Regenerated cyclic olefinic resin composition, molded article and optical component

Abstract

To provide a regenerated cyclic olefinic resin composition that yields a molded article and an optical component with mitigated transparency reduction and yellowing, and to provide a molded article and an optical component with mitigated transparency reduction and yellowing.SOLUTION: A regenerated cyclic olefinic resin composition contains a cyclic olefinic resin (A), a phenolic antioxidant (B), and a phosphorous stabilizer (C). The cyclic olefinic resin (A) contains a recovered cyclic olefin resin (A1). The phosphorous stabilizer (C) has a 10% mass loss temperature in the air of 275°C or higher, as measured with a calorimeter.SELECTED DRAWING: None

Description

[Technical field]

[0001] The present invention relates to a recycled cyclic olefin resin composition, a molded article, and an optical part. [Background technology]

[0002] Cyclic olefin resins are disclosed for use in, for example, transparent containers for food and medicine; optical lenses such as eyeglass lenses, pickup lenses, fθ lenses, and smartphone camera lenses; and optical recording media such as MO, DVD, and CD (see, for example, Patent Document 1). Molded articles for such applications are molded using molding machines such as injection molding machines, and large amounts of processing waste materials such as sprues and runners are generated during molding. Currently, most of these processing waste materials are incinerated, but the incineration of plastics such as cyclic olefin resins generates large amounts of carbon dioxide gas, which is problematic from the perspective of protecting the global environment. In recent years, recycled plastics obtained by collecting waste materials of molded bodies made of thermoplastic resin, pulverizing them as necessary, and forming them into pellets have been widely used (see, for example, Patent Document 2).

[0003] Patent Document 1 describes a resin composition that contains a polymer containing an alicyclic structure in at least a portion of the repeating structural units and a fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups, with the aim of providing a resin composition that can give a molded article that has excellent optical performance and further suppresses deterioration of the optical performance under high temperature and high humidity conditions.

[0004] Patent Document 2 describes a method for treating cyclic olefin resin molded bodies, which is characterized by contacting a molded body made of a specific cyclic olefin resin with a liquid hydrocarbon compound to soften or fluidize the cyclic olefin resin, with the aim of providing a method for treating cyclic olefin resin molded bodies that can easily soften or fluidize the cyclic olefin resin molded bodies. [Prior art documents] [Patent documents]

[0005] [Patent Document 1] JP 2015-199939 A [Patent Document 2] JP 2000-169621 A Summary of the Invention [Problem to be solved by the invention]

[0006] However, when waste materials from molded bodies containing cyclic olefin resins are reused, the resulting molded bodies or optical components may become yellowed or the transparency of the resulting molded bodies or optical components may decrease, making it impossible to use them for their intended purposes.

[0007] The present invention has been made in consideration of the above-mentioned circumstances, and provides a recycled cyclic olefin resin composition that can produce molded articles and optical components in which the decrease in transparency and the yellowing are suppressed, as well as molded articles and optical components in which the decrease in transparency and the yellowing are suppressed. [Means for solving the problem]

[0008] According to the present invention, there are provided the following recycled cyclic olefin resin composition, molded article, and optical component.

[0009] [1] A recycled cyclic olefin resin composition comprising a cyclic olefin resin (A), a phenol-based antioxidant (B), and a phosphorus-based stabilizer (C), The cyclic olefin resin (A) contains a recycled cyclic olefin resin (A1), The phosphorus-based stabilizer (C) is a recycled cyclic olefin resin composition having a 10% mass loss temperature in air of 275°C or higher as measured by a calorimeter. [2] The recycled cyclic olefin resin composition according to [1], wherein the content of the phosphorus-based stabilizer (C) is 0.01 parts by mass or more and 1.00 parts by mass or less per 100 parts by mass of the cyclic olefin resin (A). [3] The recycled cyclic olefin resin composition according to [1] or [2], wherein the content of the phenol-based antioxidant (B) is 0.01 parts by mass or more and 0.50 parts by mass or less per 100 parts by mass of the cyclic olefin resin (A). [4] The recycled cyclic olefin resin composition according to any one of [1] to [3] above, wherein the mass ratio (C / B) of the content of the phosphorus-based stabilizer (C) to the content of the phenol-based antioxidant (B) is 0.1 or more and 2.5 or less. [5] The recycled cyclic olefin resin composition according to any one of [1] to [4], wherein the phosphorus-based stabilizer (C) comprises at least one selected from the group consisting of phosphorus-based stabilizers represented by the following formula (1) and phosphorus-based stabilizers represented by the following formula (3). [ka] (In the above formula (1), R 501 ~R 505 may be the same or different and are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) [ka] (In the above formula (3), R 700 is a hydrocarbon group having 1 to 29 carbon atoms, R 701 ~R 708 may be the same or different and are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) [6] The recycled cyclic olefin resin composition according to any one of [1] to [5] above, wherein the phenol-based antioxidant (B) is at least one selected from the group consisting of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene. [7] The cyclic olefin resin (A) is At least one olefin-derived repeating unit (a) represented by the following formula (I); At least one repeating unit (b) derived from a cyclic olefin monomer selected from the group consisting of a repeating unit (AA) represented by the following formula (II), a repeating unit (AB) represented by the following formula (III), and a repeating unit (AC) represented by the following formula (IV), The recycled cyclic olefin resin composition according to any one of the above [1] to [6], comprising a cyclic olefin copolymer (P1) having the following formula: [ka] (In the above formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. [ka] (In the above formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 78 And R a1 and R b1may be the same or different, and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring. [ka] In the formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1, or 2, and R 81 ~R 99 may be the same or different, and each is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group; R 89 and R 90 and the carbon atom to which R is bonded. 93 or the carbon atom to which R 91 may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R 95 and R 92 or R 95 and R 99 may be bonded to each other to form a monocyclic or polycyclic aromatic ring. [ka] (In the formula (IV), R 100 and R 101 may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is an integer satisfying 1≦f≦18. [8] The cyclic olefin resin (A) contains a cyclic olefin copolymer (P2) having a repeating unit (AA) represented by the following formula (II) and a repeating unit (C) derived from a cyclic olefin having an aromatic ring, The repeating unit (AA) does not contain an aromatic ring, The recycled cyclic olefin resin composition according to any one of [1] to [7] above, wherein the cyclic olefin having an aromatic ring comprises at least one selected from the group consisting of a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), and a compound represented by the following formula (C-3): [ka] (In the above formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R 61 ~R 78 And R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms; R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring. [ka] In the formula (C-1), n ​​and q each independently represent 0, 1, or 2; 1 ~R 17 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom; R 10 ~R 17 One of them is a bond, and when q=0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, or the monocyclic or polycyclic ring may be an aromatic ring. [ka] (In the formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, and R 18 ~R 31 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and when q=1, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , R 31 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring. [ka] (In the formula (C-3), q is 1, 2 or 3; R 32 ~R 39each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 36 and R 36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring. [9] The recycled cyclic olefin resin composition according to any one of the above [1] to [8], which is in the form of pellets.

[10] A molded article comprising the recycled cyclic olefin resin composition according to any one of [1] to [9] above.

