Resin composition, optical molded article, method for manufacturing the resin composition, and method for manufacturing the optical molded article

Abstract

To provide a resin composition that can suppress mold contamination. [Solution] A resin composition comprising a pentaerythritol derivative composition represented by a specific general formula and a polymer represented by a specific general formula, wherein the content of the pentaerythritol derivative composition per 100 parts by mass of the polymer is 1.0 part by mass or more and 5.0 parts by mass or less, the pentaerythritol derivative composition comprises pentaerythritol and a pentaerythritol ester compound, and the mass ratio of RCOO groups having 20 to 24 carbon atoms in the pentaerythritol derivative composition, with the mass of RCOO groups having 18 to 24 carbon atoms being 1, is 0.90 to 0.99.

Description

[Technical Field]

[0001] The present invention relates to a resin composition, an optically molded article, a method for producing a resin composition, and a method for producing an optically molded article. [Background technology]

[0002] Cyclic olefin resin compositions are widely used as raw materials for various optical components because they exhibit excellent transparency and can withstand use under high-temperature conditions.

[0003] Patent Document 1 describes "a thermoplastic resin composition characterized by comprising (A) a cyclic olefin-based thermoplastic resin and (B) an ester compound of glycerin and a saturated fatty acid." Furthermore, Patent Document 1 states, "The present invention was made against the background of the above-mentioned problems, and its objective is to provide a thermoplastic resin composition that retains the various properties of conventionally known cyclic olefin-based thermoplastic resins, has excellent release properties during molding and surface coating properties of molded products, and has excellent stability at high temperatures." [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2003-238774 [Overview of the project] [Problems that the invention aims to solve]

[0005] This invention provides a resin composition that can suppress mold contamination. [Means for solving the problem]

[0006] According to the present invention, the following resin composition, optical molded article, method for producing the resin composition, and method for producing the optical molded article are provided.

[0007] 1. A resin composition comprising a pentaerythritol derivative composition represented by the following general formula (1) and a polymer represented by the following general formula (2), [ka] (In general formula (1), R is a hydrocarbon group, the number of carbon atoms in the RCOO group is between 18 and 24, and n is a real number between 0 and 4.) [ka] (In general formula (2), x and y represent the copolymerization ratio and are real numbers satisfying 0 / 100 ≤ y / x ≤ 95 / 5. x and y are based on moles. n represents the number of substitutions of substituent Q and is a real number 0 ≤ n ≤ 2. a R is a 2+n valent group selected from the group consisting of hydrocarbon groups with 2 to 20 carbon atoms. b R is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 28 carbon atoms. c Q is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms. Q is a halogen atom, an alkyl halide, an alkoxy group, or a -COOR group. d That is. R d (This refers to a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) The content of the pentaerythritol derivative composition per 100 parts by mass of the polymer is 1.0 part by mass or more and 5.0 parts by mass or less. The aforementioned pentaerythritol derivative composition comprises pentaerythritol and a pentaerythritol ester compound. A resin composition in which, when the mass of RCOO groups having 18 to 24 carbon atoms is set to 1, the mass ratio of RCOO groups having 20 to 24 carbon atoms is 0.90 to 0.99. 2. The resin composition according to 1, wherein the pentaerythritol derivative composition comprises a pentaerythritol monoester compound having n=1 in general formula (1), a pentaerythritol diester compound having n=2 in general formula (1), a pentaerythritol triester compound having n=3 in general formula (1), and a pentaerythritol tetraester compound having n=4 in general formula (1). 3. The resin composition according to 2., wherein, in a chart obtained by gel permeation chromatography (GPC) of the pentaerythritol derivative composition under the following conditions, the ratio of the sum of the peak area of ​​the pentaerythritol monoester compound and the peak area of ​​the pentaerythritol diester compound, with the total peak area being 1, is 0.60 or more and 0.80 or less. Column: G2000HXL+G1000HXL Solvent: THF Flow rate: 1.0mL / min Column temperature: 40℃ Sample concentration: 0.3% Injection volume: 100μL Detector: RI Standard material: Polystyrene (manufactured by Tosoh Corporation, Mw=500, 2630, 10200) 4. The resin composition according to 2. or 3., wherein, in a chart obtained by gel permeation chromatography (GPC) of the pentaerythritol derivative composition under the following conditions, the ratio of the sum of the peak area of ​​the pentaerythritol triester compound and the peak area of ​​the pentaerythritol tetraester compound, with the total peak area being 1, is 0.18 or more and less than 0.40. Column: G2000HXL+G1000HXL Solvent: THF Flow rate: 1.0mL / min Column temperature: 40℃ Sample concentration: 0.3% Injection volume: 100μL Detector: RI Standard material: Polystyrene (manufactured by Tosoh Corporation, Mw=500, 2630, 10200) 5. The resin composition according to any one of 1. to 4., wherein when the total mass of the pentaerythritol derivative composition is 1, the content of the pentaerythritol is 0.002 or more and 0.010 or less. 6. The resin composition according to any one of 1. to 5., wherein the polymer comprises (i) a copolymer of ethylene or an α-olefin and a cyclic olefin. 7. The polymer comprises a copolymer formed from ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 [[ID=8>]]-3-dodecene, the resin composition according to 6. 8. An optical molded article comprising the resin composition according to any one of 1. to 7. 9. The optical molded article according to 8., wherein the optical molded article comprises a lens. 10. The optical molded article according to 8. or 9., wherein the maximum thickness portion of the optical molded article is 1.0 mm or more and 20.0 mm or less. 11. A method for producing a resin composition, comprising a pentaerythritol derivative represented by the following general formula (1) and a polymer represented by the following general formula (2),

Chemical formula

Chemical formula

[0008] According to the present invention, a resin composition that can suppress mold contamination can be provided. [Brief explanation of the drawing]

[0009] [Figure 1] This is a stereomicroscope image of the mold from Example 1. [Figure 2]This is a stereomicroscope image of the mold from Example 2. [Figure 3] This is a stereomicroscope image of the mold for Comparative Example 1. [Figure 4] This is a stereomicroscope image of particulate gas contamination generated in the mold of Comparative Example 1. [Modes for carrying out the invention]

[0010] In this embodiment, unless otherwise specified, "A~B" indicating a numerical range represents A or greater and B or less.

[0011] In this embodiment, "having substituents" of an alkyl group, unless otherwise specified, means that hydrogen atoms present in its structure are substituted by substituents. The position of the substituents and the number of substituents are not particularly limited. Note that if the substituent has carbon atoms, the number of carbon atoms in the substituent is not included in the total number of carbon atoms of the substituted group. For example, an ethyl group having a phenyl group as a substituent is considered an alkyl group with 2 carbon atoms.

[0012] 1.Resin composition The resin composition of this embodiment will be described below.

[0013] The resin composition of this embodiment is a resin composition comprising a pentaerythritol derivative composition represented by the following general formula (1) and a polymer represented by the following general formula (2).

[0014] [ka]

[0015] In general formula (1), R is a hydrocarbon group, the number of carbon atoms in the RCOO group is between 18 and 24, and n is a real number between 0 and 4.

[0016] [ka]

[0017] In general formula (2), x and y represent the copolymerization ratio and are real numbers satisfying 0 / 100 ≤ y / x ≤ 95 / 5. x and y are based on moles. n represents the number of substituents Q and is a real number 0 ≤ n ≤ 2. a R is a 2+n valent group selected from the group consisting of hydrocarbon groups with 2 to 20 carbon atoms. b R is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 28 carbon atoms. c Q is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms. Q is a halogen atom, an alkyl halide, an alkoxy group, or a -COOR group. d That is. R d This is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0018] In the resin composition of this embodiment, the content of the pentaerythritol derivative composition represented by general formula (1) per 100 parts by mass of the polymer represented by general formula (2) is 1.0 part by mass or more and 5.0 parts by mass or less. The pentaerythritol derivative composition represented by general formula (1) contains pentaerythritol and a pentaerythritol ester compound. In the pentaerythritol derivative composition represented by general formula (1), the mass ratio of RCOO groups having 20 to 24 carbon atoms to the mass of RCOO groups having 18 to 24 carbon atoms is 0.90 to 0.99.

[0019] Although the mechanism by which the resin composition of this embodiment can suppress mold fouling is not clear, it is presumed that by combining the polymer represented by general formula (2) with the pentaerythritol derivative composition represented by general formula (1), the formation of lower carboxylic acids that cause mold fouling is suppressed, thereby suppressing mold fouling.

[0020] Furthermore, as a result of the inventors' investigations, it became clear that mold contamination becomes an even greater problem when molding large molded bodies. Since the resin composition of this embodiment can suppress mold contamination, the resin composition of this embodiment is useful when molding large molded bodies. Here, a large molded body in this embodiment refers to a molded body with a diameter of approximately several tens of millimeters to several hundred millimeters.

[0021] The following describes each component in the resin composition of this embodiment.

[0022] <Pentaerythritol derivative composition represented by general formula (1)> The following describes pentaerythritol derivative compositions represented by general formula (1). In this embodiment, unless otherwise specified, "pentaerythritol derivative composition represented by general formula (1)" means a composition containing two or more pentaerythritol derivatives represented by general formula (1).

[0023] The pentaerythritol derivative composition contained in the resin composition of this embodiment is a composition containing a pentaerythritol derivative represented by the following general formula (1).

[0024] [ka]

[0025] In general formula (1), R is a hydrocarbon group, the number of carbon atoms in the RCOO group is between 18 and 24, and n is a real number between 0 and 4.

[0026] The pentaerythritol derivative composition represented by general formula (1) comprises pentaerythritol and a pentaerythritol ester compound.

[0027] Furthermore, when n=0 in general formula (1), general formula (1) represents pentaerythritol; when n=1 in general formula (1), general formula (1) represents a pentaerythritol monoester compound; when n=2 in general formula (1), general formula (1) represents a pentaerythritol diester compound; when n=3 in general formula (1), general formula (1) represents a pentaerythritol triester compound; and when n=4 in general formula (1), general formula (1) represents a pentaerythritol tetraester compound.

[0028] In general formula (1), R is, for example, an aliphatic hydrocarbon group or an aromatic hydrocarbon group. From the viewpoint of compatibility with the resin, it is preferably an aliphatic hydrocarbon group, more preferably an alkyl group, a halogenated alkyl group, an alkenyl group, or a halogenated alkenyl group, even more preferably an alkyl group, even more preferably a linear or branched alkyl group, and even more preferably a linear alkyl group.

[0029] In a pentaerythritol derivative composition represented by general formula (1), the mass ratio of RCOO groups having 20 to 24 carbon atoms to the mass of RCOO groups having 18 to 24 carbon atoms is 0.90 or more, preferably 0.92 or more, more preferably 0.94 or more, even more preferably 0.95 or more, and 0.99 or less, and 0.90 to 0.99 or less, and even more preferably 0.95 to 0.99 or less, and even more preferably 0.95 to 0.99 or less, from the viewpoint of further suppressing mold contamination.

