Recycled cyclic olefin-based resin composition, molded body, and optical component

Abstract

To provide: a recycled cyclic olefin-based resin composition capable of providing a molded body and an optical component in which deterioration of transparency is suppressed; and a molded body and an optical component in which deterioration of transparency is suppressed.SOLUTION: Provided is a recycled cyclic olefin-based resin composition, comprising: a recycled cyclic olefin-based resin (A); and a phenol-based antioxidant (B) having, in the molecule, a structure represented by the general formula (X).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] Among polyolefin resins, cyclic olefin resins are particularly excellent in transparency. Cyclic olefin resins have low water absorption and moisture permeability, and since they do not have polar groups, they are unlikely to adsorb chemicals having polar groups. Taking advantage of these properties, it has been disclosed that cyclic olefin resins are used for, 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).

[0003] 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). [Prior art documents] [Patent documents]

[0004] [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]

[0005] However, when waste materials from molded articles containing cyclic olefin resins are reused, the quality of the resulting molded articles and optical components, such as their transparency, may be reduced, and they may not be usable for their intended purposes.

[0006] The present invention has been made in consideration of the above circumstances, and provides a recycled cyclic olefin resin composition that can produce molded articles and optical components in which the decrease in transparency is suppressed, as well as molded articles and optical components in which the decrease in transparency is suppressed. [Means for solving the problem]

[0007] The present inventors have conducted extensive research to solve the above problems, and as a result have found that a combination of a recycled cyclic olefin resin and a phenolic antioxidant having a specific structure in its molecule can suppress a decrease in transparency of molded articles and optical parts made using a recycled cyclic olefin resin composition, thereby completing the present invention. According to the present invention, there are provided the following recycled cyclic olefin resin composition, molded article, and optical component.

[0008] [1] A recovered cyclic olefin resin (A); A phenol-based antioxidant (B) having a structure represented by the following general formula (X) in its molecule; A recycled cyclic olefin resin composition comprising: [ka] (In general formula (X), n is 1 or more, R1 represents an alkyl group having 1 to 4 carbon atoms, R2 and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and tBu represents a tert-butyl group.) [2] The recycled cyclic olefin resin composition according to [1], wherein n in the general formula (X) is 1 or 2. [3] The recycled cyclic olefin resin composition according to [1] or [2], wherein R1 in the general formula (X) is a tert-butyl group. [4] The recycled cyclic olefin resin composition according to any one of [1] to [3], wherein the phenol-based antioxidant (B) has 2 to 4 structures represented by the general formula (X) in the molecule. [5] The recycled cyclic olefin resin composition according to any one of [1] to [4], wherein the molecular weight of the phenol-based antioxidant (B) is 600 or more and 1,300 or less. [6] The recycled cyclic olefin resin composition according to any one of [1] to [5], wherein the phenol-based antioxidant (B) contains a compound having a structure containing one selected from the group consisting of a triazine skeleton, a pentaerythritol tetrakis skeleton, and a tetraoxaspiro[5.5]undecane skeleton, and a structure represented by general formula (X). [7] The recycled cyclic olefin resin composition according to any one of [1] to [6], wherein the content of the phenol-based antioxidant (B) is 0.05 parts by mass or more and 0.4 parts by mass or less when the content of the recycled cyclic olefin resin (A) is 100 parts by mass. [8] The recovered cyclic olefin resin (A) is The recycled cyclic olefin resin composition according to any one of [1] to [7], comprising 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). [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 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. [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. [9] The recovered cyclic olefin resin (A) contains a cyclic olefin copolymer (P2) having a repeating unit (AA) represented by the following formula (II) and a structural 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], 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 , R15 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 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 each independently represent 0, 1, or 2, q represents 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 31may 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 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 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.

[10] The recycled cyclic olefin resin composition according to any one of [1] to [9], which is in the form of pellets.

[11] A molded article comprising the recycled cyclic olefin resin composition according to any one of [1] to

[10] .

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

[11] . Effect of the Invention

[0009] According to the present invention, it is possible to provide a recycled cyclic olefin resin composition capable of producing molded articles and optical components in which the decrease in transparency is suppressed, as well as molded articles and optical components in which the decrease in transparency is suppressed. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0010] Hereinafter, the present invention will be described based on the embodiments. In the present embodiments, "A to B" indicating a numerical range means A or more and B or less unless otherwise specified.

