examples 1-1 to Examples 1-8), Table 2 (Comparative Examples 1-1 to Comparative Examples 1-6), Table 3 (Examples 2-1 to Examples 2-11), and Table 4 (Comparative Examples 2-1 to Comparative Examples 2-6), blended with a tumbler, and melt-kneaded using a co-rotating twin screw kneading extruder (manufactured by LABO PLASTMILL, using a twin screw extrusion unit) to obtain pellets (a transparent resin composition and a resin composition). The extrusion condition was the discharge rate of 4 kg/h, the screw rotation rate was 48 rpm, and the extrusion temperature was 270° C. from the first supply port to the die portion. The obtained pellets were dried at 120° C. for eight hours by a hot air circulation drier, and molded using an injection molding machine at a cylinder temperature of 290° C. and a mold temperature of 70° C. to prepare a specimen for optical measurement and a specimen for measuring flame retardancy.

[0168] Next, in accordance with the following test method, the specimen for optical measurement and the specimen for measuring flame retardancy prepared above were used for evaluating the total light transmittance (%), haze (%), the flame retardancy, and durability.

[0169] [Test Method for Total Light Transmittance]

[0170] Using a haze meter NDH2000 (manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.), the total light transmittance was measured in accordance with JIS K 7136 for a flat plate specimen having a thickness of 1.0 mm.

[0171] [Test Method for Haze]

[0172] Using a haze meter NDH2000 (manufactured by NIPPON DENSHOKU INDUSTRIES Co., LTD.), the haze was measured in accordance with JIS K 7136 for a flat plate specimen having a thickness of 1.0 mm.

[0173] [Test Method for Flame Retardancy]

[0174] Combustion tests in accordance with UL standard 94 were performed with a thickness of 1.6 mm, the grades thereof were evaluated, and it was determined that not less than V-1 were good. The UL94V standard and determination criteria are shown in the following Table 5.

[0175] [Test Method for Durability]

[0176] Using the value of total light transmittance obtained by causing the molded article (specimen for optical measurement) obtained in the above to stand under high temperature and high humidity conditions of 120° C. and 100% RH to accelerate degradation, evaluation was performed. In the case where the total light transmittance after the acceleration test maintains not less than 75% that represents the transparency, it is determined as good (indicated by a circle).

[0177] The results of Examples 1-1 to 1-8, the results of Comparative Examples 1-1 to 1-6, the results of Examples 2-1 to 2-11, and the results of Comparative Examples 1-1 to 1-6 and 2-1 to 2-6 are respectively shown in the following Table 1, Table 2, Table 3, and Table 4.

[0178] As is clear from Examples 1-1 to 1-8 shown in Table 1 and Examples 2-1 to 2-11 shown in Table 3, it was confirmed that the transparent resin compositions according to Examples 1-1 to 1-8 shown in Table 1 and the transparent resin compositions according to Examples 2-1 to 2-11 shown in Table 3 had excellent flame retardancy and durability as compared with the existing flame retardant polycarbonate resin composition, the resin compositions according to Comparative Examples 1-1 to 1-6 shown in Table 2, and the resin compositions according to Comparative Examples 2-1 to 2-6. Further, it is considerable that the transparent resin composition according to the present technology is compatible with a thin molded article and is a flame retardant resin composition having excellent flame retardancy, moldability, flexural modulus, and durability as compared with the existing flame retardant polycarbonate resin composition.

[0179] Note that the results of Comparative Examples are shown in the following.

Comparative Examples 1-1 and Comparative Examples 2-1

[0180] As a result of durability test, the total light transmittance was significantly reduced in the case where the water-soluble flame retardant (b-2) was used.

Comparative Examples 1-2 and Comparative Examples 2-2

[0181] As a result of durability test, the total light transmittance was significantly reduced in the case where the water-soluble flame retardant (b-3) was used.

Comparative Examples 1-3 and 1-4, and Comparative Examples 2-3 and 2-4

[0182] Regardless of the content of PTFE (D-1: drip preventing agent), the total light transmittance was significantly reduced in the case where the water-soluble flame retardant (b-2) was used.

Comparative Examples 1-5 and 1-6, and Comparative Examples 2-5 and 2-6

[0183] Regardless of the presence or absence of the recovered polycarbonate resin (A-3), the degree of reduction in total light transmittance was unchanged.