[11] An optical component comprising the molded article according to

[10] above. Effect of the Invention

[0010] According to the present invention, it is possible to provide a recycled cyclic olefin resin composition which can produce molded articles and optical components in which the decrease in transparency and the yellowing are suppressed, as well as molded articles and optical components in which the decrease in transparency and the yellowing are suppressed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0011] Hereinafter, the present invention will be described based on the embodiments. In the present embodiments, "A to B" indicating a numerical range indicates A or more and B or less unless otherwise specified.

[0012] [Recycled cyclic olefin resin composition] The recycled cyclic olefin resin composition of this embodiment is a recycled cyclic olefin resin composition comprising a cyclic olefin resin (A), a phenol-based antioxidant (B), and a phosphorus-based stabilizer (C), wherein the cyclic olefin resin (A) comprises a recovered cyclic olefin resin (A1), and the phosphorus-based stabilizer (C) has a 10% mass loss temperature in air of 275°C or higher as measured by a calorimeter. In this specification, a cyclic olefin resin recovered from used molded bodies, products, and waste materials according to a known method is called a recovered cyclic olefin resin (A1). A cyclic olefin resin composition containing the recovered cyclic olefin resin (A1) is called a recycled cyclic olefin resin composition. Hereinafter, unless otherwise specified, "10% mass loss temperature" means "10% mass loss temperature in air measured by a calorimeter."

[0013] As described above, when waste materials of molded bodies containing cyclic olefin resins are reused, the resulting molded bodies or optical components may become yellowed or the transparency of the resulting molded bodies or optical components may decrease, making it impossible to use them for their intended purposes. In addition, the cyclic olefin resin composition may be molded into a pellet shape, a film shape, etc. When the cyclic olefin resin composition is molded, a step of heating the cyclic olefin resin composition to a molten state may be included, but the cyclic olefin resin composition may be yellowed and its transparency may be reduced due to thermal oxidative deterioration. As a result of extensive research, the present inventors have found that a cyclic olefin resin composition containing a specific phosphorus-based stabilizer (C) can produce molded articles and optical components in which the decrease in transparency and yellowing are suppressed, even when the cyclic olefin resin composition contains recycled cyclic olefin resin (A1).

[0014] The cyclic olefin resin (A) of the present embodiment includes a recycled cyclic olefin resin (A1). The cyclic olefin resin (A) may also include a virgin cyclic olefin resin. Hereinafter, the "content of cyclic olefin resin (A)" means the total of the content of the recovered cyclic olefin resin (A1) and the content of the unused cyclic olefin resin, unless otherwise specified. In addition, "100 parts by mass of cyclic olefin resin (A)" means the total of the parts by mass of the recovered cyclic olefin resin (A1) and the parts by mass of the unused cyclic olefin resin, which is 100 parts by mass, unless otherwise specified.

[0015] The content of cyclic olefin resin (A) in the recycled cyclic olefin resin composition of this embodiment, when the entire recycled cyclic olefin resin composition is taken as 100 mass%, is preferably 95.0 mass% or more, more preferably 96.0 mass% or more, even more preferably 97.0 mass% or more, even more preferably 98.0 mass% or more, even more preferably 98.5 mass% or more, even more preferably 98.8 mass% or more, even more preferably 99.0 mass% or more, even more preferably 99.2 mass% or more, even more preferably 99.5 mass% or more, even more preferably 99.7 mass% or more, and is preferably 99.98 mass% or less, more preferably 99.90 mass% or less, from the viewpoint of further improving the performance balance of moldability and transparency. The content of the recovered cyclic olefin resin (A1) in the recycled cyclic olefin resin composition of this embodiment, when the entire recycled cyclic olefin resin composition is taken as 100% by mass, is preferably 30.0% by mass or more, more preferably 50.0% by mass or more, even more preferably 70.0% by mass or more, even more preferably 80.0% by mass or more, even more preferably 90.0% by mass or more, even more preferably 95.0% by mass or more, even more preferably 96.0% by mass or more, even more preferably 97.0% by mass or more, even more preferably 98.0% by mass or more, even more preferably 98.5% by mass or more, even more preferably 98.8% by mass or more, even more preferably 99.0% by mass or more, even more preferably 99.2% by mass or more, even more preferably 99.5% by mass or more, even more preferably 99.7% by mass or more, and preferably 99.98% by mass or less, more preferably 99.90% by mass or less, from the viewpoint of protecting the global environment.

[0016] The content of the phenol-based antioxidant (B) in the recycled cyclic olefin resin composition of this embodiment is, from the viewpoint of further suppressing a decrease in transparency and yellowing, preferably 0.01 parts by mass or more, more preferably 0.03 parts by mass or more, even more preferably 0.05 parts by mass or more, even more preferably 0.07 parts by mass or more, and even more preferably 0.09 parts by mass or more, per 100 parts by mass of the cyclic olefin resin (A); and, from the viewpoint of further suppressing a decrease in transparency and yellowing, preferably 0.50 parts by mass or less, more preferably 0.40 parts by mass or less, even more preferably 0.30 parts by mass or less, even more preferably 0.20 parts by mass or less, and even more preferably 0.15 parts by mass or less.

[0017] The content of the phosphorus-based stabilizer (C) in the recycled cyclic olefin resin composition of this embodiment is preferably 0.01 part by mass or more, more preferably 0.02 part by mass or more, and even more preferably 0.04 part by mass or more, per 100 parts by mass of the cyclic olefin resin (A), from the viewpoint of further suppressing a decrease in transparency and yellowing, and is preferably 1.00 part by mass or less, more preferably 0.80 part by mass or less, even more preferably 0.50 part by mass or less, even more preferably 0.30 part by mass or less, even more preferably 0.20 part by mass or less, even more preferably 0.10 part by mass or less, and even more preferably 0.07 part by mass or less, from the viewpoint of further suppressing a decrease in transparency and yellowing.

[0018] In the recycled cyclic olefin resin composition of this embodiment, the mass ratio (C / B) of the content of the phosphorus-based stabilizer (C) to the content of the phenol-based antioxidant (B) is preferably 0.1 or more, more preferably 0.2 or more, and even more preferably 0.4 or more, from the viewpoint of further suppressing a decrease in transparency and yellowing, and is preferably 2.5 or less, more preferably 2.0 or less, even more preferably 1.5 or less, even more preferably 1.0 or less, and even more preferably 0.7 or less, from the viewpoint of further suppressing a decrease in transparency and yellowing.

[0019] When the entire recycled cyclic olefin resin composition is taken as 100% by mass, from the viewpoint of further improving the performance balance between moldability and transparency, it is preferable that the content of cyclic olefin resin (A) in the recycled cyclic olefin resin composition of this embodiment is 95.0% by mass or more and 99.9% by mass or less, the content of phenol-based antioxidant (B) is 0.01% by mass or more and 0.50% by mass or less, and the content of phosphorus-based stabilizer (C) is 0.01% by mass or more and 1.00% by mass or less. In addition, the total content of the cyclic olefin resin (A), the phenol-based antioxidant (B), and the phosphorus-based stabilizer (C) in the recycled cyclic olefin resin composition of this embodiment, when the entire recycled cyclic olefin resin composition is taken as 100 mass%, is preferably 80.0 mass% or more, more preferably 90.0 mass% or more, even more preferably 93.0 mass% or more, even more preferably 95.0 mass% or more, even more preferably 97.0 mass% or more, and preferably 100 mass% or less, from the viewpoint of further improving the performance balance of moldability and transparency.