[0011] [Recycled cyclic olefin resin composition] The recycled cyclic olefin resin composition of the present embodiment is a recycled cyclic olefin resin composition comprising a recycled cyclic olefin resin (A) and a phenol-based antioxidant (B) having in its molecule a structure represented by the following general formula (X):

[0012] [ka]

[0013] In general formula (X), n is 1 or more, R1 represents an alkyl group having 1 to 4 carbon atoms, R2 and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and tBu represents a tert-butyl group.

[0014] In this specification, the cyclic olefin resin (A) recovered from used molded bodies, products, and waste materials according to known methods is referred to as recovered cyclic olefin resin (A), and the cyclic olefin resin composition that has been subjected to a regeneration process is referred to as a recycled cyclic olefin resin composition. The recycled cyclic olefin resin composition according to the present invention may also contain a virgin cyclic olefin resin (A).

[0015] (Cyclic olefin resin (A)) In this specification, the recovered cyclic olefin resin (A) and the unused cyclic olefin resin (A) are collectively referred to as "cyclic olefin resin (A)". The cyclic olefin resin (A) according to the present embodiment may be used alone or in combination of two or more kinds. Examples of the recovered cyclic olefin resin (A) that can be used include injection-molded products such as optical components described below, sprues and runners generated during molding of injection-molded products, waste materials generated in molded products after extrusion molding, and waste materials generated after cutting extrusion-molded products into desired shapes. These molded bodies, sprues, runners, waste materials, etc. may be used as they are, or may be crushed to an appropriate size before use. When crushing, the diameter after crushing is preferably 20 mm or less, more preferably 15 mm or less, and even more preferably 10 mm or less. If the diameter after crushing is within this range, it is preferable in terms of ease of melt kneading. A crusher or the like can be used for crushing.

[0016] 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).

[0017] [ka]

[0018] In the above formula (I), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0019] [ka]

[0020] In the above 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 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.

[0021] [ka]

[0022] In the above formula (III), 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 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.

[0023] [ka]

[0024] In the above 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.

[0025] 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.

[0026] [ka]

[0027] In the above 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 above 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 above 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 from 5 mol% to 95 mol%, more preferably from 20 mol% to 90 mol%, even more preferably from 40 mol% to 85 mol%, even more preferably from 50 mol% to 80 mol%, and even more preferably from 60 mol% to 70 mol%. The proportion of repeating units (a) derived from olefins is as follows: 13 It can be measured by C-NMR.

[0028] 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 above formula (II), formula (III) or formula (IV). Specifically, the cyclic olefin monomers represented by the formulas (IIa), (IIIa) and (IVa) corresponding to the above formulas (II), (III) and (IV), respectively, are used.

[0029] [ka]

[0030] In the above 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.

[0031] [ka]

[0032] In the above 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 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.

[0033] [ka]

[0034] In the above 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.

[0035] By using the olefin monomer represented by the above-mentioned formula (Ia) or the cyclic olefin monomer represented by the formula (IIa), (IIIa) or (IVa) as the copolymerization component, the solubility of the cyclic olefin resin (A) in a solvent is further improved, resulting in good moldability and improved product yield.

[0036] 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.

[0037] 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.

[0038] 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).

[0039] As the cyclic olefin monomer represented by the above 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 7,10It 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.

[0040] 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 cyclic olefin monomers 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, even more preferably 20 mol% or more and 50 mol% or less, and even more preferably 30 mol% or more and 40 mol% or less. In this embodiment, the content 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.

[0041] 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).

[0042] 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 7,10More 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.

[0043] The cyclic olefin copolymer (P1) may be used alone or in combination of two or more kinds.

[0044] 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.

[0045] 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 structural 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).

[0046] [ka]

[0047] In the above 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 Ra1 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.

[0048] [ka]

[0049] In the above formula (C-1), n ​​and q are each independently 0, 1 or 2; 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 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 R10 may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, or the monocycle or polycycle may be an aromatic ring.

[0050] [ka]

[0051] In the above 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.