[0030] In a pentaerythritol derivative composition represented by general formula (1), the mass ratio of RCOO groups having 18 to 19 carbon atoms to the mass of RCOO groups having 18 to 24 carbon atoms is, for example, 0.001 or more, 0.005 or more, 0.01 or more, and from the viewpoint of further suppressing mold contamination, preferably 0.10 or less, more preferably 0.08 or less, and even more preferably 0.05 or less, and from the viewpoint of further suppressing mold contamination, preferably 0.001 to 0.10 or less, more preferably 0.005 to 0.08 or less, and even more preferably 0.01 to 0.05 or less.

[0031] In a pentaerythritol derivative composition represented by general formula (1), the mass ratio of RCOO groups having 18 carbon atoms to the mass of RCOO groups having 18 or more carbon atoms with a mass of RCOO groups having 24 or more carbon atoms is, for example, 0.001 or more, 0.005 or more, 0.01 or more, and from the viewpoint of further suppressing mold contamination, it is preferably 0.10 or less, more preferably 0.08 or less, and even more preferably 0.05 or less, and from the viewpoint of further suppressing mold contamination, it is preferably 0.001 or more and 0.10 or less, more preferably 0.005 or more and 0.08 or less, and even more preferably 0.01 or more and 0.05 or less.

[0032] In a pentaerythritol derivative composition represented by general formula (1), the mass ratio of RCOO groups having 20 carbon atoms to the mass of RCOO groups having 18 to 24 carbon atoms is, for example, 0.01 to 0.30, 0.02 to 0.20, or 0.05 to 0.15.

[0033] In a pentaerythritol derivative composition represented by general formula (1), the mass ratio of RCOO groups having 22 carbon atoms to the mass of RCOO groups having 18 to 24 carbon atoms is preferably 0.50 or more, more preferably 0.60 or more, even more preferably 0.70 or more, and still more preferably 0.75 or more, and may be 0.95 or less, 0.90 or less, and 0.85 or less, and may be 0.50 to 0.95, more preferably 0.60 to 0.90, even more preferably 0.70 to 0.85, and still more preferably 0.75 to 0.85.

[0034] In a pentaerythritol derivative composition represented by general formula (1), the mass ratio of RCOO groups having 24 carbon atoms to the mass of RCOO groups having 18 to 24 carbon atoms is, for example, 0.001 to 0.10, 0.005 to 0.08, or 0.01 to 0.05.

[0035] In the pentaerythritol derivative composition represented by general formula (1), the mass ratio of RCOO groups having 22 carbon atoms to RCOO groups having 20 carbon atoms (RCOO groups having 22 carbon atoms / RCOO groups having 20 carbon atoms) is preferably 1 to 15, more preferably 3 to 14, and even more preferably 5 to 12, from the viewpoint of further suppressing mold contamination.

[0036] The method for calculating the mass ratio of RCOO groups with a specific number of carbon atoms is not particularly limited, but for example, when producing a pentaerythritol ester compound (Z), the mass ratio of starting carboxylic acids with a specific number of carbon atoms can be considered as the mass ratio of RCOO groups with a specific number of carbon atoms. For example, when the amount of monocarboxylic acid with 18 to 24 carbon atoms charged is set to 1, the ratio of the amount of monocarboxylic acid with 20 to 24 carbon atoms charged can be considered as the mass ratio of RCOO groups with 20 to 24 carbon atoms when the mass of RCOO groups with 18 to 24 carbon atoms is set to 1.

[0037] From the viewpoint of further suppressing mold fouling, the pentaerythritol derivative composition represented by general formula (1) preferably includes a pentaerythritol monoester compound where n=1 in general formula (1), a pentaerythritol diester compound where n=2 in general formula (1), a pentaerythritol triester compound where n=3 in general formula (1), and a pentaerythritol tetraester compound where n=4 in general formula (1).

[0038] In a chart obtained by gel permeation chromatography (GPC) of a pentaerythritol derivative composition represented by general formula (1) under the following conditions (α), the ratio of the sum of the peak areas of the pentaerythritol monoester compound and the pentaerythritol diester compound, with the total peak area being 1, is preferably 0.60 or higher, more preferably 0.62 or higher, even more preferably 0.64 or higher, and for example, it may be 0.80 or lower, 0.75 or lower, 0.70 or lower, or 0.68 or lower, and for further reasons, it may be 0.60 or higher and 0.80 or lower, more preferably 0.62 or higher and 0.75 or lower, even more preferably 0.64 or higher and 0.70 or lower, and even more preferably 0.64 or higher and 0.68 or lower.

[0039] <Condition (α)> Column: G2000HXL+G1000HXL Solvent: THF Flow rate: 1.0mL / min Column temperature: 40℃ Sample concentration: 0.3% Injection volume: 100μL Detector: RI Standard material: Polystyrene (manufactured by Tosoh Corporation, Mw=500, 2630, 10200)

[0040] The equipment used for gel permeation chromatography (GPC) is not particularly limited, but for example, the HLC-8220GPC (manufactured by Tosoh Corporation) can be used.

[0041] In a chart obtained by gel permeation chromatography (GPC) of a pentaerythritol derivative composition represented by general formula (1) under the above conditions (α), the ratio of the peak area of ​​the pentaerythritol monoester compound to the total peak area, when the total peak area is set to 1, is preferably 0.10 to 0.45, more preferably 0.15 to 0.40, even more preferably 0.20 to 0.35, and even more preferably 0.22 to 0.30, from the viewpoint of further suppressing mold contamination.

[0042] In a chart obtained by gel permeation chromatography (GPC) of a pentaerythritol derivative composition represented by general formula (1) under the above conditions (α), the ratio of the peak area of ​​the pentaerythritol diester compound to the total peak area, when the total peak area is set to 1, is preferably 0.25 to 0.55, more preferably 0.30 to 0.50, even more preferably 0.34 to 0.45, and even more preferably 0.36 to 0.43, from the viewpoint of further suppressing mold contamination.

[0043] In a chart obtained by gel permeation chromatography (GPC) of a pentaerythritol derivative composition represented by general formula (1) under the above conditions (α), the ratio of the sum of the peak areas of the pentaerythritol triester compound and the pentaerythritol tetraester compound, with the total peak area set to 1, is preferably 0.18 or more and less than 0.40, more preferably 0.24 or more and less than 0.38, even more preferably 0.28 or more and less than 0.36, and even more preferably 0.30 or more and less than 0.34, from the viewpoint of further suppressing mold contamination.

[0044] In a chart obtained by gel permeation chromatography (GPC) of a pentaerythritol derivative composition represented by general formula (1) under the above conditions (α), the ratio of the peak area of ​​the pentaerythritol triester compound to the total peak area of ​​1 is preferably 0.10 or more and less than 0.45, more preferably 0.15 or more and less than 0.35, even more preferably 0.20 or more and less than 0.30, and even more preferably 0.22 or more and less than 0.28, from the viewpoint of further suppressing mold contamination.

[0045] In a chart obtained by gel permeation chromatography (GPC) of a pentaerythritol derivative composition represented by general formula (1) under the above conditions (α), the ratio of the peak area of ​​the pentaerythritol tetraester compound to the total peak area, when the total peak area is set to 1, is preferably 0.01 or more and less than 0.25, more preferably 0.02 or more and less than 0.20, even more preferably 0.04 or more and less than 0.15, and even more preferably 0.06 or more and less than 0.10, from the viewpoint of further suppressing mold contamination.

[0046] When the total mass of the pentaerythritol derivative composition represented by general formula (1) is taken as 1, the pentaerythritol content is preferably 0.010 or less, more preferably 0.008 or less, even more preferably 0.005 or less, and even more preferably 0.003 or less, from the viewpoint of further suppressing mold contamination, improving humidity and heat resistance, suppressing filter clogging when melt-filtration of the resin composition using a polymer filter attached to the extruder, and improving transparency and homogeneity by suppressing phase separation of pentaerythritol. Furthermore, from the viewpoint of improving the balance of mold contamination suppression, humidity and heat resistance, filter clogging suppression, transparency and homogeneity, it is preferably 0.002 to 0.010, more preferably 0.003 to 0.008, and even more preferably 0.003 to 0.005.

[0047] The method for quantifying pentaerythritol is not particularly limited, but for example, it can be quantified by the following method.

[0048] First, the conditions for measuring equipment, etc., are as follows: Measuring equipment: 8890 GC System (Agilent Technologies) Column: DB-1HT (manufactured by J&W) (30m × 250μm × 0.1μm) Carrier gas: He (constant flow mode) Split ratio: 50:1 Detector: FID Inlet temperature: 330℃ Detector temperature: 330℃ Measurement temperature conditions: The temperature was increased from 100°C at a rate of 10°C / min and held at 380°C for 27 minutes. Detection sensitivity: Acquisition speed, 20Hz Minimum peak width, 0.01 min Injection volume: 1 μl (split method)

[0049] Then, prepare the calibration curve samples using the following procedure. (1) Precisely weigh approximately 0.5 mg, 1.0 mg, and 2.0 mg of pentaerythritol (Wako Pure Chemical Industries: reagent) into 10 cc screw-cap tubes. (Record the amount taken to the last digit in mg.) (2) After step (1), add 1 cc of TMS agent to the screw tube and close the cap. (TMS agent: TMSI-H: Manufactured by GL Sciences Co., Ltd.: Reagent) (3) After step (2), gently shake the screw tube in an 80°C warm bath to allow the reaction to proceed. (Approximately 10 minutes) (4) After step (3), add 5cc of deionized water to the screw tube to deactivate the TMS. (5) After step (4), add 1.00 cc of hexane to the screw-cap tube, shake well, and then let the screw-cap tube stand. (Use a volumetric pipette) (6) After step (5), water / hexane separates inside the screw tube, so the hexane layer is collected and used as a gas chromatography sample. (7) Measure the sample obtained in step (6) under the above conditions and create a calibration curve.

[0050] Furthermore, a sample for measurement is prepared from the pentaerythritol derivative composition represented by general formula (1) using the following procedure, and the amount of pentaerythritol in the pentaerythritol derivative composition represented by general formula (1) is quantified. (a) Weigh out approximately 20 mg of the pentaerythritol derivative composition represented by general formula (1) into a 10 cc screw-cap tube. (Record the amount taken to the last digit in mg.) (b) After step (a), add 1 cc of TMS agent to the screw tube and close the cap. (TMS agent: TMSI-H: Manufactured by GL Sciences: Reagent) (c) After step (b), gently shake the screw tube in an 80°C bath to allow the reaction to proceed. (Approximately 10 minutes) (d) After step (c), 5cc of deionized water is added to the screw tube to deactivate the TMS. (e) After step (d), add 1.00 cc of hexane to the screw tube, shake well, and then let stand. (Use a volumetric pipette) (f) After step (e), water / hexane is separated, so the hexane layer is collected and used as a gas chromatography sample. (g) Using the sample obtained in step (f), measurements are performed under the above conditions, and the amount of pentaerythritol in the pentaerythritol derivative composition represented by general formula (1) is quantified from the calibration curve.

[0051] The method for producing the pentaerythritol derivative composition represented by general formula (1) is not particularly limited, but it can be produced, for example, by a production method comprising the following steps (a) and (b). Step (a): Pentaerythritol is esterified by reacting 1 mole of pentaerythritol with 1.0 mole to 1.7 moles of a fatty acid having 18 to 24 carbon atoms. Step (b): The pentaerythritol esterified product obtained in step (a) is filtered.