[0020] The melt flow rate (MFR) of the recycled cyclic olefin resin composition, measured in accordance with ASTM D1238 at 260°C under a load of 2.16 kg, is, from the viewpoint of further improving moldability, preferably 5 g / 10 min or more, more preferably 8 g / 10 min or more, even more preferably 10 g / 10 min or more, and even more preferably 20 g / 10 min or more. There is no particular upper limit, but it may be, for example, 100 g / 10 min or less, or 50 g / 10 min or less.

[0021] From the viewpoint of improving the performance balance of moldability, transparency and heat resistance, the glass transition temperature (Tg) of the recycled cyclic olefin resin composition is preferably 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, even more preferably 100°C or higher, even more preferably 110°C or higher, even more preferably 120°C or higher, even more preferably 130°C or higher, and even more preferably 140°C or higher, and from the viewpoint of improving the performance balance of moldability, transparency and heat resistance, it is preferably 250°C or lower, more preferably 200°C or lower, even more preferably 180°C or lower, even more preferably 170°C or lower, and even more preferably 160°C or lower. The glass transition temperature (Tg) of the recycled cyclic olefin resin composition can be measured, for example, by the method described in the Examples.

[0022] Each of the components of the recycled cyclic olefin resin composition of this embodiment will be described below.

[0023] (Cyclic olefin resin (A)) The cyclic olefin resin (A) of the present embodiment includes a recycled cyclic olefin resin (A1). The cyclic olefin resin (A) may also include a virgin cyclic olefin resin.

[0024] The content of recovered cyclic olefin resin (A1) in the cyclic olefin resin (A) of this embodiment, when the entire cyclic olefin resin (A) is taken as 100 mass%, is, from the viewpoint of protecting the global environment, preferably 30.0 mass% or more, more preferably 50.0 mass% or more, even more preferably 70.0 mass% or more, even more preferably 80.0 mass% or more, even more preferably 90.0 mass% or more, even more preferably 95.0 mass% or more, even more preferably 97.0 mass% or more, even more preferably 99.0 mass% or more, even more preferably 99.5 mass% or more, even more preferably 99.8 mass% or more, and preferably 100 mass% or less.

[0025] The cyclic olefin resin (A) of the present embodiment is not particularly limited, and may be a cyclic olefin homopolymer or a cyclic olefin copolymer. The cyclic olefin resin (A) of the present embodiment may be used alone or in combination of two or more kinds.

[0026] A preferred embodiment of the cyclic olefin resin (A) will be described below. A preferred embodiment of the recovered cyclic olefin resin (A1) is the same as the preferred embodiment of the cyclic olefin resin (A).

[0027] From the viewpoint of further improving the heat resistance while maintaining a good balance between the transparency and refractive index of the obtained molded article and optical component, and from the viewpoint of further improving the moldability, the cyclic olefin resin (A) preferably contains a cyclic olefin copolymer (P1) having at least one olefin-derived repeating unit (a) represented by the following formula (I) and at least one cyclic olefin monomer-derived repeating unit (b) selected from the group consisting of repeating units (AA) represented by the following formula (II), repeating units (AB) represented by the following formula (III), and repeating units (AC) represented by the following formula (IV).

[0028] [ka]

[0029] In the formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0030] [ka]

[0031] In the formula (II), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 78 And R a1and R b1 may be the same or different, and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0032] [ka]

[0033] In the formula (III), x and d are 0 or an integer of 1 or more, y and z are 0, 1, or 2, and R 81 ~R 99 may be the same or different, and each is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group; R 89 and R 90 and the carbon atom to which R is bonded. 93 or the carbon atom to which R 91 may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R 95 and R 92 or R 95 and R 99 may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0034] [ka]

[0035] In the formula (IV), R 100 and R 101 may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is an integer satisfying 1≦f≦18.

[0036] The olefin monomer, which is one of the copolymerization raw materials for the cyclic olefin copolymer (P1), undergoes addition copolymerization to form the repeating unit (a) represented by the above formula (I). Specifically, the olefin monomer represented by the following formula (Ia) corresponding to the above formula (I) is used.

[0037] [ka]

[0038] In the formula (Ia), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. Examples of the olefin monomer represented by the formula (Ia) 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. From the viewpoint of obtaining a molded product having better heat resistance, mechanical properties, and optical properties, at least one selected from the group consisting of ethylene and propylene is preferred, and ethylene is more preferred. Two or more kinds of olefin monomers represented by the formula (Ia) may be used. When the total repeating units constituting the cyclic olefin copolymer (P1) is taken as 100 mol %, the proportion of the olefin-derived repeating units (a) is preferably 5 mol % or more and 95 mol % or less, more preferably 20 mol % or more and 90 mol % or less, even more preferably 40 mol % or more and 85 mol % or less, and even more preferably 50 mol % or more and 80 mol % or less. The proportion of repeating units (a) derived from olefins is as follows: 13 It can be measured by C-NMR.

[0039] The cyclic olefin monomer, which is one of the copolymerization raw materials of the cyclic olefin copolymer (P1), undergoes addition copolymerization to form the repeating unit (b) derived from the cyclic olefin monomer represented by the formula (II), the formula (III) or the formula (IV). Specifically, the cyclic olefin monomers represented by the formulas (IIa), (IIIa) and (IVa) corresponding to the formulas (II), (III) and (IV), respectively, are used.

[0040] [ka]

[0041] In the formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 78 And R a1 and R b1 may be the same or different, and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms; R 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0042] [ka]

[0043] In the formula (IIIa), x and d are 0 or an integer of 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1, y and z are 0, 1, or 2, and R 81 ~R 99 may be the same or different, and each is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms, or an alkoxy group; R 89 and R90 and the carbon atom to which R is bonded. 93 or the carbon atom to which R 91 may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y=z=0, R 95 and R 92 or R 95 and R 99 may be bonded to each other to form a monocyclic or polycyclic aromatic ring.

[0044] [ka]

[0045] In the formula (IVa), R 100 and R 101 may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is an integer satisfying 1≦f≦18.

[0046] Specific examples of the cyclic olefin monomer represented by formula (IIa), (IIIa) or (IVa) that can be used include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261.

[0047] Specifically, 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, hexacyclo-4-heptadecene derivatives, and heptacyclo-5-eicosene derivatives. conductors, heptacyclo-4-eicosene derivatives, heptacyclo-5-heneicosene derivatives, octacyclo-5-docosene derivatives, nonacyclo-5-pentacosene derivatives, nonacyclo-6-hexacosene derivatives, cyclopentadiene-acenaphthylene adducts, 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.

[0048] Among the cyclic olefin monomers represented by formula (IIa), (IIIa) or (IVa), the cyclic olefin monomer represented by formula (IIa) is preferred. It is also preferable to use a cyclic olefin represented by formula (IIa) and either a cyclic olefin represented by formula (IIIa) or (IVa).

[0049] As the cyclic olefin monomer represented by the formula (IIa), bicyclo[2.2.1]-2-heptene (also referred to as "norbornene" in this specification) and tetracyclo[4.4.0.1 2,5 .1 7,10 It is preferable to use at least one selected from the group consisting of tetracyclo[4.4.0.1]-3-dodecene (also referred to as "tetracyclododecene" in this specification), and 2,5 .1 7,10 It is more preferable to use ]-3-dodecene. These cyclic olefins have a rigid ring structure, and therefore have the advantage that the elastic modulus of the copolymer and the molded article can be easily maintained.