[0052] [ka]

[0053] In the above 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, R36 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 polycycle, the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0054] The cyclic olefin copolymer (P2) contains the repeating unit (AA) represented by the above formula (II) and the above structural unit (C) derived from a cyclic olefin having an aromatic ring, and thereby can improve moist heat resistance while maintaining good transparency.

[0055] (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.

[0056] When the total content of the repeating unit (AA) and the structural 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.

[0057] (Structural Unit (C) Derived from Cyclic Olefin Having an Aromatic Ring) The structural unit (C) is a structural 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.

[0058] [ka]

[0059] In the above 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 , R15 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, and the monocycle or polycycle may have a double bond, or the monocycle or polycycle may be an aromatic ring. Among the compounds represented by the above formula (C-1), the compound represented by the following formula (C-1A) is preferred.

[0060] [ka]

[0061] In the above formula (C-1A), n is 0, 1 or 2, preferably 0 or 1, and more preferably 0. R 1 ~R 14 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 1 ~R 14 are each independently preferably a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and more preferably a hydrogen atom. Also R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R13 and R 14 may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, or the monocycle or polycycle may be an aromatic ring.

[0062] [ka]

[0063] In the above 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 31 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 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.

[0064] [ka]

[0065] 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 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 polycycle, the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0066] 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.

[0067] 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.

[0068] When the total content of the repeating unit (AA) and the structural unit (C) in the cyclic olefin copolymer (P2) is taken as 100 mol%, the content of the structural 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 unit (AA) and the structural unit (C) are, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0069] 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.

[0070] 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.

[0071] The lower limit of 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 viewpoints of the processability and ease of production of the cyclic olefin resin (A), 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. The upper limit of the MFR of the cyclic olefin resin (A) is, for example, 100 g / 10 min or less.

[0072] 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.

[0073] 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 same viewpoint, is preferably 250°C or lower, more preferably 200°C or lower, even more preferably 180°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.

[0074] 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.

[0075] From the viewpoint of further improving the performance balance between moldability and transparency, the content of the cyclic olefin resin (A) of this embodiment in the recycled cyclic olefin resin composition of this embodiment is, when the entire recycled cyclic olefin resin composition 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. In addition, the content of recovered cyclic olefin resin (A) in the cyclic olefin resin (A) is preferably 30 mass% or more, more preferably 50 mass% or more, even 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, and preferably 100 mass% or less, when the entire recycled cyclic olefin resin composition is 100 mass%.

[0076] (Other Ingredients) In addition to the recovered cyclic olefin resin (A) and the unused cyclic olefin resin (A), 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 of this embodiment. Examples of other components include antioxidants, resins other than the cyclic olefin resin (A), 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 blending ratio of other components is an appropriate amount.

[0077] (Phenol-based antioxidant (B)) The recycled cyclic olefin resin composition of the present embodiment contains a phenol-based antioxidant (B) having a structure represented by the following general formula (X) in the molecule, which can suppress yellowing of the cyclic olefin resin composition when it is repelletized.

[0078] [ka]

[0079] In the general formula (X), n is 1 or more, and preferably 1 or 2, from the viewpoint of further suppressing yellowing when the cyclic olefin resin composition is repelletized.

[0080] In addition, from the viewpoint of further suppressing yellowing when the cyclic olefin resin composition is re-pelletized, R1 in the general formula (X) is an alkyl group having 1 to 4 carbon atoms, preferably a methyl group or a tert-butyl group, more preferably a tert-butyl group. When R1 is a tert-butyl group, both sides of the OH group in the general formula (X) become tert-butyl groups, and the steric hindrance of the OH group becomes large, and the stability of the O radical becomes high, so that yellowing when the cyclic olefin resin composition is re-pelletized can be further suppressed. Furthermore, R2 and R3 each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, preferably an alkyl group having 1 to 3 carbon atoms, more preferably a methyl group, or a hydrogen atom, further preferably a hydrogen atom, and tBu represents a tert-butyl group.

[0081] From the viewpoint of further suppressing yellowing when the cyclic olefin resin composition is re-pelletized, the phenol-based antioxidant (B) preferably has 2 to 4 structures represented by general formula (X) in the molecule, and more preferably has 3 structures represented by general formula (X).