TABLE-US-00001 TABLE 1 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple1-1 ple1-2 ple1-3 ple1-4 ple1-5 ple1-6 ple1-7 ple1-8 [A component] A-1 100 50 50 100 100 Aromatic A-2 100 polycarbonate A-3 100 50 resin A-4 100 50 <Arithmetic mean 45000 33000 46000 32000 45300 38900 45000 45000 of weight-average molecular weight (in terms of PS)> [B component] B-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Water-insoluble organic sulfonic acid and/or metal salt thereof Water-soluble b-2 flame retardant b-3 [D component] D-1 0.01 0.03 Drip preventing agent [Evaluation Total light 89 89.3 88.7 88.2 88.9 88.8 86.8 83.2 item] transmittance [%] Haze [%] 12.8 13.1 13.4 13.3 13 13.1 15.2 18.1 Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 (UL94V), thickness 1.6 mm Durability ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ (81.9%) (82.2%) (81.7%) (81.2%) (82.1%) (81.5%) (79.5%) (76.0%)

TABLE-US-00002 TABLE 2 Comparison Comparison Comparison Comparison Comparison Comparison example1-1 example 1-2 example 1-3 example 1-4 example 1-5 example 1-6 [A component] A-1 100 100 100 100 50 50 Aromatic A-2 polycarbonate A-3 50 50 resin A-4 <Arithmetic mean 45000 45000 45000 45000 45300 38900 of weight-average molecular weight (in terms of PS)> [B component] B-1 Water-insoluble organic sulfonic acid and/or metal salt thereof Water-soluble b-2 0.1 0.1 0.1 0.1 flame retardant b-3 0.1 0.1 [D component] D-1 0.01 0.03 Drip preventing agent [Evaluation Total light 88.5 88.8 86.5 84.1 88.3 88.3 item] transmittance [%] Haze [%] 12.6 12.9 15.5 17.8 12.5 12.2 Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 (UL94V), thickness 1.6 mm Durability x x x x x x (52.2%) (55.3%) (49.6%) (47.1%) (52.8%) (55.6%)

TABLE-US-00003 TABLE 3 Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- Exam- ple2-1 ple2-2 ple2-3 ple2-4 ple2-5 ple2-6 ple2-7 ple2-8 ple2-9 ple2-10 ple2-11 [A component] A-1 100 50 50 100 100 100 100 100 Aromatic A-2 100 polycarbonate A-3 100 50 resin A-4 100 50 <Arithmetic 45000 33000 46000 32000 45300 38900 45000 45000 45000 45000 45000 mean of weight-average molecular weight (in terms of PS)> [B component] B-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Water- insoluble organic sulfonic acid and/or metal salt thereof Water-soluble b-2 flame retardant b-3 [C component] C-1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 0.1 Light diffusing C-2 0.1 0.1 0.1 agent [D component] D-1 0.01 0.03 0.01 0.03 Drip preventing agent [Evaluation Total light 86.1 86.3 85.8 85.7 85.9 86 83.8 80.3 87.8 84.3 82.2 item] transmittance [%] Haze [%] 93.3 93.2 93.9 93.8 93.5 93.4 93.9 95.2 92.4 92.8 94.4 Flame V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 V-0 retardancy (UL94V), thickness 1.6 mm Durability ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ ∘ (78.8%) (79.2%) (78.3%) (78.4%) (78.8%) (78.9%) (77.2%) (75.2%) (79.1%) (77.3%) (75.1%)

TABLE-US-00004 TABLE 4 Comparison Comparison Comparison Comparison Comparison Comparison example2-1 example 2-2 example 2-3 example 2-4 example 2-5 example 2-6 [A component] A-1 100 100 100 100 50 50 Aromatic A-2 polycarbonate A-3 50 50 resin A-4 <Arithmetic mean 45000 45000 45000 45000 45300 38900 of weight-average molecular weight (in terms of PS)> [B component] B-1 Water-insoluble organic sulfonic acid and/or metal salt thereof Water-soluble b-2 0.1 0.1 0.1 0.1 flame retardant b-3 0.1 0.1 [C component] C-1 0.1 0.1 0.1 0.1 0.1 0.1 Light diffusing C-2 agent [D component] D-1 0.01 0.03 Drip preventing agent [Evaluation Total light 86.8 86.7 84.1 80.9 85.5 85.2 item] transmittance [%] Haze[%] 92.9 93.1 93.7 94.9 93.6 93.3 Flame retardancy V-0 V-0 V-0 V-0 V-0 V-0 (UL94V), thickness 1.6 mm Durability x x x x x x (51.4%) (53.5%) (48.7%) (46.3%) (52.2%) (53.9%)

TABLE-US-00005 TABLE 5 UL94V standard and determination criteria Determination Class category V-0 V-1 V-2 criteria Combustion time after first contact with flame (S) ≤10 ≤30 ≤30 Combustion time after second contact with flame (S) ≤10 ≤30 ≤30 Total combustion time of five components ≤50 ≤250 ≤250 Combustion time of each specimen + glowing time (S) ≤30 ≤60 ≤60 Combustion reaches damp No No No Cotton ignites by dropping No No Yes