[0050] When the total number of repeating units constituting the cyclic olefin copolymer (P1) is taken as 100 mol %, the proportion of repeating units (b) derived from a cyclic olefin monomer is preferably 5 mol % or more and 95 mol % or less, more preferably 10 mol % or more and 80 mol % or less, even more preferably 15 mol % or more and 60 mol % or less, and even more preferably 20 mol % or more and 50 mol % or less. In this embodiment, the ratio of the repeating unit (b) derived from a cyclic olefin monomer is, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0051] The copolymer type of the cyclic olefin copolymer (P1) is not particularly limited, and examples thereof include random copolymers, block copolymers, etc. From the viewpoint of further improving optical properties such as transparency, refractive index, and birefringence, and obtaining optical components with higher precision, it is preferable to use a random copolymer as the cyclic olefin copolymer (P1).

[0052] Cyclic olefin copolymers (P1) include ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene, random copolymers of ethylene and bicyclo[2.2.1]-2-heptene, and random copolymers of ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene and benzonorbornadiene random copolymers, and 2,5 .1 7,10 ]-3-dodecene and ethylene / tetracyclo[4.4.0.1 2,5 .1 7,10 More preferred is at least one selected from the group consisting of random copolymers of ethylene and tetracyclo[4.4.0.1]-3-dodecene and benzonorbornadiene. 2,5 .1 7,10 A random copolymer with ]-3-dodecene is more preferred.

[0053] The cyclic olefin copolymer (P1) may be used alone or in combination of two or more kinds.

[0054] The cyclic olefin copolymer (P1) can be produced by appropriately selecting the conditions according to the methods described in, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, etc.

[0055] From the viewpoint of further improving the heat resistance while maintaining a good balance between the transparency and refractive index of the obtained molded body and optical component, and from the viewpoint of further improving the moldability, the cyclic olefin resin (A) preferably comprises a cyclic olefin copolymer (P2) having a repeating unit (AA) represented by the following formula (II) and a repeating unit (C) derived from a cyclic olefin having an aromatic ring, wherein the repeating unit (AA) does not contain an aromatic ring, and the cyclic olefin having an aromatic ring contains at least one compound selected from the group consisting of a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), and a compound represented by the following formula (C-3).

[0056] [ka]

[0057] In the formula (II), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 to 2, more preferably 0 or 1, w is 0 or 1, R 61 ~R 78 And R a1 and R b1 may be the same or different and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms; R 75 ~R 78may be bonded to each other to form a monocyclic or polycyclic ring.

[0058] [ka]

[0059] In the formula (C-1), n ​​and q each independently represent 0, 1, or 2; 1 ~R 17 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom; R 10 ~R 17 One of them is a bond, and when q=0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10 may be bonded to each other to form a monocycle or polycycle, the monocycle or polycycle may have a double bond, or the monocycle or polycycle may be an aromatic ring.

[0060] [ka]

[0061] In the formula (C-2), n and m are each independently 0, 1 or 2, q is 1, 2 or 3, and R 18 ~R 31 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and when q=1, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , R 31 and R 31 may be bonded to each other to form a monocycle or polycycle, the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0062] [ka]

[0063] In the formula (C-3), q is 1, 2 or 3; R 32 ~R 39 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 36 and R36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39 and R 39 may be bonded to each other to form a monocycle or polycycle, the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0064] The cyclic olefin copolymer (P2) contains the repeating unit (AA) represented by the formula (II) and the repeating unit (C) derived from a cyclic olefin having an aromatic ring, and thus can improve the moist heat resistance while maintaining good transparency.

[0065] (Repeating units derived from cyclic olefins (AA)) The repeating unit (AA) is a repeating unit represented by the above formula (II). By including the repeating unit (AA), the refractive index of the obtained molded article can be further improved. Furthermore, the repeating unit (AA) in the cyclic olefin copolymer (P2) does not contain an aromatic ring. When the repeating unit (AA) does not contain an aromatic ring, the moldability of the obtained molded article can be further improved.

[0066] When the total content of the repeating unit (AA) and the repeating unit (C) in the cyclic olefin copolymer (P2) is taken as 100 mol%, the content of the repeating unit (AA) in the cyclic olefin copolymer (P2) is preferably 5 mol% or more and 95 mol% or less, more preferably 30 mol% or more and 95 mol% or less, and even more preferably 50 mol% or more and 95 mol% or less. In this embodiment, the content of the repeating unit (AA) is, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0067] (Repeating unit (C) derived from cyclic olefin having an aromatic ring) The repeating unit (C) is a repeating unit derived from a cyclic olefin having an aromatic ring. Examples of the cyclic olefin having an aromatic ring include a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), a compound represented by the following formula (C-3), etc. These cyclic olefins having an aromatic ring may be used alone or in combination of two or more.

[0068] [ka]

[0069] In the formula (C-1), n ​​and q each independently represent 0, 1, or 2. n is preferably 0 or 1, and more preferably 0. q is preferably 0 or 1, and more preferably 0. R 1 ~R 17 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom; R 10 ~R 17 One of them is a bond, and R 15 is preferably a bond. R 1 ~R 17 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=1 or 2, R 10 and R 11 , R 11 and R 17 , R17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10 may be bonded to each other to form a monocycle or polycycle, the monocycle or polycycle may have a double bond, or the monocycle or polycycle may be an aromatic ring. Among the compounds represented by formula (C-1), the compound represented by formula (C-1A) below is preferred.

[0070] [ka]

[0071] In the above formula (C-1A), n is 0, 1 or 2, preferably 0 or 1, and more preferably 0.

[0072] [ka]

[0073] In the formula (C-2), n and m are each independently 0, 1 or 2, and q is 1, 2 or 3. m is preferably 0 or 1, and more preferably 1. n is preferably 0 or 1, and more preferably 0. q is preferably 1 or 2, and more preferably 1. R 18 ~R 31 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom. R 18 ~R 31are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=1, R 28 and R 29 , R 29 and R 30 , R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , R 31 and R 31 may be bonded to each other to form a monocycle or polycycle, the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0074] [ka]

[0075] In the above formula (C-3), q is 1, 2 or 3, preferably 1 or 2, and more preferably 1. R 32 ~R 39 each independently represents a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom. R 32 ~R 39 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also, when q=1, R 36 and R 37 , R 37 and R 38 , R 38 and R 39 may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R 36 and R36 , R 36 and R 37 , R 37 and R 38 , R 38 and R 39 , R 39 and R 39 may be bonded to each other to form a monocycle or polycycle, the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0076] Examples of the hydrocarbon group having 1 to 20 carbon atoms include, independently, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group. More specifically, examples of the alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an amyl group, a hexyl group, an octyl group, a decyl group, a dodecyl group, and an octadecyl group. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aromatic hydrocarbon group include an aryl group or an aralkyl group such as a phenyl group, a tolyl group, a naphthyl group, a benzyl group, and a phenylethyl group. These hydrocarbon groups may be substituted with a halogen atom other than a fluorine atom.

[0077] Among these, the cyclic olefin having an aromatic ring is preferably at least one selected from the group consisting of, for example, benzonorbornadiene, indenenorbornene, and methylphenylnorbornene.