[0082] The molecular weight of the phenol-based antioxidant (B) is preferably 600 or more, more preferably 650 or more, and even more preferably 700 or more, from the viewpoint of more stable retention when the cyclic olefin resin composition is re-pelletized, and is preferably 1300 or less, more preferably 1250 or less, and even more preferably 1200 or less, from the viewpoint of good dispersion in the cyclic olefin resin composition. The melting point of the phenolic antioxidant (B) is preferably 90° C. or higher, more preferably 100° C. or higher, and is preferably 250° C. or lower, more preferably 240° C. or lower, and further preferably 230° C. or lower.

[0083] In addition, the phenol-based antioxidant (B) may be, for example, a compound having a structure containing one selected from the group consisting of a triazine skeleton, a pentaerythritol tetrakis skeleton, and a tetraoxaspiro[5.5]undecane skeleton, and a structure represented by general formula (X). From the viewpoint of further suppressing yellowing when the cyclic olefin resin composition is repelletized, the phenol-based antioxidant (B) is preferably a compound in which a structure represented by general formula (X) is added to a triazine skeleton. Commercially available products of such phenol-based antioxidants (B) include AO-20 (manufactured by ADEKA Corporation), AO-60 (manufactured by ADEKA Corporation), and AO-80 (manufactured by ADEKA Corporation).

[0084] The content of the phenolic antioxidant (B) is preferably 0.05 parts by mass or more, more preferably 0.08 parts by mass or more, and preferably 0.40 parts by mass or less, 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, relative to 100 parts by mass of the recovered cyclic olefin resin (A). By having the content of the phenolic antioxidant (B) within the above range, the effect of preventing oxidative deterioration can be further improved, yellowing when the cyclic olefin resin composition is repelletized can be further suppressed, and deterioration in the quality of the obtained recycled cyclic olefin resin composition, such as mechanical strength, can be further suppressed.

[0085] (Resins other than cyclic olefin resin (A)) Examples of resins other than the cyclic olefin resin (A) include polyolefins; halogen-containing vinyl polymers such as polyvinyl chloride and chlorinated rubber; polymers derived from α,β-unsaturated acids and their derivatives, such as polyacrylate, polymethacrylate, and acrylonitrile-butadiene-styrene copolymer; polyvinyl alcohol; polyvinyl acetate; polymers derived from epoxides, such as polyethylene oxide; polyacetals; polyphenylene oxide; polycarbonates; polysulfones; polyurethanes; urea resins; polyamides; copolyamides; polyesters such as polyethylene terephthalate; polymers having a crosslinked structure derived from aldehydes and phenols, urea, or melamine, such as phenol-formaldehyde resins; alkyd resins; unsaturated polyester resins and halogen-containing modified resins derived from copolyesters of saturated and unsaturated dicarboxylic acids and polyhydric alcohols, and obtained by using a vinyl compound as a crosslinking agent; natural polymers such as cellulose and rubber; and soft polymers such as α-olefin copolymers and α-olefin-diene copolymers.

[0086] The cyclic olefin resin (A) and other components can be mixed by a known method, such as by simultaneously mixing the components. The other components may be mixed with unused cyclic olefin resin (A) and then mixed with the recovered cyclic olefin resin (A).

[0087] [Method of producing recycled cyclic olefin resin composition] The method for producing a recycled cyclic olefin resin composition according to this embodiment can include, for example, a step (1) of mixing a recycled cyclic olefin resin (A) with at least one phenol-based antioxidant (B). The step (1) of mixing the recovered cyclic olefin resin (A) with the phenolic antioxidant (B) can be carried out using, for example, a blender such as a Henschel mixer. Furthermore, the method may include a step of pulverizing the recovered cyclic olefin resin (A) before the step (1), as described above.

[0088] The method for producing the recycled cyclic olefin resin composition according to the present embodiment can include a step (2) of kneading a mixture of the recycled cyclic olefin resin (A) and the phenol-based antioxidant (B) in an extruder to form pellets. That is, the recycled cyclic olefin resin composition according to the present embodiment can be formed into pellets. In step (2), the recovered cyclic olefin resin (A) and the phenolic antioxidant (B) are fed into an extruder, kneaded, and extruded into pellets. The extruder is not particularly limited, and a single-screw extruder or a twin-screw extruder can be used.