[0052] In step (a), for example, a predetermined amount of pentaerythritol and a predetermined amount of a fatty acid having 18 to 24 carbon atoms are subjected to a dehydration reaction under nitrogen blowing at a temperature of 220°C to 240°C (more preferably 230°C to 240°C) to esterify the pentaerythritol. The fatty acid having 18 to 24 carbon atoms is preferably a linear or branched saturated or unsaturated fatty acid, such as stearic acid, oleic acid, arachidic acid, behenic acid, lignoceric acid, or erucic acid. From the viewpoint of further suppressing mold contamination, linear or branched saturated fatty acids are preferred, with linear saturated fatty acids being more preferred. Reduced pressure during the dehydration reaction is undesirable because it causes distillation of the fatty acid out of the system and changes the charge ratio.

[0053] The molar ratio of fatty acids added is, for example, 1.0 mole to 1.7 moles per 1.0 mole of pentaerythritol, preferably 1.1 mole to 1.5 moles, and more preferably 1.2 mole to 1.4 moles.

[0054] In step (a), the pentaerythritol used as the raw material preferably has a sodium content of 100 ppm or less, more preferably 90 ppm or less. Since sodium derived from the raw materials for the production of pentaerythritol affects the coloring during the esterification reaction, it is preferable to use pentaerythritol with a reduced sodium content within the above range.

[0055] In step (b), the pentaerythritol esterified product obtained in step (a) is filtered. Filtration can be performed by adjusting the temperature of the obtained pentaerythritol esterified product to preferably 70°C to 100°C, more preferably 80°C to 90°C, and maintaining the temperature while preferably using a filtration aid such as radiolite (manufactured by Showa Chemical Industry Co., Ltd.) by vacuum filtration preferably at 60 kPa or less, more preferably at 40 kPa or less, or by pressure filtration preferably at 100 kPa to 600 kPa, more preferably at 200 kPa to 510 kPa. This allows for adjustment of the amount of pentaerythritol in the pentaerythritol derivative composition represented by general formula (1).

[0056] As described above, the method for producing the pentaerythritol derivative composition represented by general formula (1) includes an esterification reaction step between pentaerythritol and a fatty acid. Therefore, discoloration may occur during this esterification reaction. In addition, the ester obtained by the reaction may undergo transesterification in a molten state, resulting in a change in composition, which may also cause discoloration. Effective means of suppressing discoloration include (1) treating the pentaerythritol derivative composition with hydrogen peroxide, (2) if it is necessary to melt the pentaerythritol derivative composition, keeping the melting temperature below a certain level (preferably 80°C or below), and (3) spray-cooling the molten pentaerythritol derivative composition after melting. By suppressing the coloration of the pentaerythritol derivative composition, the transparency (light transmittance) when it is added to a resin composition can be improved.

[0057] <Polymer represented by general formula (2)> The polymer represented by general formula (2) will be described below.

[0058] The polymer contained in the resin composition of this embodiment is represented by the following general formula (2).

[0059] [ka]

[0060] In general formula (2), x and y represent the copolymerization ratio and are real numbers satisfying 0 / 100 ≤ y / x ≤ 95 / 5. x and y are based on moles. n represents the number of substitutions of substituent Q, and is a real number between 0 and 2, preferably 0. R a This is a 2+n valent group selected from the group consisting of hydrocarbon groups having 2 to 20, preferably 2 to 12, carbon atoms. R b This is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 28 carbon atoms. R c This is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10, preferably 2 to 5, carbon atoms. Q is a halogen atom, a halogenated alkyl group, an alkoxy group, or a -COOR group. d That is. R d This is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms, and is preferably a hydrogen atom or a hydrocarbon group having 1 to 3 carbon atoms. Note, R a , R b , R c Q may each consist of only one type, or it may consist of two or more types in any proportion.

[0061] In general formula (2), R a Preferably, is one or more divalent groups selected from hydrocarbon groups having 2 to 12 carbon atoms, more preferably, when n=0, is a divalent group represented by the following general formula (3), and even more preferably, is a divalent group in the following general formula (3) where p is 0 or 1. a The structure may be of one type or two or more types may be used in combination.

[0062] [ka]

[0063] In general formula (3), p is an integer between 0 and 2.

[0064] Furthermore, in general formula (2), R b Examples include hydrogen atoms, methyl groups, ethyl groups, n-propyl groups, i-propyl groups, n-butyl groups, and 2-methylpropyl groups, but preferably hydrogen atoms and / or methyl groups, and more preferably hydrogen atoms.

[0065] Furthermore, in general formula (2), when n=0, the following general formula [ka] Examples of divalent groups represented by the following general formulas (4) to (6) include the groups represented by the following general formulas.

[0066] [ka]

[0067] In general formulas (4) to (6), R a This is as stated above. Furthermore, the type of polymerization is not limited at all in this embodiment, and various known polymerization types such as addition polymerization and ring-opening polymerization can be applied. Examples of addition polymerization include random copolymers, block copolymers, and alternating copolymers. In this embodiment, it is preferable to use a random copolymer from the viewpoint of suppressing the deterioration of optical performance.

[0068] If the polymer structure used as the main component of the resin composition in this embodiment is as described above, then optical properties such as transparency, refractive index, and birefringence are excellent, and high-precision optical components can be obtained.

[0069] Polymers represented by general formula (2) can be broadly classified into the following four types of polymers: (i) to (iv). (i) Copolymer of ethylene or α-olefin and cyclic olefin (ii) Ring-opening polymer or its hydrogenated version (iii) Vinyl alicyclic hydrocarbon polymers (iv) Other polymers The following explains the process step by step.

[0070] (i) Copolymer of ethylene or α-olefin and cyclic olefin) (i) Copolymers of ethylene or α-olefins and cyclic olefins are, for example, cyclic olefin copolymers represented by general formula (7). For example, they consist of constituent units (A) derived from ethylene or linear or branched α-olefins having 3 to 30 carbon atoms and constituent units (B) derived from cyclic olefins.

[0071] [ka]

[0072] In general formula (7), R a This is a divalent group selected from the group consisting of hydrocarbon groups having 2 to 20, preferably 2 to 12, carbon atoms. R b This is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 28 carbon atoms, preferably 1 to 10, more preferably 1 to 5 carbon atoms. Note, R a and R b Each of these may be of one type, or it may be of two or more types in any proportion. x and y represent the copolymerization ratio and are real numbers that preferably satisfy 5 / 95 ≤ y / x ≤ 95 / 5, more preferably 50 / 50 ≤ y / x ≤ 95 / 5, and even more preferably 55 / 45 ≤ y / x ≤ 80 / 20. x and y are based on moles.

[0073] (Constituent units (A) derived from ethylene or α-olefin) The constituent unit (A) derived from ethylene or α-olefin is, for example, ethylene or a constituent unit derived from a linear or branched α-olefin having 3 to 30 carbon atoms.

[0074] Specifically, examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among these, ethylene is preferred. Two or more of these ethylene or α-olefin-derived constituent units may be included in an amount that does not impair the effects of this embodiment.

[0075] (Constituent unit (B) derived from cyclic olefins) The constituent unit (B) derived from a cyclic olefin consists of at least one selected from the group consisting of constituent units derived from a cyclic olefin represented by, for example, general formulas (8), (9), and (10) below.

[0076] The general formula (8) is shown below.

[0077] [ka]

[0078] In general formula (8), u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. Note that when w is 1, the ring expressed using w is a 6-membered ring, and when w is 0, this ring is a 5-membered ring. 61 ~R 78 Furthermore, R a1 and R b1 These may be the same or different atoms, and are hydrogen atoms, halogen atoms, or hydrocarbon groups.

[0079] Examples of halogen atoms include fluorine, chlorine, bromine, or iodine atoms. Examples of hydrocarbon groups include alkyl groups with 1 to 20 carbon atoms, halogenated alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 15 carbon atoms, or aromatic hydrocarbon groups.

[0080] More specifically, examples of alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl. Examples of halogenated alkyl groups include groups in which one or more halogen atoms are substituted on the above alkyl groups having 1 to 20 carbon atoms. Examples of cycloalkyl groups include cyclohexyl, and examples of aromatic hydrocarbon groups include phenyl and naphthyl.

[0081] Furthermore, in general formula (8), R 75 and R 76 Toga, R 77 and R 78 Toga, R 75 and R 77 Toga, R 76 and R 78 Toga, R 75 and R 78 toga, or R 76 and R 77 These may bond together, that is, cooperate with each other, to form a monocyclic or polycyclic group. Furthermore, the monocyclic or polycyclic group thus formed may have a double bond. Polycyclic groups are preferred from the viewpoint of heat resistance because they can produce copolymers with a high glass transition temperature (Tg) with a lower polycyclic content than monocyclic groups. In addition, they have the advantage of being able to be manufactured with a small amount of cyclic olefin. Specific examples of monocyclic or polycyclic groups formed here include the following.

[0082] [ka]

[0083] In the above example, the carbon atoms numbered 1 or 2 correspond to R in the above general formula (8), respectively.75 (R 76 ) or R 77 (R 78 ) represents the carbon atom to which the atom is bonded.

[0084] R 75 and R 76 And, or R 77 and R 78 These may form an alkylidene group. This alkylidene group has, for example, 2 to 20 carbon atoms. Specific examples of alkylidene groups include ethylidene, propyridene, and isopropylidene.

[0085] The general formula (9) is shown below.

[0086] [ka]

[0087] In general formula (9), x and d are 0 or positive integers greater than or equal to 1, and y and z are 0, 1, or 2. Also, R 81 ~R 99 These may be the same or different from each other, and are a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or an alkoxy group, R 89 and R 90 The carbon atom to which it is bonded, and R 93 The carbon atom or R to which it is bonded 91 The carbon atom to which it is bonded may be directly bonded or bonded via an alkylene group having 1 to 3 carbon atoms. Also, when y=z=0, R 95 and R 92 or R 95 and R 99 These elements may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Examples of halogen atoms include those identical to the halogen atoms in general formula (8).

[0088] Examples of aliphatic hydrocarbon groups include alkyl groups with 1 to 20 carbon atoms or cycloalkyl groups with 3 to 15 carbon atoms. More specifically, examples of alkyl groups include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl. Examples of cycloalkyl groups include cyclohexyl.

[0089] Aromatic hydrocarbon groups include aryl groups and aralkyl groups, specifically phenyl, tolyl, naphthyl, benzyl, and phenylethyl.

[0090] Examples of alkoxy groups include methoxy, ethoxy, and propoxy groups.

[0091] Here, R 89 and R 90 The carbon atom to which it is bonded, and R 93 The carbon atom or R to which it is bonded 91 The carbon atom to which is bonded may be directly bonded or via an alkylene group having 1 to 3 carbon atoms. That is, if the two carbon atoms mentioned above are bonded via an alkylene group, R 89 and R 93 or R 90 and R 91 These groups work together to form an alkylene group consisting of a methylene group (-CH2-), an ethylene group (-CH2CH2-), or a propylene group (-CH2CH2CH2-).