[0078] When the total content of the repeating unit (AA) and the repeating unit (C) in the cyclic olefin copolymer (P2) is taken as 100 mol %, the content of the repeating unit (C) in the cyclic olefin copolymer (P2) is preferably 5 mol % or more and 95 mol % or less, more preferably 5 mol % or more and 70 mol % or less, and even more preferably 5 mol % or more and 50 mol % or less. In this embodiment, the contents of the repeating units (AA) and the repeating units (C) are, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0079] The copolymer type of the cyclic olefin copolymer (P2) is not particularly limited, and examples thereof include random copolymers, block copolymers, etc. In this embodiment, from the viewpoint of obtaining optical components having excellent transparency and heat resistance, the cyclic olefin copolymer (P2) is preferably a random copolymer.

[0080] The cyclic olefin copolymer (P2) can be produced by appropriately selecting the conditions according to the methods described in, for example, JP-A-60-168708, JP-A-61-120816, JP-A-61-115912, JP-A-61-115916, JP-A-61-271308, JP-A-61-272216, JP-A-62-252406, JP-A-62-252407, JP-A-2007-314806, JP-A-2010-241932, etc.

[0081] It is preferable that the cyclic olefin resin (A) does not contain a carbon-carbon double bond, but if it does, the amount is preferably 0.5 g or less per 100 g of the cyclic olefin resin (A). By substantially not containing a carbon-carbon double bond, deterioration of the resin composition can be suppressed, which is preferable. The content of the carbon-carbon double bond in the cyclic olefin resin (A) is determined by the iodine value method (titration method) according to JIS K0070.

[0082] The melt flow rate (MFR) of the cyclic olefin resin (A), measured in accordance with ASTM D1238 at 260°C under a load of 2.16 kg, is, from the viewpoint of further improving moldability, preferably 5 g / 10 min or more, more preferably 8 g / 10 min or more, even more preferably 10 g / 10 min or more, and still more preferably 20 g / 10 min or more, and the upper limit is not particularly limited, and may be, for example, 100 g / 10 min or less, or 50 g / 10 min or less.

[0083] The glass transition temperature (Tg) of the cyclic olefin resin (A) is, from the viewpoint of improving the performance balance of moldability, transparency and heat resistance, preferably 70°C or higher, more preferably 80°C or higher, even more preferably 90°C or higher, even more preferably 100°C or higher, even more preferably 110°C or higher, even more preferably 120°C or higher, even more preferably 130°C or higher, and even more preferably 140°C or higher, and from the viewpoint of improving the performance balance of moldability, transparency and heat resistance, it is preferably 250°C or lower, more preferably 200°C or lower, even more preferably 180°C or lower, even more preferably 170°C or lower, and even more preferably 160°C or lower. The glass transition temperature (Tg) of the cyclic olefin resin (A) can be measured, for example, by the method described in the Examples.

[0084] The intrinsic viscosity η [dl / g] (in decalin at 135°C) of the cyclic olefin resin (A) is, from the viewpoint of further improving the performance balance between moldability and optical properties, preferably 0.05 dl / g or more, more preferably 0.1 dl / g or more, even more preferably 0.2 dl / g or more, and even more preferably 0.3 dl / g or more, and from the same viewpoint, is preferably 5.0 dl / g or less, more preferably 4.0 dl / g or less, even more preferably 2.0 dl / g or less, and even more preferably 1.0 dl / g or less. The intrinsic viscosity η [dl / g] of the cyclic olefin resin (A) can be measured in accordance with ASTM J1601.

[0085] (Phenol-based antioxidant (B)) The recycled cyclic olefin resin composition of the present embodiment contains a phenol-based antioxidant (B). The phenol-based antioxidant (B) may be used alone or in combination of two or more kinds. By including a phenol-based antioxidant (B) in the recycled cyclic olefin resin composition, yellowing during molding of the recycled cyclic olefin resin composition can be suppressed, and a decrease in the transparency of the molded body can be suppressed.

[0086] The phenol-based antioxidant (B) is not particularly limited, and for example, a known phenol-based antioxidant can be used. However, it is preferable that the phenol-based antioxidant (B) contains at least one selected from the group consisting of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene.

[0087] (Phosphorus-based stabilizer (C)) The phosphorus-based stabilizer (C) has a 10% mass loss temperature in the air of 275°C or higher as measured by a calorimeter. The 10% mass loss temperature of the phosphorus-based stabilizer (C) is preferably 280°C or higher, more preferably 285°C or higher, and more preferably 290°C or higher. The upper limit is not particularly limited, but may be, for example, 310°C or lower, 305°C or lower, or 300°C or lower. When the 10% mass loss temperature of the phosphorus-based stabilizer (C) is equal to or higher than the lower limit, yellowing during molding of the recycled cyclic olefin resin composition can be suppressed, and a decrease in the transparency of the molded product can be suppressed. The 10% mass loss temperature of the phosphorus-based stabilizer (C) means a temperature measured by the method described in the Examples.

[0088] If the recycled cyclic olefin resin composition contains a phosphorus-based stabilizer with a 10% mass loss temperature of less than 275°C, yellowing of the recycled cyclic olefin resin composition during molding may be promoted. Therefore, the content of the phosphorus-based stabilizer having a 10% mass loss temperature of less than 275°C per 100 parts by mass of the cyclic olefin resin (A) is preferably less than 0.05 parts by mass, more preferably less than 0.03 parts by mass, even more preferably less than 0.01 parts by mass, and even more preferably 0.00 parts by mass.

[0089] In other words, the inventors have discovered that it is important to set the 10% mass loss temperature of the phosphorus-based stabilizer contained in the recycled cyclic olefin resin composition within a specific range in order to obtain molded bodies and optical components in which loss of transparency and yellowing are suppressed.

[0090] The phosphorus-based stabilizer (C) is not particularly limited as long as the 10% mass loss temperature is within the range of the present invention, but it is preferable that the phosphorus-based stabilizer (C) contains at least one type selected from the group consisting of phosphorus-based stabilizers represented by the following formula (1) and phosphorus-based stabilizers represented by the following formula (3).

[0091] [ka]

[0092] In the above formula (1), R 501 ~R 505 may be the same or different and are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R 501 ~R 505 In the above formula, specific examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an iso-propyl group, an n-butyl group, a tert-butyl group, and a nonyl group.

[0093] Examples of the phosphorus-based stabilizer represented by (1) above include triphenyl phosphite, tris(4-methylphenyl) phosphite, tris(4-tert-butylphenyl) phosphite, tris(2-methyl-4-ethylphenyl) phosphite, tris(2-methyl-4-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, tris(2,6-di-tert-butylphenyl) phosphite, tris(2,4-di-tert-butylphenyl) phosphite, The phosphite composition may include at least one selected from the group consisting of tris(2,4-di-tert-butylphenyl)phosphite, tris(nonylphenyl)phosphite, and tris(di-nonylphenyl)phosphite, and preferably includes one or two selected from the group consisting of tris(2,6-di-tert-butylphenyl)phosphite, and more preferably includes tris(2,4-di-tert-butylphenyl)phosphite.