[0089] In the above step (2), the screw rotation speed during kneading in the extruder is preferably 20 rpm or more, more preferably 30 rpm or more, and preferably 420 rpm or less, more preferably 400 rpm or less, even more preferably 350 rpm or less, even more preferably 300 rpm or less, even more preferably 250 rpm or less, even more preferably 200 rpm or less, and even more preferably 180 rpm or less. When the screw rotation speed during kneading in the extruder is within the above range, it is possible to better control the shear force applied to the recycled cyclic olefin resin composition during kneading while improving the meltability of the resin, and the occurrence of defects and yellowing in appearance can be further suppressed.

[0090] In the above step (2), when the screw rotation speed during kneading in the extruder is N [rpm] and the supply rate of the recycled cyclic olefin resin composition is Q [kg / hr], the Q / N during the kneading treatment is preferably 0.05 or more, more preferably 0.10 or more, even more preferably 0.12 or more, and preferably 1.0 or less, more preferably 0.90 or less, even more preferably 0.85 or less, even more preferably 0.60 or less. When the Q / N during the kneading treatment is within the above range, it is possible to better control the shear force on the recycled cyclic olefin resin composition during kneading, and the occurrence of defects and yellowing in appearance can be further suppressed.

[0091] The melt-kneaded recycled cyclic olefin resin composition can be extruded in the form of strands, which can then be processed into pellets by water cooling and cutting. Furthermore, after the pellets are dried, they are put into an injection molding machine, and a molded body can be obtained, for example, in a mold heated to 125 to 145° C. After the molten resin is injected into the mold, it is preferable to apply an appropriate dwell pressure to transfer the shape of the mold, and to hold the mold closed for a certain period of time to solidify the filled resin.

[0092] In the manufacturing method of the recycled cyclic olefin resin composition according to this embodiment, a polymer filter is attached to the outlet of the extruder and the molten recycled cyclic olefin resin composition is passed through it, thereby removing any foreign matter that has become mixed into the resin. The opening size of the filter is preferably 30 μm or less, more preferably 25 μm or less, and further preferably 20 μm or less.

[0093] [Molded bodies and optical components] The molded article according to this embodiment is a molded article containing the recycled cyclic olefin resin composition according to this embodiment described above. Since the molded article of this embodiment contains the recycled cyclic olefin resin composition of this embodiment, it has a good balance of heat resistance, chemical resistance, low moisture absorption, etc., and the decrease in transparency is suppressed.

[0094] From the viewpoint of further improving the performance balance between moldability and optical properties, the content of the cyclic olefin resin (A) according to this embodiment in the molded article according to this embodiment is, when the entire molded article 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.

[0095] The molded article according to the present embodiment can be obtained by molding the recycled cyclic olefin resin composition according to the present embodiment into a predetermined shape in a mold. The method for molding the recycled cyclic olefin resin composition according to the present embodiment to obtain a molded article is not particularly limited, and a 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.

[0096] The molded article according to this 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.

[0097] 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 of this embodiment. Examples of other components include antioxidants, resins other than the cyclic olefin resin (A), 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 blending ratio of other components is an appropriate amount.

[0098] The molded article according to this embodiment can be suitably used as an optical component. Optical components are components used in optical devices and the like, and specifically, the optical components can be particularly suitably used for optical components that require heat resistance, 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.

[0099] 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

[0100] 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.

[0101] First, the measurement and evaluation methods performed in the examples and comparative examples will be described.

[0102] [Measurement and evaluation methods] (1) Melt flow rate (MFR) of cyclic olefin resin (A) The MFR of the recycled cyclic olefin resin composition was measured at 260°C and a load of 2.16 kg in accordance with ASTM D1238.

[0103] (2) Glass transition temperature (Tg) of cyclic olefin resin (A) The glass transition temperature (Tg) of the recycled cyclic olefin resin composition was measured under a nitrogen atmosphere using a Discovery DSC-2500 manufactured by TA Instruments. The recycled cyclic olefin resin composition 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 recycled cyclic olefin resin composition was then determined from the endothermic curve when the temperature was raised to 200°C at a heating rate of 10°C / min.