[0092] Furthermore, when y=z=0, R 95 and R 92 or R 95 and R 99 These may be bonded to each other to form a monocyclic or polycyclic aromatic ring. Specifically, when y=z=0, R 95 and R 92Examples include aromatic rings formed by the above, represented by the following formula. Since a copolymer having a high glass transition temperature (Tg) can be obtained with a lower content of polycyclic structures than monocyclic structures, polycyclic structures are preferred from the viewpoint of heat resistance. This also has the advantage that production can be achieved with a smaller charged amount of cyclic olefin.

[0093]

Chemical Formula

[0094] l is the same as d in general formula (9).

[0095] General formula (10) is shown below.

[0096]

Chemical Formula

[0097] In general formula (10), R 100 and R 101 may be the same or different from each other, and are each a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f satisfies 1≤f≤18. Preferable examples of the hydrocarbon group having 1 to 5 carbon atoms include an alkyl group, a halogenated alkyl group, and a cycloalkyl group. Specific examples of these are clear from the specific examples of R 61 to R 78 in general formula (8).

[0098] Specifically, the constituent units (B) derived from cyclic olefins represented by general formulas (8), (9), or (10) include bicyclo-2-heptene derivatives (bicyclohept-2-ene derivatives), tricyclo-3-decene derivatives, tricyclo-3-undecene derivatives, tetracyclo-3-dodecene derivatives, pentacyclo-4-pentadecene derivatives, pentacyclopentadecadiene derivatives, pentacyclo-3-pentadecene derivatives, pentacyclo-4-hexadecene derivatives, pentacyclo-3-hexadecene derivatives, and hexacyclo-4-heptadecene derivatives. Examples include conductors, heptacyclo-5-eicosene derivatives, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-docosene derivatives, nonacyclo-5-pentacosene derivatives, nonacyclo-6-hexacosene derivatives, cyclopentadiene-acenaphthylene adduct derivatives, 1,4-methano-1,4,4a,9a-tetrahydrofluorene derivatives, 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene derivatives, and cycloalkylene derivatives having 3 to 20 carbon atoms.

[0099] The constituent unit (B) derived from a cyclic olefin represented by general formula (8), (9), or (10) is preferably tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene derivatives, hexacyclo[6.6.1.1 3,6 .1 10,13 .0 2,7 . 09,14-4-heptadecene derivative, 5-phenyl-bicyclo[2.2.1]hept-2-ene, 5-methyl-5-phenyl-bicyclo[2.2.1]hept-2-ene, 5-tolyl-bicyclo[2.2.1]hept-2-ene, 5-(ethylphenyl)-bicyclo[2.2.1]hept-2-ene, 5-(isopropylphenyl)-bicyclo[2.2.1]hept-2-ene, 5-(α-naphthyl)-bicyclo[2.2.1]hept-2-ene, 5-(biphenyl)-bicyclo[2.2.1]hept-2-ene, 5,6-(diphenyl)-bicyclo[2.2.1]hept-2-ene, 1,4-methano-1,4,4a,9a-tetrahydrofluorene, 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene, cyclopentadiene-acenaphthylene adduct, cyclopentadiene-benzyne adduct, and benzonorbornadiene derivative, more preferably tetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene, 1,4-methano-1,4,4a,9a-tetrahydrofluorene, cyclopentadiene-benzyne adduct, and cyclopentadiene-acenaphthylene adduct, still more preferably tetracyclo[4.4.0.1 2,5 .1 7,10 -3-dodecene.

[0100] The cyclic olefin represented by general formula (8) or (9) can be produced by subjecting cyclopentadiene and an olefin having a corresponding structure to a Diels-Alder reaction.

[0101] Two or more types of the structural unit (B) derived from the cyclic olefin represented by general formula (8), (9) or (10) may be contained. A polymer obtained by polymerization using the above monomers can be modified as needed, and in this case, the structure of the monomer-derived structural unit can be changed. For example, by hydrogenation treatment, a benzene ring or the like in the monomer-derived structural unit can be converted into a cyclohexyl ring depending on the conditions.

[0102] The polymer represented by general formula (2) preferably comprises (i) a copolymer of ethylene or α-olefin and a cyclic olefin, and more preferably ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 It contains a copolymer consisting of ]-3-dodecene.

[0103] Furthermore, the type of copolymerization is not limited in any way in this embodiment, and various known copolymerization types such as random copolymers, block copolymers, and alternating copolymers can be applied, but random copolymers are preferred.

[0104] (ii) Ring-opening polymers or their hydrogenated products (ii) The ring-opening polymer or its hydrogenated product is a cyclic olefin polymer containing a structural unit represented by general formula (5) among the structures listed as preferred examples in general formula (2).

[0105] Here, the cyclic olefin polymer containing the constituent units represented by general formula (5) may have polar groups. Examples of polar groups include hydroxyl groups, carboxyl groups, alkoxy groups, epoxy groups, glycidyl groups, oxycarbonyl groups, carbonyl groups, amino groups, and ester groups.

[0106] Cyclic olefin polymers can be obtained, for example, by polymerizing cyclic olefins, specifically by ring-opening polymerization of alicyclic olefins. Cyclic olefin polymers having polar groups can be obtained, for example, by introducing a compound having polar groups into a cyclic olefin polymer through a modification reaction, or by copolymerizing a monomer containing polar groups as a copolymer component.

[0107] Specific examples of alicyclic olefins used to obtain cyclic olefin polymers include bicyclo[2.2.1]-hept-2-ene (common name: norbornene), 5-methyl-bicyclo[2.2.1]-hept-2-ene, 5,5-dimethyl-bicyclo[2.2.1]-hept-2-ene, 5-ethyl-bicyclo[2.2.1]-hept-2-ene, 5-butyl-bicyclo[2.2.1]-hept-2-ene, 5-hexyl-bicyclo[2.2.1]-hept-2-ene, and 5-octyl-bicyclo[2.2.1]-hept-2-ene. To-2-ene, 5-octadecyl-bicyclo[2.2.1]-hept-2-ene, 5-ethylidene-bicyclo[2.2.1]-hept-2-ene, 5-methylidene-bicyclo[2.2.1]-hept-2-ene, 5-vinyl-bicyclo[2.2.1]-hept-2-ene, 5-propenyl-bicyclo[2.2.1]-hept-2-ene, 5-methoxy-carbinyl-bicyclo[2.2.1]-hept-2-ene, 5-cyano-bicyclo[2.2.1]-hept-2-ene, 5-methyl-5-methoxycarbonyl-bi Cyclo[2.2.1]-hept-2-ene, 5-ethoxycarbonyl-bicyclo[2.2.1]-hept-2-ene, bicyclo[2.2.1]-hept-5-enyl-2-methylpropionate, bicyclo[2.2.1]-hept-5-enyl-2-methyloctanate, bicyclo[2.2.1]-hept-2-ene-5,6-dicarboxylic acid anhydride, 5-hydroxymethylbicyclo[2.2.1]-hept-2-ene, 5,6-di(hydroxymethyl)-bicyclo[2.2.1]-hept-2-ene, 5-hydroxy cy-i-propylbicyclo[2.2.1]-hept-2-ene, 5,6-dicarboxy-bicyclo[2.2.1]-hept-2-ene, bicyclo[2.2.1]-hept-2-ene-5,6-dicarboxylimide, 5-cyclopentyl-bicyclo[2.2.1]-hept-2-ene, 5-cyclohexyl-bicyclo[2.2.1]-hept-2-ene, 5-cyclohexenyl-bicyclo[2.2.1]-hept-2-ene, 5-phenyl-bicyclo[2.2.1]-hept-2-ene, tricyclo[4.3.0.1 2,5 Deca-3,7-diene (common name: dicyclopentadiene), tricyclo [4.3.0.1 2,5Deca-3-en, tricyclo[4.4.0.1 2,5 ] Undeca-3,7-diene, tricyclo[4.4.0.1 2,5 ] Undeca-3,8-diene, tricyclo[4.4.0.1 2,5 ] Undeca-3-ene, tetracyclo[7.4.0.1 10,13 .0 2,7 ]-Trideca-2,4,6-11-tetraene (also known as 1,4-methano-1,4,4a,9a-tetrahydrofluorene), tetracyclo[8.4.0.1 11,14 .0 3,8 ]-Tetradeca-3,5,7,12-11-tetraene (also known as: 1,4-methano-1,4,4a,5,10,10a-hexahydroanthracene), tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene (common name: tetracyclododecene), 8-methyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene, 8-ethyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene, 8-methylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene, 8-Ethylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 )-Dodeca-3-ene, 8-vinyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene, 8-propenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene,8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene,8-hydroxymethyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene, 8-carboxytetracyclo[4.4.0.1 2,5 .17,10 )-Dodeca-3-ene,8-cyclopentyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene, 8-Cyclohexyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene, 8-Cyclohexenyl-Tetracyclo[4.4.0.1 2,5 .1 7,10 ]-Dodeca-3-ene,8-phenyl-tetracyclo[4.4.0.1 2,5 .1 7,10 )-Dodeca-3-ene, pentacyclo[6.5.1.1 3,6 .0 2,7 .0 9,13 )-pentadeca-3,10-diene, pentacyclo[7.4.0.1 3,6 .1 10,13 .0 2,7 Examples include norbornene monomers such as ]-pentadeca-4,11-diene; monocyclic cycloalkenes such as cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, cyclooctene, 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene, and cycloheptene; vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane; and alicyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene. Alicyclic olefins can be used individually or in combination of two or more.

[0108] Furthermore, copolymerizable monomers can be copolymerized as needed. Specific examples include ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, 1-eicosene, and other carbon atoms. Examples include ethylene or α-olefins with 2 to 20 atoms; cycloolefins such as cyclobutene, cyclopentene, cyclohexene, 3,4-dimethylcyclopentene, 3-methylcyclohexene, 2-(2-methylbutyl)-1-cyclohexene, cyclooctene, and 3a,5,6,7a-tetrahydro-4,7-methano-1H-indene; and non-conjugated dienes such as 1,4-hexadiene, 4-methyl-1,4-hexadiene, 5-methyl-1,4-hexadiene, and 1,7-octadiene. These monomers can be used individually or in combination of two or more.

[0109] There are no particular restrictions on the polymerization method of alicyclic olefins, and they can be carried out according to known methods. These ring-opened polymers are preferably used after hydrogenation due to their heat resistance, stability, and optical properties. Known methods can be used for hydrogenation.

[0110] (iii) Vinyl alicyclic hydrocarbon polymers (iii) Vinyl alicyclic hydrocarbon polymers are hydrogenated (co)polymers obtained using vinyl aromatic hydrocarbon compounds as monomers, or (co)polymers obtained using vinyl alicyclic hydrocarbon compounds as monomers. Examples of vinyl compounds include vinyl aromatic compounds and vinyl alicyclic hydrocarbon compounds.

[0111] Examples of vinyl aromatic compounds include styrene, α-methylstyrene, α-ethylstyrene, α-propylstyrene, α-isopropylstyrene, α-t-butylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2,4-diisopropylstyrene, 2,4-dimethylstyrene, 4-t-butylstyrene, 5-t-butyl-2-methylstyrene, monochlorostyrene, dichlorostyrene, monofluorostyrene, 4-phenylstyrene, and other styrene compounds.