[0094] [ka]

[0095] In the formula (3), R 700 is a hydrocarbon group having 1 to 29 carbon atoms, R 701 ~R 708 may be the same or different and are a hydrogen atom or an alkyl group having 1 to 20 carbon atoms. R 700 In the above, examples of the hydrocarbon group having 1 to 29 carbon atoms include an alkyl group having 1 to 29 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. More specifically, examples of the alkyl group include an octyl group, a hexyl group, and an octadecyl group. Examples of the cycloalkyl group include a cyclohexyl group. Examples of the aromatic hydrocarbon group include a phenyl group and a benzyl group. R 701 ~R 708In the above formula, examples of the alkyl group having 1 to 20 carbon atoms include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a tert-butyl group, and a nonyl group.

[0096] Examples of the phosphorus-based stabilizer represented by the formula (3) include 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite, 2,2'-methylenebis(4,6-dimethylphenyl)octyl phosphite, 2,2'-methylenebis(4-tert-butyl-6-methylphenyl)octyl phosphite, 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, 2,2'-methylenebis(4,6-dimethylphenyl)hexyl phosphite, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)hexyl phosphite. )hexyl phosphite, and 2,2'-methylenebis(4,6-di-tert-butylphenyl)stearyl phosphite, etc., preferably one or two selected from the group consisting of 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite and 2,2'-methylenebis(4,6-di-tert-butylphenyl)octyl phosphite, more preferably 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite.

[0097] The phosphorus-based stabilizer (C) may be used alone or in combination of two or more kinds.

[0098] (Other Ingredients) In addition to the cyclic olefin resin (A), the phenol-based antioxidant (B), and the phosphorus-based stabilizer (C), the recycled cyclic olefin resin composition of this embodiment may contain other known optional components within a range that does not impair the good physical properties of the recycled cyclic olefin resin composition. Examples of other components include resins other than the cyclic olefin resin (A), surfactants, hydrophilic agents, weather stabilizers, heat stabilizers, antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers, etc. The amount of other components to be blended is an appropriate amount.

[0099] [Method of producing recycled cyclic olefin resin composition] The recycled cyclic olefin resin composition of the present embodiment is obtained by mixing each component. The order of mixing each component is not particularly limited, and it can be mixed in any manner such as all at once or in portions. The device for mixing each component is also not particularly limited, and it can be mixed in any device capable of stirring and mixing, such as a batch type or a continuous type.

[0100] The recycled cyclic olefin resin composition of the present embodiment can also be in the form of pellets. The pellet-shaped recycled cyclic olefin resin composition can be obtained, for example, by kneading the resin in an extruder and molding the mixture into pellets by water cooling and cutting.

[0101] [Molded bodies and optical components] The molded article of the present embodiment contains the recycled cyclic olefin resin composition of the present embodiment. Since the molded article of the present embodiment contains the recycled cyclic olefin resin composition of the present embodiment, it has a good balance of heat resistance, chemical resistance, low moisture absorption, etc., and is suppressed from decreasing transparency and yellowing. In addition, since the molded article of the present embodiment contains the recycled cyclic olefin resin composition of the present embodiment, it is also preferable from the viewpoint of protecting the global environment.

[0102] From the viewpoint of further improving the performance balance between moldability and optical properties, the content of the recycled cyclic olefin resin composition of this embodiment in the molded body of this embodiment is, when the entire molded body is taken as 100 mass%, preferably 50 mass% or more, more preferably 70 mass% or more, even more preferably 80 mass% or more, even more preferably 90 mass% or more, even more preferably 95 mass% or more, even more preferably 98 mass% or more, even more preferably 99 mass% or more, and preferably 100 mass% or less.

[0103] The molded article of this embodiment can be obtained by molding the recycled cyclic olefin resin composition of this embodiment into a predetermined shape in a mold. The method of molding the recycled cyclic olefin resin composition of this embodiment to obtain a molded article is not particularly limited, and any known method can be used. Depending on the application and shape, for example, extrusion molding, injection molding, compression molding, inflation molding, blow molding, extrusion blow molding, injection blow molding, press molding, vacuum molding, powder slush molding, calendar molding, foam molding, etc. can be applied. Among these, injection molding and extrusion molding are preferred from the viewpoint of moldability and productivity, and injection molding is more preferred. Furthermore, molding conditions are appropriately selected depending on the purpose of use or molding method, and 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, more preferably 230°C to 330°C.

[0104] The molded article of the present embodiment can be used in various forms, such as a lens shape, a sphere shape, a rod shape, a plate shape, a cylinder shape, a tube shape, a fiber shape, a film shape, or a sheet shape.

[0105] In addition to the recycled cyclic olefin resin composition of this embodiment, the molded article of this embodiment may contain other known optional components within a range that does not impair the good physical properties of the molded article. Examples of other components include resins other than the cyclic olefin resin (A), surfactants, hydrophilic agents, weather stabilizers, heat stabilizers, antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, dyes, pigments, natural oils, synthetic oils, waxes, organic or inorganic fillers, etc. The amount of other components to be blended is an appropriate amount.

[0106] The optical component of this embodiment includes the molded article of this embodiment. The molded article of the present embodiment has good transparency and can therefore be suitably used as an optical component. Optical components are components used in optical devices and the like, and specifically, they can be particularly suitably used in optical components that require heat resistance and transparency, such as sensor lenses, pickup lenses, projector lenses, prisms, fθ lenses, imaging lenses, light guide plates, in-vehicle camera lenses, and camera lenses for mobile devices (mobile phones, smartphones, tablets, etc.). Examples of in-vehicle camera lenses and camera lenses for mobile devices include view camera lenses, sensing camera lenses, lenses for light convergence in head-up displays, lenses for light diffusion in head-up displays, and lenses in various optical devices such as cameras for personal computers, cameras for mobile phones, cameras for smartphones, cameras for tablet terminals, cameras for mobile devices, digital cameras, and cameras for medical devices. Other uses include automobile interior panels, automobile lamp lenses, automobile inner lenses, automobile lens protective covers, automobile light guides, and the like.

[0107] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various configurations other than those described above can also be adopted. Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope of the present invention that can achieve the object of the present invention are included in the present invention. EXAMPLES

[0108] Hereinafter, the present embodiment will be described in detail with reference to examples, etc. However, the present embodiment is not limited to the description of these examples.

[0109] First, the measurement and evaluation methods performed in the examples and comparative examples will be described.

[0110] [Measurement and evaluation methods] (1) Melt flow rate (MFR) of cyclic olefin resin (A) The MFR of the cyclic olefin resin (A) was measured at 260° C. and a load of 2.16 kg in accordance with ASTM D1238.

[0111] (2) Glass transition temperature (Tg) of cyclic olefin resin (A) The glass transition temperature (Tg) of the cyclic olefin resin (A) was measured under a nitrogen atmosphere using a Discovery DSC-2500 manufactured by TA Instruments. The cyclic olefin resin (A) was heated from room temperature (23°C) to 200°C at a heating rate of 10°C / min, and then held for 5 minutes. The temperature was then lowered to -20°C at a heating rate of 10°C / min, and then held for 5 minutes. The glass transition temperature (Tg) of the cyclic olefin resin (A) was obtained from the endothermic curve when the temperature was raised to 200°C at a heating rate of 10°C / min.

[0112] (3) Content of repeating units (b) derived from cyclic olefin monomers in the cyclic olefin resin (A) Using a nuclear magnetic resonance spectrometer (Bruker Biospin, ADVANCEIII cryo-500), the cyclic olefin resin (A) 1 H-NMR or 13 C-NMR was measured. The content of the repeating unit (b) derived from the cyclic olefin monomer in the cyclic olefin resin (A) was calculated from the integral ratio of the obtained spectrum.