[0104] (3) The content of repeating units (b) derived from cyclic olefin monomers in the cyclic olefin resin (A) is 1 H-NMR or 13 Measurements were performed by C-NMR.

[0105] <Synthesis of Cyclic Olefin Resin (A)> (Catalyst Preparation) Ethyl aluminum sesquichloride (C2H5)3Al2Cl3 was diluted with cyclohexane to prepare an organoaluminum compound catalyst solution.

[0106] (polymerization) In a stirred polymerization vessel, ethylene and tetracyclo[4.4.0.1 were polymerized using the organoaluminum compound catalyst solution prepared by the above method. 2,5 .1 7,10A copolymerization reaction of ethylene with 3-dodecene (hereinafter also referred to as "TD") was carried out to obtain a cyclic olefin copolymer solution. Here, ethylene was fed into the polymerization vessel together with hydrogen gas.

[0107] (Decalcification) Water and an aqueous solution of sodium hydroxide were added to the obtained cyclic olefin copolymer solution to terminate the polymerization reaction and remove (decalcify) the catalyst residue present in the cyclic olefin copolymer solution. Also, the catalyst residue present in the cyclic olefin copolymer was removed (decalcify) from the cyclic olefin copolymer solution.

[0108] (Desolvation) The deashed cyclic olefin copolymer solution was mixed with a stabilizer and heated to 180°C to remove the solvent and unreacted monomers, resulting in the molten ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 A random copolymer with 1-(2-dodecene) (cyclic olefin resin (A)) was obtained.

[0109] (Pelletization) Using a vented twin-screw kneading extruder, the molten cyclic olefin resin (A) obtained above was charged from the resin charging section of the extruder. Next, it was pelletized by an underwater pelletizer attached to the extruder outlet, and the obtained pellets were dried for 4 hours with hot air at a temperature of 100°C. The glass transition temperature (Tg) of the cyclic olefin resin (A) was 151°C, the MFR was 28g / 10min (260°C, 2.16kg load), and the content ratio of structural units derived from TD: 37mol%.

[0110] <Preparation of recycled cyclic olefin resin composition (re-pelletization)> <Example 1> The sprue and runner of the pellets (injection molded products) made of the cyclic olefin resin (A) 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 Tg of 151°C and an MFR of 30g / 10min. Next, 0.1 parts by mass of AO-20 (1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by ADEKA CORPORATION) was added as a phenolic antioxidant (B1) 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 with synchronous rotation, screw diameter: 44 mm, and L / D = 30, and melt-kneaded under conditions of screw rotation speed: 150 rpm and motor power: 30 kW. 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) and the phenol-based antioxidant (B1).

[0111] <Example 2> A recycled cyclic olefin resin composition containing a recovered cyclic olefin resin (A1) and a phenolic antioxidant (B2) was obtained in the same manner as in Example 1, except that AO-60 (Pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by ADEKA Corporation) was used as the phenolic antioxidant (B2) instead of the phenolic antioxidant (B1).

[0112] <Example 3> A recycled cyclic olefin resin composition containing a recovered cyclic olefin resin (A1) and a phenolic antioxidant (B3) was obtained in the same manner as in Example 1, except that AO-80 (3,9-Bis{2-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy]-1,1-dimethylethyl}-2,4,8,10-tetraoxaspiro[5.5]undecane, manufactured by ADEKA Corporation) was used as the phenolic antioxidant (B3) instead of the phenolic antioxidant (B1).

[0113] <Comparative Example 1> A recycled cyclic olefin resin composition containing a recovered cyclic olefin resin (A1) and a phenolic antioxidant (B4) was obtained in the same manner as in Example 1, except that AO-30 (4,4',4''-(1-methylpropanyl-3-ylidene)tris(6-tert-butyl-m-cresol, manufactured by ADEKA Corporation) was used as the phenolic antioxidant (B4) instead of the phenolic antioxidant (B1).