[0112] Examples of vinyl alicyclic hydrocarbon compounds include vinylcyclohexanes such as vinylcyclohexane and 3-methylisopropenylcyclohexane; vinylcyclohexenes such as 4-vinylcyclohexene, 4-isopropenylcyclohexene, 1-methyl-4-vinylcyclohexene, 1-methyl-4-isopropenylcyclohexene, 2-methyl-4-vinylcyclohexene, and 2-methyl-4-isopropenylcyclohexene; and others.

[0113] In this embodiment, the aforementioned monomers may be copolymerized with other monomers copolymerizable with them. Examples of copolymerizable monomers include α-olefin monomers such as ethylene, propylene, isobutene, 2-methyl-1-butene, 2-methyl-1-pentene, and 4-methyl-1-pentene; cyclopentadiene monomers such as cyclopentadiene, 1-methylcyclopentadiene, 2-methylcyclopentadiene, 2-ethylcyclopentadiene, 5-methylcyclopentadiene, 5,5-dimethylcyclopentadiene, and dicyclopentadiene; monocyclic olefin monomers such as cyclobutene, cyclopentene, and cyclohexene; butadiene, isoprene, 1,3-pentadiene, furan, thiophene, and 1, Examples include conjugated diene monomers such as 3-cyclohexadiene; nitrile monomers such as acrylonitrile, methacrylonitrile, and α-chloroacrylonitrile; (meth)acrylic acid ester monomers such as methyl methacrylate, ethyl methacrylate, propyl methacrylate, butyl methacrylate, methyl acrylate, ethyl acrylate, propyl acrylate, and butyl acrylate; unsaturated fatty acid monomers such as acrylic acid, methacrylic acid, and maleic anhydride; phenylmaleimide; methyl vinyl ether; heterocyclic vinyl compound monomers such as N-vinylcarbazole and N-vinyl-2-pyrrolidone; and others.

[0114] The monomer mixture used for polymerization preferably contains, for example, 50% by mass or more, preferably 70-100% by mass, and more preferably 80-100% by mass, vinyl aromatic compounds and / or vinyl alicyclic hydrocarbon compounds, from the viewpoint of heat resistance, low birefringence, and mechanical strength. The monomer mixture may contain both vinyl aromatic compounds and vinyl alicyclic hydrocarbon compounds.

[0115] The polymerization method for vinyl aromatic hydrocarbon compounds or vinyl alicyclic hydrocarbon compounds is not particularly limited and can be carried out according to known methods. The (co)polymers obtained from vinyl aromatic hydrocarbon compounds are preferably used as hydrogenated products due to their heat resistance, stability, and optical properties. Known hydrogenation methods can be used.

[0116] Hydrogenated (co)polymers obtained from vinyl aromatic hydrocarbon compounds can have a hydrogenation rate of phenyl groups of preferably 95% or more, more preferably 99% or more. Hydrogenation treatment hydrogenates the phenyl groups in the resin structure, converting them to cyclohexyl groups. Molded articles containing this resin exhibit improved light transmittance on the short-wavelength side and reduced birefringence and optical anisotropy. Simultaneously, unreacted monomers and impurities are hydrogenated, improving resistance to heat and light. These effects are particularly pronounced when the hydrogenation rate is within the above range.

[0117] (iv) Other polymers (iv) Other polymers include, for example, polymers of monocyclic cycloalkenes, polymers of alicyclic conjugated diene monomers, and aromatic olefin polymers. However, structures not included in (i) to (iii) can be arbitrarily selected within the range of general formula (2). For example, polymers obtained by copolymerizing (i) to (iii) with each other, or with known copolymerizable monomers.

[0118] Furthermore, the type of copolymerization is not limited in any way in this embodiment, and various known copolymerization types such as random copolymers, block copolymers, and alternating copolymers can be applied, but random copolymers are preferred.

[0119] Of the four polymers broadly classified as (i) to (iv) above, those preferred in terms of optical properties are (i) copolymers of ethylene or α-olefin and cycloolefin, and among these, the most preferred is ethylene-tetracyclo[4.4.0.1 2,5 .1 7,10 It is a ]-3-dodecene copolymer.

[0120] The polymer represented by general formula (2) may, if necessary, have repeating structural units derived from other copolymerizable monomers, as long as it does not impair the good physical properties of the resin composition of this embodiment. The copolymerization ratio is not limited, but is preferably 20 mol% or less, more preferably 0 mol% to 10 mol%, and if the copolymerization amount is 20 mol% or less, high-precision optical components can be obtained without impairing the optical properties. Furthermore, the type of copolymerization is not limited.

[0121] The molecular weight of the polymer represented by general formula (2) is not limited, but when intrinsic viscosity [η] is used as an alternative indicator to molecular weight, the intrinsic viscosity [η] measured in decalin at a temperature of 135°C is preferably 0.03 dl / g or more and 10 dl / g or less, more preferably 0.05 dl / g or more and 5 dl / g or less, and even more preferably 0.10 dl / g or more and 2 dl / g or less. When the intrinsic viscosity [η] is within the above range, good moldability can be obtained without impairing the mechanical strength of the molded product.

[0122] The glass transition temperature (Tg) of the polymer represented by general formula (2) is preferably 50°C to 240°C, more preferably 50°C to 160°C, and even more preferably 100°C to 150°C. When the glass transition temperature (Tg) is within the above range, sufficient heat resistance and good moldability can be obtained when the molded product is used as an optical component.

[0123] The devices used to measure the glass transition temperature are not limited. For example, a differential scanning calorimeter (DSC) can be used to measure the glass transition temperature of a thermoplastic amorphous resin. For instance, a method using a SEIKO DSC-20 manufactured by SEIKO Electronics Industries, Ltd. at a heating rate of 10°C / min can be used.

[0124] The method for producing the polymer represented by general formula (2) is not limited, but (i) a copolymer of ethylene or α-olefin and a cyclic olefin can be produced by selecting appropriate conditions according to the methods described in, for example, Japanese Patent Publication No. 60-168708, Japanese Patent Publication No. 61-120816, Japanese Patent Publication No. 61-115912, Japanese Patent Publication No. 61-115916, Japanese Patent Publication No. 61-271308, Japanese Patent Publication No. 61-272216, Japanese Patent Publication No. 62-252406, and Japanese Patent Publication No. 62-252407. (ii) Ring-opening polymers or their hydrogenated products can be produced by selecting appropriate conditions according to methods such as those described in Japanese Patent Publication No. 60-26024, Japanese Patent Publication No. 9-268250, Japanese Patent Publication No. 63-145324, and Japanese Patent Publication No. 2001-72839; (iii) Vinyl alicyclic hydrocarbon polymers can be produced by selecting appropriate conditions according to methods such as those described in International Publication No. 01 / 092412, Japanese Patent Publication No. 2003-276047, and Japanese Patent Publication No. 2004-83813.

[0125] In the manufacturing process of a polymer represented by general formula (2), the optical properties of the polymer, such as heat resistance and transparency, can be improved by contacting the polymer or a system containing the polymer and its monomer raw materials with a hydrogenation catalyst and hydrogen at least once to hydrogenate at least a portion of the unsaturated bonds of the polymer and / or monomers. This hydrogenation, or hydrogenation, can be carried out by conventionally known methods.

[0126] The manufacturing process of the polymer represented by general formula (2), or the manufacturing process of the resin composition, preferably includes a process for reducing unreacted monomers. Examples of reduction processes include melt defoliation, polymer crystallization, phase separation processes, and hydrogenation reactions to double bonds by hydrogenation processes. Reducing residual monomers improves the thermal stability of the resin, reduces appearance defects during molding, improves light transmittance and diffraction efficiency, and reduces gas generation during molding. The amount of residual monomers is preferably 5000 ppm or less, more preferably 1000 ppm, and most preferably 500 ppm or less.

[0127] <Resin composition> The resin composition of this embodiment will be described below.

[0128] In the resin composition of this embodiment, the content of the pentaerythritol derivative composition represented by general formula (1) per 100 parts by mass of the polymer represented by general formula (2) is 1.0 part by mass or more, preferably 1.5 parts by mass or more, more preferably 1.8 parts by mass or more, even more preferably 2.0 parts by mass or more, even more preferably 2.2 parts by mass or more, and 5.0 parts by mass or less, and from the viewpoint of further suppressing mold contamination, preferably 4.5 parts by mass or less, more preferably 4.0 parts by mass or less. More preferably, the amount is 3.5 parts by mass or less, even more preferably 3.0 parts by mass or less, even more preferably 2.8 parts by mass or less, and 1.0 part by mass or more and 5.0 parts by mass or less. From the viewpoint of improving the balance between moisture and heat resistance and mold fouling suppression, the amount is preferably 1.5 parts by mass or more and 4.5 parts by mass or less, more preferably 1.8 parts by mass or more and 4.0 parts by mass or less, even more preferably 2.0 parts by mass or more and 3.5 parts by mass or less, even more preferably 2.2 parts by mass or more and 3.0 parts by mass or less, and even more preferably 2.2 parts by mass or more and 2.8 parts by mass or less.

[0129] In addition to the pentaerythritol derivative composition represented by general formula (1) and the polymer represented by general formula (2), the resin composition of this embodiment may also use known additives as optional components, as long as they do not impair the good physical properties of the resin composition of this embodiment. Examples of additives that can be added include known antioxidants, secondary antioxidants, lubricants, mold release agents, anti-fogging agents, weather stabilizers, light stabilizers, UV absorbers, antistatic agents, and metal deactivators.

[0130] The resin composition of this embodiment preferably contains an antioxidant, from the viewpoint of suppressing deterioration during molding, and the antioxidant preferably includes a phenolic antioxidant.

[0131] The phenolic antioxidant of this embodiment is a stabilizer having a phenol skeleton in its structure, and includes, for example, a group consisting of a 3,5-dimethyl-4-hydroxyphenyl group, a 2,4-dimethyl-3-hydroxyphenyl group, a 3-methyl-2-hydroxyphenyl group, or a derivative thereof.

[0132] The phenolic antioxidants of this embodiment include, for example, acrylate-based phenolic compounds described in Japanese Patent Publication No. 63-179953 and Japanese Patent Publication No. 1-168643, such as 2-3-butyl-6-(3-3-butyl-2-hydroxy-5-methylbenzyl)-4-methylphenyl acrylate and 2,4-di-3-amyl-6-(1-(3,5-di-3-amyl-2-hydroxyphenyl)ethyl)phenyl acrylate; 2,6-di- 3-butyl-4-methylphenol, 2,6-di-3-butyl-4-ethylphenol, octadecyl-3-(3,5-di-3-butyl-4-hydroxyphenyl)propionate, 2,2′-methylene-bis(4-methyl-6-3-butylphenol), 4,4′-butylidene-bis(6-3-butyl-m-cresol), 4,4′-thiobis(3-methyl-6-3-butylphenol), bis(3-cyclohexyl-2-hydroxyphenyl) C-5-methylphenyl)methane, 3,9-bis(2-(3-(3-3-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5]undecane, 1,1,3-tris(2-methyl-4-hydroxy-5-3-butylphenyl)butane, 1,3,5-trimethyl-2,4,6-tris(3,5-di-3-butyl-4-hydroxybenzyl) Benzene, tetrakis(methylene-3-(3′,5′-di-3-butyl-4′-hydroxyphenylpropionate))methane [i.e., pentaerythrimethyl-tetrakis(3-(3,5-di-3-butyl-4-hydroxyphenylpropionate))], triethylene glycol bis(3-(3-3-butyl-4-hydroxy-5-methylphenyl)propionate), tocopherol, and other alkyl-substituted phenolic compounds;The compound comprises one or more triazine group-containing phenolic compounds selected from the group consisting of 6-(4-hydroxy-3,5-di-tertiary butylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3,5-dimethylanilino)-2,4-bisoctylthio-1,3,5-triazine, 6-(4-hydroxy-3-methyl-5-tertiary butylanilino)-2,4-bisoctylthio-1,3,5-triazine, and 2-octylthio-4,6-bis-(3,5-di-tertiary butyl-4-oxyanilino)-1,3,5-triazine, and preferably contains tetrakis(methylene-3-(3′,5′-di-tertiary butyl-4′-hydroxyphenylpropionate))methane, which can improve heat resistance and stability.