[0113] (4) 10% mass loss temperature of phosphorus-based stabilizer (C) A TG-DTA device (TG / DTA7300, Hitachi High-Tech Science Corporation) was used as a calorimeter, and 5 mg of phosphorus-based stabilizer (C) was weighed into a sample pan and heated from 30°C to 500°C at a heating rate of 10°C / min in an air atmosphere to measure the mass loss of the sample. The temperature at which the weight decreased by 10% from the thermogravimetric curve was determined as the 10% mass loss temperature of the phosphorus-based stabilizer (C). Here, the atmospheric atmosphere means an atmosphere using atmospheric air containing 21 mass % oxygen and 78 mass % nitrogen, under atmospheric pressure.

[0114] (5) Light transmittance of molded body at a wavelength of 450 nm Using an injection molding machine (SE30DUZ, manufactured by Sumitomo Heavy Industries, Ltd.), the pellet-shaped recycled cyclic olefin resin composition was injection molded under conditions of a cylinder temperature of 270°C and a mold temperature of 126°C to produce a test piece with an optical surface measuring 65 mm in length, 35 mm in width, and 3 mm in thickness. The light transmittance at a wavelength of 450 nm of the obtained test pieces was measured using a UV-Vis-NIR spectrophotometer UH4150 (manufactured by Hitachi High-Tech Science Corp.) The transparency was evaluated as follows: when the light transmittance at a wavelength of 450 nm was 87.0% or more, it was rated as A (good), and when it was less than 87.0%, it was rated as B (poor).

[0115] (6) Evaluation of yellowing The test pieces obtained in (5) were visually observed. The evaluation of yellowing was rated as A (good) when no yellowing was observed on the test pieces, and B (bad) when yellowing was observed on the test pieces.

[0116] [Example 1] <Synthesis of Cyclic Olefin Resin (A)> (Catalyst Preparation) Ethyl aluminum sesquichloride (Al(C2H5) 1.5 Cl 1.5 ) was diluted with cyclohexane to prepare an organoaluminum compound catalyst solution.

[0117] (polymerization) In a stirred polymerization vessel, ethylene and tetracyclo[4.4.0.1 are polymerized using the organoaluminum compound catalyst solution prepared by the above method as a catalyst. 2,5 .1 7,10 A copolymerization reaction was carried out with ethylene and 3-dodecene (hereinafter also referred to as "TD") to obtain a copolymer solution. Here, ethylene was fed into the polymerization vessel together with hydrogen gas.

[0118] (Decalcification) Water and an aqueous solution of sodium hydroxide were added to the obtained copolymer solution to terminate the polymerization reaction and to remove (demineralize) the catalyst residues present in the copolymer solution. Also, the catalyst residues present in the copolymer were removed (demineralized) from the copolymer solution.

[0119] (Desolvation) The deashed copolymer solution is mixed with a stabilizer and heated to 180°C to remove the solvent and unreacted monomers, resulting in the cyclic olefin resin (A) consisting of molten ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 A random copolymer with ]-3-dodecene was obtained.

[0120] (Pelletization) The obtained molten cyclic olefin resin (A) was charged into a vented twin-screw kneading extruder through a resin charging section of the extruder, and then pelletized with an underwater pelletizer attached to the outlet of the extruder. The pellets were dried with hot air at 100° C. for 4 hours to obtain pelletized cyclic olefin resin (A). The pellet-shaped cyclic olefin resin (A) thus obtained had a glass transition temperature (Tg) of 151° C. and an MFR of 28 g / 10 min (260° C., 2.16 kg load). The content of TD-derived repeating units (corresponding to the repeating units (b) derived from the cyclic olefin monomer) in the cyclic olefin resin (A) was 37 mol%.

[0121] <Preparation of Recycled Cyclic Olefin Resin (A1)> The sprue and runner of the pellet-shaped cyclic olefin resin (A) (injection molded product) obtained in the above <Synthesis of cyclic olefin resin (A)> were crushed with a crusher to produce 3 mm square recovered cyclic olefin resin (A1). The recovered cyclic olefin resin (A1) had a glass transition temperature (Tg) of 151°C and an MFR of 30 g / 10 min (260°C, 2.16 kg load).

[0122] <Preparation of Recycled Cyclic Olefin Resin Composition> 0.10 parts by mass of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] (ADEKA Corporation, Adeka STAB (registered trademark) AO-60) as a phenol-based antioxidant (B1) and 0.05 parts by mass of tris(2,4-di-tert-butylphenyl)phosphite (ADEKA Corporation, Adeka STAB 2112) as a phosphorus-based stabilizer (C1) were added to 100 parts by mass of the recovered cyclic olefin resin (A1) and mixed. The mixture was charged into the resin charging section of a twin-screw extruder (manufactured by Japan Steel Works, Ltd., TEX44) with unidirectional rotation, screw diameter: 44 mm, and L / D = 30, and melt-kneaded under conditions of screw rotation speed: 150 rpm, motor power: 30 kW, and the extruded strands were cut with a pelletizer to obtain a pellet-shaped recycled cyclic olefin resin composition containing the recovered cyclic olefin resin (A1), a phenol-based antioxidant (B1), and a phosphorus-based stabilizer (C1).

[0123] [Example 2] In the above <Preparation of recycled cyclic olefin resin composition>, a pellet-shaped recycled cyclic olefin resin composition was obtained in the same manner as in Example 1, except that 2,2'-methylenebis(4,6-di-tert-butylphenyl)-2-ethylhexyl phosphite (ADEKA Corporation, Adeka STAB HP-10) was used as the phosphorus-based stabilizer (C2) instead of the phosphorus-based stabilizer (C1).

[0124] [Comparative Example 1] In the above <Preparation of recycled cyclic olefin resin composition>, a pellet-shaped recycled cyclic olefin resin composition was obtained in the same manner as in Example 1, except that tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene-diphosphite (Hostanox (registered trademark) P-EPQ, manufactured by Clariant Chemicals) was used as the phosphorus-based stabilizer (C3) instead of the phosphorus-based stabilizer (C1).

[0125] [Comparative Example 2] In the above <Preparation of recycled cyclic olefin resin composition>, a pellet-shaped recycled cyclic olefin resin composition was obtained in the same manner as in Example 1, except that 3,9-bis(octadecyloxy)-2,4,8,10-tetraoxa-3,9-diphosphaspiro[5,5]undecane (ADEKA Corporation, Adeka STAB PEP-8) was used as the phosphorus-based stabilizer (C4) instead of the phosphorus-based stabilizer (C1).

[0126] [Comparative Example 3] A pellet-shaped recycled cyclic olefin resin composition was obtained in the same manner as in Example 1, except that in the above <Preparation of recycled cyclic olefin resin composition>, no phosphorus-based stabilizer was used.

[0127] Table 1 shows the results of measuring the 10% mass loss temperature for each of the phosphorus-based stabilizers (C1) to (C4) used in the examples and comparative examples. The evaluation of transparency and yellowing of the molded articles containing the recycled cyclic olefin resin compositions obtained in Examples 1 and 2 and Comparative Examples 1 to 3 are shown in Table 2.

