Method for producing cycloolefin resin molded article

Abstract

To provide a method for producing a cyclic olefin-based resin molded article, capable of reducing generation of bubbles.SOLUTION: A method for producing a cyclic olefin-based resin molded article includes a step (1) including a step of subjecting a cyclic olefin-based resin composition to vacuum treatment and a step of subjecting the cyclic olefin-based resin composition to inert gas treatment, a step (2) of melting the cyclic olefin-based resin composition, and a step (3) of injecting the molten cyclic olefin-based resin composition into a mold, in this order.SELECTED DRAWING: None

Description

[Technical Field]

[0001] The present invention relates to a method for producing a cyclic olefin resin molded article. [Background technology]

[0002] Cyclic olefin copolymers are used in optical lenses such as imaging lenses, XR device lenses, fθ lenses, pickup lenses, etc. Cyclic olefin copolymers used in molded articles such as optical lenses are required to have excellent appearance so as not to scatter light. Patent Document 1 is an example of a method for producing a cyclic olefin copolymer.

[0003] Patent Document 1 discloses a method for producing a molded product made of a cyclic olefin resin, which comprises, when supplying a cyclic olefin resin selected from the group consisting of formulae [I-1], [I-2], [I-3], and [I-4] to a molding apparatus and molding the cyclic olefin resin, subjecting the cyclic olefin resin to a degassing treatment under reduced pressure before supplying the cyclic olefin resin to the molding apparatus; [I-1] an ethylene-cyclic olefin random copolymer obtained by copolymerizing ethylene with a cyclic olefin represented by formula [I] or [II]; [I-2] a ring-opening polymer or copolymer of a cyclic olefin represented by formula [I] or [II]; [I-3] a hydrogenated product of the ring-opening polymer or copolymer of formula [I-2]; and [I-4] a graft-modified product of formula [I-1], [I-2], or [I-3]. The method for producing a molded article made of a cyclic olefin resin provides a method for producing a molded article with excellent appearance, such as an injection molded article, an injection compression molded article, or an injection blow molded article, from a cyclic olefin resin using an injection device, and further provides a method for easily producing a molded article with a low bubble content without making any improvements to the molding device. [Prior art documents] [Patent documents]

[0004] [Patent Document 1] Japanese Patent Application Publication No. 9-40787 Summary of the Invention [Problem to be solved by the invention]

[0005] The present invention provides a method for producing a cyclic olefin resin molded article, which can reduce the generation of bubbles. [Means for solving the problem]

[0006] According to the present invention, there is provided the following method for producing a cyclic olefin resin molded article.

[0007] [1] A method for producing a cyclic olefin resin molded product, comprising: Step (1) includes a step of subjecting a cyclic olefin resin composition to a vacuum treatment and a step of subjecting the composition to an inert gas treatment; Step (2) of melting the cyclic olefin resin composition; and (3) injecting the molten cyclic olefin resin composition into a mold, in this order. [2] The method for producing a cyclic olefin resin molded product according to [1], wherein in the step (1), the vacuum treatment step is followed by the inert gas treatment step. [3] The method for producing a cyclic olefin resin molded article according to [1] or [2], wherein the inert gas treatment step is carried out at an oxygen concentration of 5% or less. [4] The method for producing a cyclic olefin resin molded product according to any one of [1] to [3], wherein the vacuum treatment step is carried out at 10° C. or higher. [5] The method for producing a cyclic olefin resin molded product according to any one of [1] to [4], wherein the vacuum treatment step is carried out at a vacuum degree of −30 kPa or less. [6] The method for producing a cyclic olefin resin molded product according to any one of [1] to [5], wherein the vacuum treatment is carried out for 6 hours or more. [7] The method for producing a cyclic olefin resin molded product according to any one of [1] to [6], wherein the inert gas treatment step is carried out at 50° C. or higher. [8] The method for producing a cyclic olefin resin molded product according to any one of [1] to [7], wherein the inert gas treatment step is carried out for 6 hours or more. [9] The method for producing a cyclic olefin resin molded article according to any one of [1] to [8], wherein the cyclic olefin resin composition contains a cyclic olefin copolymer (A) and an additive (X).

[10] The method for producing a cyclic olefin resin molded article according to [9], wherein the additive (X) contains a hydrophilic agent.