[0133] The amount of antioxidant added in this embodiment is not particularly limited, but is preferably 0.05 parts by mass or more and 1.2 parts by mass or less per 100 parts by mass of the polymer represented by general formula (2). Furthermore, when tetrakis(methylene-3-(3′,5′-di-3-butyl-4′-hydroxyphenylpropionate))methane is used as the antioxidant in this embodiment, the amount added is preferably 0.1 parts by mass or more and 0.5 parts by mass or less per 100 parts by mass of the polymer represented by general formula (2).

[0134] If the value is above the lower limit mentioned above, the antioxidant effect will be sufficient, reducing color changes and deterioration of optical performance during molding pauses or continuous molding when molding the resin composition. Furthermore, if the value is below the upper limit mentioned above, the solubility of the phenolic antioxidant in the resin composition will be sufficient, reducing mold contamination during injection molding and suppressing phase separation of the phenolic antioxidant in the molded product, thus enabling the production of molded articles with excellent transparency and homogeneity.

[0135] The method for producing the resin composition of this embodiment is not particularly limited and can be produced by known methods. For example, a polymer represented by general formula (2) can be mixed with a pentaerythritol derivative composition represented by general formula (1) and known additives, and then mixed using a Henschel mixer, ribbon blender, melt blender, homomixer, etc., and pelletized using an extruder to obtain a pelletized resin composition. Furthermore, depending on the desired shape of the molded product, it can be obtained as a molded article by injection molding, extrusion molding, blow molding, vacuum molding, slush molding, etc.

[0136] When the resin composition of this embodiment is used for optical applications, it is essential that light rays are transmitted, so good light transmittance is preferable. Light transmittance is defined by spectral light transmittance or total light transmittance depending on the application.

[0137] When intended for use across the entire spectrum of light or multiple wavelengths, good total light transmittance is necessary. Without an anti-reflective coating on the surface, the total light transmittance should be, for example, 85% or higher, preferably 88% to 93%. If the total light transmittance is above the lower limit mentioned above, the required amount of light can be secured. While known methods can be used to measure total light transmittance, and the measuring equipment is not limited, examples include methods conforming to ASTM D1003.

[0138] Furthermore, in the case of optical systems used only in a specific wavelength range, such as laser optical systems, even if the total light transmittance is not high, they can be used if the spectral light transmittance in that wavelength range is good. In this case, the spectral light transmittance at the wavelength of use, without an anti-reflective coating on the surface, is preferably 85% or higher, more preferably 86% to 93%. If the spectral light transmittance is above the lower limit of the above, the required amount of light can be secured. Also, known methods can be applied as measurement methods and apparatus.

[0139] 2.Optical molded body The optical molded body of this embodiment will be described below.

[0140] The optically molded article of this embodiment contains the resin composition of this embodiment.

[0141] The content of the resin composition of this embodiment in the optical molded body of this embodiment is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, and even more preferably 95% by mass or more, when the total mass of the optical molded body of this embodiment is considered to be 100% by mass, from the viewpoint of further improving mold contamination, and may be, for example, 100% by mass or less, and from the viewpoint of further improving mold contamination, preferably 50% by mass or more and 100% by mass or less, more preferably 70% by mass or more and 100% by mass or less, even more preferably 80% by mass or more and 100% by mass or less, even more preferably 90% by mass or more and 100% by mass or less, and even more preferably 95% by mass or more and 100% by mass or less.

[0142] The optical molded article of this embodiment can be obtained by molding the resin composition of this embodiment into a predetermined shape in a mold. The method for obtaining the molded article by molding the resin composition of this embodiment is not particularly limited, and known methods can be used. Depending on the application and shape, applicable methods include extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendering, and foam molding. Among these, injection molding and extrusion molding are preferred from the viewpoint of moldability and productivity, with injection molding being more preferred. Furthermore, molding conditions are appropriately selected depending on the intended use or molding method, but for example, the resin temperature in injection molding is appropriately selected within the range of, for example, 150°C to 400°C, preferably 200°C to 350°C, and more preferably 230°C to 330°C.

[0143] The optical molded body of this embodiment can be used in various forms such as lens shape, spherical shape, rod shape, plate shape, cylindrical shape, tubular shape, fiber shape, film shape, or sheet shape.

[0144] The applications of the optical molded body of this embodiment are not particularly limited, but they can be used, for example, as optical components such as automotive camera lenses and camera lenses for portable devices, as well as optical recording media such as DVDs and CDs.

[0145] The optically molded body of this embodiment preferably includes a lens.

[0146] Examples of lenses in this embodiment include sensor lenses, pickup lenses, projector lenses, prisms, fθ lenses, imaging lenses, light guide plates, automotive camera lenses, camera lenses for portable devices (mobile phones, smartphones, tablets, laptops, digital cameras, etc.), and camera lenses for medical devices. Furthermore, examples of lenses in this embodiment include spherical lenses, aspherical lenses, biconvex lenses, plano-convex lenses, convex meniscus lenses, biconcave lenses, plano-concave lenses, and concave meniscus lenses. Furthermore, examples of lenses in this embodiment include virtual reality lenses (VR lenses), mixed reality lenses (MR lenses), augmented reality lenses (AR lenses), cross-reality lenses (xR lenses), and head-mounted display lenses (HMD lenses).

[0147] The maximum thickness of the optically molded body in this embodiment is not particularly limited, but is preferably 1.0 mm or more and 20.0 mm or less, more preferably 5.0 mm or more and 15.0 mm or less, and even more preferably 7.0 mm or more and 12.0 mm or less.

[0148] 3. Method for producing resin compositions The method for producing the resin composition of this embodiment will be described below.

[0149] The method for producing the resin composition of this embodiment is a method for producing a resin composition comprising a pentaerythritol derivative composition represented by the following general formula (1) and a polymer represented by the following general formula (2),

[0150] [ka]

[0151] In general formula (1), R is a hydrocarbon group, the number of carbon atoms in the RCOO group is between 18 and 24, and n is a real number between 0 and 4.

[0152] [ka]

[0153] In general formula (2), x and y represent the copolymerization ratio and are real numbers satisfying 0 / 100 ≤ y / x ≤ 95 / 5. x and y are based on moles. n represents the number of substituents Q and is a real number 0 ≤ n ≤ 2. a R is a 2+n valent group selected from the group consisting of hydrocarbon groups with 2 to 20 carbon atoms. b R is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 28 carbon atoms. c Q is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms. Q is a halogen atom, an alkyl halide, an alkoxy group, or a -COOR group. d That is. R d This is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0154] The present invention comprises the steps of (I) preparing a pentaerythritol derivative composition represented by general formula (1) by mixing 1.0 mole of pentaerythritol with 1.0 mole to 1.7 moles of an aliphatic monocarboxylic acid having 18 to 24 carbon atoms and carrying out an esterification reaction, and (II) mixing 1.0 to 5.0 parts by mass of the pentaerythritol derivative composition represented by general formula (1) with 100 parts by mass of a polymer represented by general formula (2). The pentaerythritol derivative composition of this embodiment contains pentaerythritol and a pentaerythritol ester compound, and the mass ratio of aliphatic monocarboxylic acid having 20 to 24 carbon atoms to the mass of aliphatic monocarboxylic acid having 18 to 24 carbon atoms is 0.90 to 0.99.

[0155] The method for producing the resin composition of this embodiment can suppress mold contamination.

[0156] In step (I), the amount of aliphatic monocarboxylic acid having 18 to 24 carbon atoms per 1.0 mole of pentaerythritol is 1.0 mole to 1.7 moles, preferably 1.1 mole to 1.5 moles, and more preferably 1.2 moles to 1.4 moles.

[0157] In step (II), the amount of the pentaerythritol derivative composition represented by general formula (1) per 100 parts by mass of the polymer represented by general formula (2) is 1.0 part by mass or more, preferably 1.5 parts by mass or more, more preferably 1.8 parts by mass or more, even more preferably 2.0 parts by mass or more, even more preferably 2.2 parts by mass or more, and 5.0 parts by mass or less, and from the viewpoint of further suppressing mold contamination, preferably 4.5 parts by mass or less, more preferably 4.0 parts by mass or less, More preferably, the amount is 3.5 parts by mass or less, even more preferably 3.0 parts by mass or less, even more preferably 2.8 parts by mass or less, and 1.0 part by mass or more and 5.0 parts by mass or less. From the viewpoint of improving the balance between moisture and heat resistance and mold fouling suppression, the amount is preferably 1.5 parts by mass or more and 4.5 parts by mass or less, more preferably 1.8 parts by mass or more and 4.0 parts by mass or less, even more preferably 2.0 parts by mass or more and 3.5 parts by mass or less, even more preferably 2.2 parts by mass or more and 3.0 parts by mass or less, and even more preferably 2.2 parts by mass or more and 2.8 parts by mass or less.

[0158] In the method for producing the resin composition of this embodiment, the mass ratio of aliphatic monocarboxylic acids having 20 to 24 carbon atoms to the mass of aliphatic monocarboxylic acids having 18 to 24 carbon atoms is 0.90 or more, preferably 0.92 or more, more preferably 0.94 or more, even more preferably 0.95 or more, and 0.99 or less, and 0.90 to 0.99 or less, and even more preferably 0.95 to 0.99 or less, and even more preferably 0.95 to 0.99 or less, from the viewpoint of further suppressing mold contamination.

[0159] In the method for producing the resin composition of this embodiment, the mass ratio of aliphatic monocarboxylic acids having 18 to 19 carbon atoms, with respect to the mass of aliphatic monocarboxylic acids having 18 to 24 carbon atoms being 1, may be, for example, 0.001 or more, 0.005 or more, or 0.01 or more. From the viewpoint of further suppressing mold contamination, it is preferably 0.10 or less, more preferably 0.08 or less, and even more preferably 0.05 or less. From the viewpoint of further suppressing mold contamination, it is preferably 0.001 to 0.10, more preferably 0.005 to 0.08, and even more preferably 0.01 to 0.05.

[0160] 4. Method for manufacturing optically molded articles The method for manufacturing the optical molded article of this embodiment will be described below.