[0128] [Table 1]

[0129] [Table 2]

[0130] From Table 2, it can be seen that the molded articles containing the recycled cyclic olefin resin compositions of the examples were evaluated as being good in both transparency and yellowing. In other words, it can be seen that the recycled cyclic olefin resin composition of the present embodiment can provide molded articles and optical parts in which the decrease in transparency and yellowing are suppressed.

Claims

1. A recycled cyclic olefin resin composition comprising a cyclic olefin resin (A), a phenolic antioxidant (B), and a phosphorus stabilizer (C), wherein the cyclic olefin resin (A) contains a recovered cyclic olefin resin (A1), and the phosphorus stabilizer (C) is a recycled cyclic olefin resin composition having a 10% mass loss temperature in the atmosphere measured by a calorimeter of 275 °C or higher.

2. The recycled cyclic olefin resin composition according to claim 1, wherein the content of the phosphorus stabilizer (C) is 0.01 part by mass or more and 1.00 part by mass or less with respect to 100 parts by mass of the cyclic olefin resin (A).

3. The recycled cyclic olefin resin composition according to claim 1 or 2, wherein the content of the phenolic antioxidant (B) is 0.01 part by mass or more and 0.50 part by mass or less with respect to 100 parts by mass of the cyclic olefin resin (A).

4. The recycled cyclic olefin resin composition according to claim 1 or 2, wherein the mass ratio (C / B) of the content of the phosphorus stabilizer (C) to the content of the phenolic antioxidant (B) is 0.1 or more and 2.5 or less.

5. The recycled cyclic olefin resin composition according to claim 1 or 2, wherein the phosphorus stabilizer (C) contains at least one selected from the group consisting of a phosphorus stabilizer represented by the following formula (1) and a phosphorus stabilizer represented by the following formula (3). 【Chemical 1】 (In the formula (1), R ５０１ ~R ５０５ may be the same as or different from each other, and is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.) 【Chemical 2】 (In the formula (3), R ７００ is a hydrocarbon group having 1 to 29 carbon atoms, and R ７０１ to R ７０８ may be the same as or different from each other, and is a hydrogen atom or an alkyl group having 1 to 20 carbon atoms.)

6. The recycled cyclic olefin resin composition according to claim 1 or 2, wherein the phenolic antioxidant (B) contains at least one selected from the group consisting of pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, 3,9-bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, and 1,3,5-tris(3,5-di-tert-butyl-4-hydroxyphenylmethyl)-2,4,6-trimethylbenzene.

7. The cyclic olefin resin (A) is a repeating unit (a) derived from at least one olefin represented by the following formula (I), The repeating unit (b) derived from at least one cyclic olefin monomer selected from the group consisting of the repeating unit (AA) represented by the following formula (II), the repeating unit (AB) represented by the following formula (III), and the repeating unit (AC) represented by the following formula (IV), The recycled cyclic olefin-based resin composition according to claim 1 or 2, comprising a cyclic olefin-based copolymer (P1) having [Chemical Formula 3] (In the formula (I), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.) 【Chemical Formula 4】 (In the formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, R ６１ ~R ７８ as well as R ａ１ and R ｂ１ may be the same as or different from each other, and each is a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, or an aromatic hydrocarbon group having 6 to 20 carbon atoms, and R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring.) 【Chemical Formula 5】 (In the formula (III), x and d are integers of 0 or 1 or more, y and z are 0, 1 or 2, and R ８１ ~R ９９ may be the same as or different from each other, and is a hydrogen atom, a halogen atom, an aliphatic hydrocarbon group which is an alkyl group having 1 to 20 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms, an aromatic hydrocarbon group having 6 to 20 carbon atoms or an alkoxy group, and R ８９ and R ９０ The carbon atom to which is bonded, the carbon atom to which R ９３ is bonded or the carbon atom to which R ９１ is bonded may be bonded directly or via an alkylene group having 1 to 3 carbon atoms, and when y = z = 0, R ９５ and R ９２ or R ９５ and R ９９ may be bonded to each other to form a monocyclic or polycyclic aromatic ring.) 【Chemical Formula 6】 (In the formula (IV), R １００ and R １０１ may be the same as or different from each other, and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is an integer of 1 ≦ f ≦ 18.)

8. The cyclic olefin-based resin (A) includes a cyclic olefin-based copolymer (P2) having a repeating unit (AA) represented by the following formula (II) and a repeating unit (C) derived from a cyclic olefin having an aromatic ring, The repeating unit (AA) does not contain an aromatic ring, The cyclic olefin having an aromatic ring includes at least one selected from the group consisting of a compound represented by the following formula (C-1), a compound represented by the following formula (C-2), and a compound represented by the following formula (C-3). The recycled cyclic olefin-based resin composition according to claim 1 or 2. [Chemical Formula 7] (In the above formula (II), u is 0 or 1, v is 0 or a positive integer, w is 0 or 1, and R ６１ ~R ７８ as well as R ａ１ and R ｂ１ may be the same as or different from each other, and are a hydrogen atom, a halogen atom, an alkyl group having 1 to 20 carbon atoms, a halogenated alkyl group having 1 to 20 carbon atoms, or a cycloalkyl group having 3 to 15 carbon atoms. R ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring.) 【Chemical Formula 8】 (In the formula (C-1), n and q are each independently 0, 1, or 2, and R １ ~R １７ are each independently a halogen atom excluding a hydrogen atom or a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom. One of R １０ ~R １７ is a bond. When q = 0, R １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １０ may be bonded to each other to form a monocyclic or polycyclic ring. When q = 1 or 2, R １０ and R １１ , R １１ and R １７ , R １７ and R １７ , R １７ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １６ , R １６ and R １６ , R １６ and R １０ may be bonded to each other to form a monocyclic or polycyclic ring, the monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring.) 【Chemical Formula 9】 (In the formula (C-2), n and m are each independently 0, 1, or 2, q is 1, 2, or 3, and R １８ ~R ３１ are each independently a hydrogen atom, a halogen atom excluding a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom excluding a fluorine atom. When q = 1, R ２８ and R ２９ , R ２９ and R ３０ , R ３０ and R ３１ may be bonded to each other to form a monocyclic or polycyclic ring. When q = 2 or 3, R ２８ and R ２８ , R ２８ and R ２９ , R ２９ and R ３０ , R ３０ and R ３１ , R ３１ and R ３１ may be bonded to each other to form a monocyclic or polycyclic ring. The monocyclic or polycyclic ring may have a double bond, and the monocyclic or polycyclic ring may be an aromatic ring.) 【Chemical Formula 10】 (In the formula (C-3), q is 1, 2 or 3, and R ３２ ~R ３９ are each independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group having 1 to 20 carbon atoms which may be substituted with a halogen atom other than a fluorine atom, and when q=1, R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ may be bonded to each other to form a monocyclic or polycyclic ring, and when q=2 or 3, R ３６ and R ３６ , R ３６ and R ３７ , R ３７ and R ３８ , R ３８ and R ３９ , R ３９ and R ３９ may be bonded to each other to form a monocycle or a polycycle, the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring.

9. The recycled cyclic olefin-based resin composition according to claim 1 or 2, which is in pellet form.

10. A molded article comprising the recycled cyclic olefin-based resin composition according to claim 1 or 2.

11. An optical component comprising the molded article according to claim 10.

Images