[0114] <Comparative Example 2> A recycled cyclic olefin resin composition containing a recovered cyclic olefin resin (A1) and a phenolic antioxidant (B5) was obtained in the same manner as in Comparative Example 1, except that AO-40 (6,6'-di-tert-butyl-4,4'-butylidenedi-m-cresol, manufactured by ADEKA Corporation) was used as the phenolic antioxidant (B5) instead of the phenolic antioxidant (B4).

[0115] (Method of evaluating molded body) (1) Square plate forming Using an injection molding machine (Sumitomo Heavy Industries; SE30DUZ), the recycled cyclic olefin resin compositions obtained in the Examples and Comparative Examples were injection molded under conditions of a cylinder temperature of 270°C and a mold temperature of 126°C to produce test pieces with optical surfaces measuring 35 mm x 65 mm x 3 mm thick.

[0116] (2) Transmittance measurement The light transmittance of each of the test pieces of 35 mm × 65 mm × 3 mm thickness obtained by the above (1) square plate molding was measured using a UV-Vis-NIR spectrophotometer UH4150 (manufactured by Hitachi High-Tech Science Corp.) When the transmittance at a wavelength of 400 nm was 78.0% or more, it was rated as A (good), and when it was less than 78.0%, it was rated as B (poor).

[0117] (3) Internal haze The test piece obtained above, measuring 35 mm×65 mm×3 mm thick, was measured using benzyl alcohol with a haze meter in accordance with JIS K7136:2000.

[0118]

Table 1

Claims

1. A recovered cyclic olefin resin (A), a phenolic antioxidant (B) having a structure represented by the following general formula (X) in its molecule; A recycled cyclic olefin resin composition comprising: 【Chemical 1】 (n in general formula (X) is 1 or more, R １ represents an alkyl group having 1 to 4 carbon atoms, and R ２ and R ３ each independently represents a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and tBu represents a tert-butyl group.

2. The recycled cyclic olefin resin composition according to claim 1, wherein n in the general formula (X) is 1 or 2.

3. R in the general formula (X) １ The recycled cyclic olefin resin composition according to claim 1 or 2, wherein is a tert-butyl group.

4. The recycled cyclic olefin resin composition according to claim 1 or 2, wherein the phenolic antioxidant (B) has 2 to 4 structures represented by the general formula (X) in the molecule.

5. The recycled cyclic olefin resin composition according to claim 1 or 2, wherein the molecular weight of the phenolic antioxidant (B) is 600 or more and 1,300 or less.

6. 3. The recycled cyclic olefin resin composition according to claim 1, wherein the phenolic antioxidant (B) comprises a compound having a structure containing one selected from the group consisting of a triazine skeleton, a pentaerythritol tetrakis skeleton, and a tetraoxaspiro[5.5]undecane skeleton, and a structure represented by general formula (X):

7. 3. The recycled cyclic olefin resin composition according to claim 1, wherein the content of the phenolic antioxidant (B) is 0.05 parts by mass or more and 0.4 parts by mass or less when the content of the recycled cyclic olefin resin (A) is 100 parts by mass.

8. The recovered cyclic olefin resin (A) is The recycled cyclic olefin resin composition according to claim 1 or 2, comprising 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 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). 【Chemistry 2】 (In the formula (I), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Chemistry 3】 (In the 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, 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.) 【Chemistry 4】 (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 or different and are 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 a carbon atom to which R 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. 【Chemistry 5】 (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 the condition 1≦f≦18.

9. The recovered cyclic olefin resin (A) comprises a cyclic olefin copolymer (P2) having a repeating unit (AA) represented by the following formula (II) and a structural 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 claim 1 or 2, 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): 【Chemistry 6】 (In the 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.) 【Chemistry 7】 (In the formula (C-1), n and q each independently represent 0, 1, or 2; R １ ~R １７ 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 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 a polycycle, and the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring. 【Chemistry 8】 (In the formula (C-2), n and m each independently represent 0, 1, or 2, q represents 1, 2, or 3, and R １８ ~R ３１ 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 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 a polycycle, the monocycle or the polycycle may have a double bond, or the monocycle or the polycycle may be an aromatic ring. 【Chemistry 9】 (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.

10. The recycled cyclic olefin resin composition according to claim 1 or 2, which is in the form of pellets.

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

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

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