[0161] A method for producing an optical molded article according to the present embodiment uses an injection molding apparatus comprising: an injection unit consisting of a cylinder and a screw inserted into the cylinder; a cavity for molding the optical molded article; and a mold having a gate section that serves as an injection passage for a resin composition from the injection unit into the cavity. The method comprises: step (i) of melting a resin composition containing a pentaerythritol derivative composition represented by the following general formula (1) and a polymer represented by the following general formula (2) in the cylinder; and step (ii) of injecting the molten resin composition through the gate section using the screw and filling the cavity with the same, wherein the following (condition 1) and (condition 2) are satisfied. (Condition 1) The method comprises a continuous drying step of continuously drying the resin composition, and a nitrogen dryer is used in the continuous drying step. (Condition 2) A molding cycle is 120 seconds or more per cycle.

[0162]

Chemical Formula

[0163] In general formula (1), R is a hydrocarbon group, the number of carbon atoms in the RCOO group is 18 or more and 24 or less, and n is a real number of 0 or more and 4 or less.

[0164]

Chemical Formula

[0165] In general formula (2), x and y represent copolymerization ratios, and are real numbers satisfying 0 / 100 ≤ y / x ≤ 95 / 5. x and y are on a molar basis. n represents the number of substitutions of the substituent Q, and is a real number satisfying 0 ≤ n ≤ 2. R a is a (2+n)-valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms. R b is a monovalent group selected from the group consisting of a hydrogen atom and hydrocarbon groups having 1 to 28 carbon atoms. R cis a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms. Q is a halogen atom, a halogenated alkyl group, an alkoxy group or -COOR d . R d is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.

[0166] In the method for producing an optical molded article according to the present embodiment, the content of the pentaerythritol derivative composition according to the present embodiment relative to 100 parts by mass of the polymer according to the present embodiment is 1.0 part by mass or more and 5.0 parts by mass or less. The pentaerythritol derivative composition according to the present embodiment contains pentaerythritol and a pentaerythritol ester compound, where when the mass of RCOO groups having 18 to 24 carbon atoms in the pentaerythritol derivative composition of the present embodiment is taken as 1, the mass ratio of RCOO groups having 20 to 24 carbon atoms is 0.90 or more and 0.99 or less.

[0167] According to the method for producing an optical molded article of the present embodiment, mold staining can be suppressed.

[0168] In the method for producing an optical molded article according to the present embodiment, the time per molding cycle of (Condition 2) is not particularly limited, but for example, it may be 150 seconds or longer, may be 170 seconds or longer, and for example, may be 300 seconds or shorter, may be 240 seconds or shorter, or may be 200 seconds or shorter.

[0169] When the method for producing an optical molded article of the present embodiment includes a continuous injection molding step, the duration of the continuous injection molding step is not particularly limited, but for example, it may be 1 day (24 hours) or longer, may be 2 days or longer, or may be 4 days or longer. According to the method for producing an optical molded article of the present embodiment, mold staining can be suppressed, so the method for producing an optical molded article of the present embodiment is suitable for long-term continuous molding.

[0170] Although embodiments of the present invention have been described above, these are merely examples, and various other configurations can be adopted. Furthermore, the present invention is not limited to the embodiments described above, and any modifications, improvements, etc., that can achieve the objectives of the present invention are included in the present invention. [Examples]

[0171] The present invention will now be described in detail with reference to examples, but the present invention is not limited to these examples.

[0172] <Synthesis of Pentaerythritol Derivative Compositions> [Synthesis Example 1] Pentaerythritol derivative composition (1) was prepared by the following method. 250.3 g (1.84 mol) of pentaerythritol and 811.9 g (2.39 mol) of aliphatic monocarboxylic acid (aliphatic monocarboxylic acid with a mass ratio of 18, 20, 22, and 24 carbon atoms of 3:10:85:2, respectively) were weighed into a 2000 mL four-necked glass flask. The dehydration esterification reaction was carried out while controlling the reaction system temperature at 235°C and blowing nitrogen at a rate of 20 mL / min until the acid value was 2.0 or less. Subsequently, the reaction system was cooled to 80-90°C, and while maintaining this temperature, suction filtration was performed using No. 2 filter paper (manufactured by ADVANTEC) to obtain 987.7 g of pentaerythritol derivative composition (1). In this synthesis example, the mass ratio of starting carboxylic acids with a specific number of carbon atoms in the production of the pentaerythritol ester compound (Z) was considered to be the mass ratio of RCOO groups with a specific number of carbon atoms. Specifically, in this synthesis example, aliphatic monocarboxylic acids with 18, 20, 22, and 24 carbon atoms were used as raw materials, with mass ratios of 3:10:85:2. Therefore, in the pentaerythritol derivative composition (1), when the mass of RCOO groups with 18 to 24 carbon atoms is set to 1, the mass ratio of RCOO groups with 18 carbon atoms is 0.03, the mass ratio of RCOO groups with 20 carbon atoms is 0.10, the mass ratio of RCOO groups with 22 carbon atoms is 0.85, and the mass ratio of RCOO groups with 24 carbon atoms is 0.02. Then, from the above mass ratio, the mass ratio of RCOO groups having 20 to 24 carbon atoms in pentaerythritol derivative composition (1), with the mass of RCOO groups having 18 to 24 carbon atoms set to 1, is calculated to be 0.97.

[0173] <Quantitative determination of pentaerythritol (gas chromatography)> First, the conditions for the measuring equipment, etc., were as follows: Measuring equipment: 8890 GC System (Agilent Technologies) Column: DB-1HT (manufactured by J&W) (30m × 250μm × 0.1μm) Carrier gas: He (constant flow mode) Split ratio: 50:1 Detector: FID Inlet temperature: 330℃ Detector temperature: 330℃ Measurement temperature conditions: The temperature was increased from 100°C at a rate of 10°C / min and held at 380°C for 27 minutes. Detection sensitivity: Acquisition speed, 20Hz Minimum peak width, 0.01 min Injection volume: 1 μl (split method)

[0174] Then, the calibration curve samples were prepared using the following procedure. (1) Accurately weigh approximately 0.5 mg, 1.0 mg, and 2.0 mg of pentaerythritol (Wako Pure Chemical Industries: Reagent) into 10 cc screw-cap tubes. (Record the amount collected to the last digit in mg.) After step (2) (1), add 1 cc of TMS derivatizing agent into the screw tube and close the cap. (TMS derivatizing agent: TMSI-H, manufactured by GL Sciences Inc., reagent) After step (3) (2), gently shake the screw tube in a warm bath at 80°C to allow the reaction to proceed. (About 10 minutes) After step (4) (3), add 5 cc of ion-exchanged water into the screw tube to deactivate TMS. After step (5) (4), add 1.00 cc of hexane into the screw tube, shake well, and then leave the screw tube stand still. (Volumetric pipette used) After step (6) (5), water / hexane separates into layers in the screw tube, so collect the hexane layer to obtain a gas chromatography sample. (7) Measure the sample obtained in step (6) under the above conditions to prepare a calibration curve

[0175] Further, a sample for measurement was prepared from pentaerythritol derivative composition (1) according to the following procedure, and pentaerythritol in pentaerythritol derivative composition (1) was quantified, and the result was 0.3% by mass. (a) Weigh out about 20 mg of pentaerythritol derivative composition (1) into a 10 cc screw tube. (Collected amount: record to the ones place of mg) (b) After step (a), add 1 cc of TMS derivatizing agent into the screw tube and close the cap. (TMS derivatizing agent: TMSI-H, manufactured by GL Sciences Inc., reagent:) (c) After step (b), gently shake the screw tube in a warm bath at 80°C to allow the reaction to proceed. (About 10 minutes) (d) After step (c), add 5 cc of ion-exchanged water into the screw tube to deactivate TMS. (e) After step (d), add 1.00 cc of hexane into the screw tube, shake well, and then leave it stand still. (Volumetric pipette used) (f) After step (e), water / hexane separates into layers, so collect the hexane layer to obtain a gas chromatography sample. (g) Perform measurement using the sample obtained in step (f), and quantify the content of pentaerythritol in pentaerythritol derivative composition (1) from the calibration curve.

[0176] <Quantitative determination of mono, di, tri, and tetraesters (gel permeation chromatography)> A pentaerythritol derivative composition (1) was subjected to gel permeation chromatography (GPC) under the following conditions to obtain a GPC chart. The peak area ratios corresponding to the mono, di, tri, and tetraesters in the obtained GPC chart were then determined. The peak area ratio corresponding to pentaerythritol was also determined. The results are shown in Table 1. Measuring instrument: HLC-8420GPC (manufactured by Tosoh Corporation) Column: G2000HXL+G1000HXL Solvent: THF Flow rate: 1.0mL / min Column temperature: 40℃ Sample concentration: 0.3% Injection volume: 100μL Detection sensitivity: 0.100mV / min Detector: RI Standard material: Polystyrene (manufactured by Tosoh Corporation, Mw=500, 2630, 10200)

[0177] [Table 1]

[0178] <Manufacturing of resin compositions> [Example 1] (Preparation of catalyst) A vanadium catalyst was prepared by diluting VO(OC2H5)Cl2 with cyclohexane. Also, ethyl aluminum sesquichloride Al(C2H5) 1.5 Cl 1.5 The solution was diluted with cyclohexane to prepare an organoaluminum compound catalyst solution.

[0179] (polymerization) In a stirred polymerizer, the vanadium catalyst and organoaluminum compound catalyst solution prepared by the above method are used as catalysts to polymerize ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10A copolymerization reaction of ]-3-dodecene was carried out to obtain a cyclic olefin copolymer solution. Here, ethylene was supplied into the polymerizer along with hydrogen gas.

[0180] (Decalcification) Water and an aqueous sodium hydroxide solution were added to the obtained cyclic olefin copolymer solution to stop the polymerization reaction and remove the catalyst residue present in the cyclic olefin copolymer solution (decalcification). Pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] was added as a phenolic antioxidant to the decalcified cyclic olefin copolymer solution and mixed in a stirring tank for 1 hour.

[0181] (Solvent removal) A cyclic olefin copolymer solution mixed with a phenolic antioxidant is heated to 180°C to remove the solvent and unreacted monomers, thereby obtaining the molten cyclic olefin copolymer (ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 A random copolymer with ]-3-dodecene was obtained. Furthermore, the glass transition temperature (Tg) of the obtained cyclic olefin copolymer was evaluated to be 152°C.

[0182] (Extrusion) 100 parts by mass of the obtained cyclic olefin copolymer and 2.5 parts by mass of the pentaerythritol derivative composition (1) were kneaded together and pelletized. The resulting pellets were dried with hot air at a temperature of 100°C for 4 hours to obtain the resin composition.

[0183] [Example 2] A resin composition was obtained in the same manner as in Example 1, except that 4.5 parts by mass of the pentaerythritol derivative composition (1) was added.

[0184] [Comparative Example 1] A resin composition was obtained in the same manner as in Example 1, except that instead of the pentaerythritol derivative composition (1), 2.5 parts by mass of pentaerythritol tetrastearate (manufactured by NOF Corporation, product name: WE-476-H) was kneaded with a cyclic olefin polymer and pelletized.

[0185] <Evaluation of compatibility and heat / moisture resistance> (Nitrogen drying) The resin composition obtained by the above method was immediately placed in a continuous nitrogen dryer (DO-15N, manufactured by Kawata Co., Ltd.) and nitrogen-dried at 120°C and an oxygen concentration of 1% for 20 hours.

[0186] (injection molding) A nitrogen-dried resin composition was transported to the cylinder of an injection molding machine, where it was melted and metered by screw rotation. Injection molding was then performed on a mold having a cavity and gate section under the following conditions to produce a test piece with an optical surface of 65 mm × 35 mm × 3 mm thickness. Injection molding machine: α-S30iA, manufactured by Fanuc Mold: 65mm x 35mm x 3mm thick mold Cylinder temperature: 260℃ Back pressure: 30kgf / cm 2 Screw rotation speed: 30 rpm Cycle time: 130s

[0187] (Heat and humidity resistance test) The test pieces obtained by the above method were treated at 65°C, 90%RH, and for 504 hours, and then allowed to stand at 23°C, 50%RH, and for 24 hours.

[0188] (Internal haze measurement, and evaluation of compatibility and heat / moisture resistance) Test pieces were immersed in benzyl alcohol before and after the humidity and heat resistance test, and internal haze was measured using a haze meter (SH7000: manufactured by Nippon Denshoku Industries Co., Ltd.). The results are shown in Table 2. Note that the internal haze value before the humidity and heat resistance test is an indicator of compatibility; a smaller value indicates improved compatibility. The difference in internal haze values ​​before and after the humidity and heat resistance test, obtained by subtracting the internal haze value before the humidity and heat resistance test from the internal haze value after the test, is an indicator of humidity and heat resistance; a smaller value indicates improved humidity and heat resistance.

[0189] <Evaluation of mold contamination> (Nitrogen drying) The resin composition obtained by the above method was immediately placed in a continuous nitrogen dryer (DO-15N, manufactured by Kawata Co., Ltd.) and dried at 120°C and 1% oxygen concentration for 20 hours.

[0190] (injection molding) A nitrogen-dried resin composition was transported to the cylinder of an injection molding machine, where it was melted and metered by screw rotation. Continuous injection molding was performed on a mold having a cavity and gate section under the following conditions, with 150 shots per day for a total of 4 days, to produce a convex meniscus lens with an optical surface of 56 mm in diameter and a maximum thickness of 9 mm. Injection molding machine: α-S100iA, manufactured by Fanuc Mold: φ56 convex meniscus mold Cylinder temperature: 260℃ Back pressure: 30kgf / cm 2 Screw rotation speed: 30 rpm Cycle time: 170s

[0191] (Mold observation) The molds after continuous injection molding were observed using a stereomicroscope (SZX16, manufactured by Olympus Corporation), and the contamination (mold contamination) adhering to the molds was evaluated according to the following criteria. The results are shown in Table 2. Figures 1 and 2 show stereomicrographs of the molds of Examples 1 and 2. Figure 3 shows a stereomicrograph of the mold of Comparative Example 1. Figure 4 shows a stereomicrograph of the particulate gas contamination generated in the mold of Comparative Example 1.

[0192] (standard) A: No significant gas contamination was observed on the entire mold core. B: A thin layer of streaky gas stains is attached to the mold gate area. C: Particulate gas contaminants are attached to the mold core, or streaky gas contaminants are attached to the mold gate.

[0193] [Table 2]

[0194] As described above, mold contamination was suppressed in the embodiment compared to the comparative example. From this, it can be seen that the resin composition of this embodiment can suppress mold contamination.

Claims

1. A resin composition comprising a pentaerythritol derivative composition represented by the following general formula (1) and a polymer represented by the following general formula (2), 【Chemistry 1】 (In general formula (1), R is a hydrocarbon group, the number of carbon atoms in the RCOO group is between 18 and 24, and n is a real number between 0 and 4.) 【Chemistry 2】 (In general formula (2), x and y represent the copolymerization ratio and are real numbers satisfying 0 / 100 ≤ y / x ≤ 95 / 5. x and y are based on moles. n represents the number of substitutions of substituent Q and is a real number 0 ≤ n ≤ 2. ａ R is a 2+n valent group selected from the group consisting of hydrocarbon groups with 2 to 20 carbon atoms. ｂ R is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 28 carbon atoms. ｃ Q is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms. Q is a halogen atom, an alkyl halide, an alkoxy group, or -COOR ｄ That is. R ｄ (This is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) The content of the pentaerythritol derivative composition relative to 100 parts by mass of the polymer is 1.0 part by mass or more and 5.0 parts by mass or less. The aforementioned pentaerythritol derivative composition comprises pentaerythritol and a pentaerythritol ester compound. A resin composition in which, when the mass of RCOO groups having 18 to 24 carbon atoms is taken as 1, the mass ratio of RCOO groups having 20 to 24 carbon atoms is 0.90 to 0.

99.

2. The resin composition according to claim 1, wherein the pentaerythritol derivative composition comprises a pentaerythritol monoester compound having n=1 in the general formula (1), a pentaerythritol diester compound having n=2 in the general formula (1), a pentaerythritol triester compound having n=3 in the general formula (1), and a pentaerythritol tetraester compound having n=4 in the general formula (1).

3. The resin composition according to claim 2, wherein in a chart obtained by gel permeation chromatography (GPC) of the pentaerythritol derivative composition under the following conditions, the ratio of the sum of the peak area of ​​the pentaerythritol monoester compound and the peak area of ​​the pentaerythritol diester compound, with the total peak area being 1, is 0.60 or more and 0.80 or less. Columns: G2000HXL + G1000HXL Solvent: THF Flow rate: 1.0mL / min Column temperature: 40°C Sample concentration: 0.3% Injection volume: 100μL Detector: RI Standard material: Polystyrene (manufactured by Tosoh Corporation, Mw = 500, 2630, 10200)

4. The resin composition according to claim 2 or 3, wherein in a chart obtained by gel permeation chromatography (GPC) of the pentaerythritol derivative composition under the following conditions, the ratio of the sum of the peak area of ​​the pentaerythritol triester compound and the peak area of ​​the pentaerythritol tetraester compound, with the total peak area being 1, is 0.18 or more and less than 0.

40. Columns: G2000HXL + G1000HXL Solvent: THF Flow rate: 1.0mL / min Column temperature: 40°C Sample concentration: 0.3% Injection volume: 100μL Detector: RI Standard material: Polystyrene (manufactured by Tosoh Corporation, Mw = 500, 2630, 10200)

5. The resin composition according to any one of claims 1 to 4, wherein the content of pentaerythritol is 0.002 or more and 0.010 or less when the total mass of the pentaerythritol derivative composition is 1.

6. The resin composition according to any one of claims 1 to 5, wherein the polymer comprises (i) a copolymer of ethylene or an α-olefin and a cyclic olefin.

7. The polymer is composed of ethylene and tetracyclo[4.4.0.1 ２，５ 1. ７，１０ The resin composition according to claim 6, comprising a copolymer consisting of ]-3-dodecene.

8. An optically molded article comprising the resin composition described in any one of claims 1 to 7.

9. The optical molded body according to claim 8, wherein the optical molded body includes a lens.

10. The optical molded body according to claim 8 or 9, wherein the maximum thickness of the optical molded body is 1.0 mm or more and 20.0 mm or less.

11. A method for producing a resin composition comprising a pentaerythritol derivative composition represented by the following general formula (1) and a polymer represented by the following general formula (2), 【Transformation 3】 (In general formula (1), R is a hydrocarbon group, the number of carbon atoms in the RCOO group is between 18 and 24, and n is a real number between 0 and 4.) 【Chemistry 4】 In general formula (2), x and y each represent a copolymerization ratio, and are real numbers satisfying 0 / 100 ≤ y / x ≤ 95 / 5. x and y are on a molar basis. n represents the number of substitutions of the substituent Q, and is a real number satisfying 0 ≤ n ≤ 2. R ａ is a (2+n)-valent group selected from the group consisting of hydrocarbon groups having 2 to 20 carbon atoms. R ｂ is a monovalent group selected from the group consisting of a hydrogen atom and hydrocarbon groups having 1 to 28 carbon atoms. R ｃ is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms. Q is a halogen atom, a halogenated alkyl group, an alkoxy group or -COOR ｄ R ｄ is a monovalent group selected from the group consisting of a hydrogen atom and hydrocarbon groups having 1 to 10 carbon atoms.) The process comprises the steps of (I) preparing the pentaerythritol derivative composition by mixing 1.0 mole of pentaerythritol with 1.0 mole to 1.7 moles of an aliphatic monocarboxylic acid having 18 to 24 carbon atoms and carrying out an esterification reaction, and (II) mixing 1.0 to 5.0 parts by mass of the pentaerythritol derivative composition with 100 parts by mass of the polymer. The aforementioned pentaerythritol derivative composition comprises pentaerythritol and a pentaerythritol ester compound. A method for producing a resin composition, wherein the mass ratio of aliphatic monocarboxylic acids having 20 to 24 carbon atoms is 0.90 or more and 0.99 or less, when the mass of aliphatic monocarboxylic acids having 18 to 24 carbon atoms is taken as 1.

12. A method for manufacturing an optical molded article using an injection molding apparatus, comprising: an injection unit consisting of a cylinder and a screw inserted into the cylinder; a cavity for molding an optical molded article; and a mold having a gate section that serves as an injection passage for a resin composition from the injection unit into the cavity, The process includes (i) melting a resin composition in the cylinder, the resin composition comprising a pentaerythritol derivative composition represented by the following general formula (1) and a polymer represented by the following general formula (2), and (ii) injecting the molten resin composition through the gate section using the screw and filling the cavity. The following conditions (1) and (2) must be met: (Condition 1) The process includes a continuous drying step for continuously drying the resin composition, and a nitrogen dryer is used in the continuous drying step. (Condition 2) The molding cycle must be 120 seconds or longer per cycle. 【Transformation 5】 (In general formula (1), R is a hydrocarbon group, the number of carbon atoms in the RCOO group is between 18 and 24, and n is a real number between 0 and 4.) 【Transformation 6】 (In general formula (2), x and y represent the copolymerization ratio and are real numbers satisfying 0 / 100 ≤ y / x ≤ 95 / 5. x and y are based on moles. n represents the number of substitutions of substituent Q and is a real number 0 ≤ n ≤ 2. ａ R is a 2+n valent group selected from the group consisting of hydrocarbon groups with 2 to 20 carbon atoms. ｂ R is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 28 carbon atoms. ｃ Q is a tetravalent group selected from the group consisting of hydrocarbon groups having 2 to 10 carbon atoms. Q is a halogen atom, an alkyl halide, an alkoxy group, or -COOR ｄ That is. R ｄ (This is a monovalent group selected from the group consisting of a hydrogen atom or a hydrocarbon group having 1 to 10 carbon atoms.) The content of the pentaerythritol derivative composition relative to 100 parts by mass of the polymer is 1.0 part by mass or more and 5.0 parts by mass or less. The aforementioned pentaerythritol derivative composition comprises pentaerythritol and a pentaerythritol ester compound. A method for producing an optically molded article, wherein the mass ratio of RCOO groups having 20 to 24 carbon atoms to the mass of RCOO groups having 18 to 24 carbon atoms in the pentaerythritol derivative composition is 0.90 to 0.99.

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