[11] The cyclic olefin copolymer (A) is At least one olefin-derived repeating unit (a) represented by the following general formula (I), a repeating unit (b) derived from at least one cyclic olefin monomer selected from the group consisting of a repeating unit (AA) represented by the following general formula (II), a repeating unit (AB) represented by the following general formula (III), and a repeating unit (AC) represented by the following general formula (IV); The method for producing a cyclic olefin resin molded article according to [9] or

[10] , comprising: [ka] (In the above general 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 general 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 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. [ka] (In the above general formula (III), x and d are each independently an integer of 0 or 1 or more, y and z are each independently 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 the carbon atom to which R is bonded. 93 or the carbon atom to which R is attached 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 above general 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 1≦f≦18.

[12] The cyclic olefin copolymer (A) is A repeating unit (AA) represented by the following general formula (II), and having a repeating unit (C) derived from a cyclic olefin having an aromatic ring, the repeating unit (AA) does not contain an aromatic ring, The method for producing a cyclic olefin resin molded article according to [9] or

[10] , wherein the cyclic olefin having an aromatic ring comprises one or more compounds selected from the group consisting of a compound represented by the following general formula (C-1), a compound represented by the following general formula (C-2), and a compound represented by the following general formula (C-3): [ka] (In the above general 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 above 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 10and 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, and the monocyclic or polycyclic ring may have a double bond, or the monocyclic or polycyclic ring may be an aromatic ring. [ka] (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 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 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 above 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 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.

[13] The method for producing a cyclic olefin resin molded article according to any one of [1] to

[12] , wherein the cyclic olefin resin molded article is an optical member. [Effects of the Invention]

[0008] According to the present invention, it is possible to provide a method for producing a cyclic olefin resin molded article, which can reduce the generation of bubbles. DETAILED DESCRIPTION OF THE INVENTION

[0009] 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.

[0010] <Method of manufacturing cyclic olefin resin molded product> The method for producing a cyclic olefin resin molded article of this embodiment includes, in this order: step (1) including a step of vacuum treating a cyclic olefin resin composition and a step of treating it with an inert gas; step (2) of melting the cyclic olefin resin composition; and step (3) of injecting the molten cyclic olefin resin composition into a mold.

[0011] According to the method for producing a cyclic olefin resin molded article of this embodiment, the generation of bubbles in the obtained molded article can be reduced. For example, when optical components are manufactured by injection molding, an increase in the reject rate due to bubbles in the molded product has become a problem. In manufacturing methods in which cyclic olefin resins are subjected to either vacuum treatment or inert gas treatment before molding, the reduction of bubbles has sometimes been insufficient. In particular, when molded products are large, the rate of bubble generation increases, and it has sometimes been difficult to reduce the reject rate due to bubbles using either vacuum treatment or inert gas treatment alone. In the method for producing a cyclic olefin resin molded article of this embodiment, it is believed that by performing both a vacuum treatment step and an inert gas treatment step in step (1), oxygen in the cyclic olefin resin composition can be removed and the generation of bubbles in the molded article can be reduced.

[0012] (Process (1)) Step (1) is a step of subjecting the cyclic olefin resin composition to a vacuum treatment and an inert gas treatment, thereby reducing the generation of bubbles in the cyclic olefin resin composition. In step (1), it is preferable to perform a vacuum treatment step followed by an inert gas treatment step. By performing step (1) in this order, oxygen contained in the cyclic olefin resin can be more effectively removed, and the generation of bubbles in the resulting molded product can be reduced.

[0013] (Vacuum processing process) The vacuum treatment step is a step of removing oxygen from the cyclic olefin resin composition by drying the cyclic olefin resin composition under vacuum conditions. The vacuum treatment step can be carried out using, for example, a vacuum dryer, which can be equipped with a vacuum generator that generates a vacuum using a vacuum pump or compressed air.

[0014] The vacuum treatment step is preferably carried out at a temperature of 10°C or higher and 50°C or lower, more preferably 15°C or higher and 40°C or lower, and even more preferably 20°C or higher and 30°C or lower. By carrying out the vacuum treatment at a temperature equal to or higher than the lower limit, the generation of bubbles in the resulting molded body can be further reduced, and by carrying out the vacuum treatment at a temperature equal to or lower than the upper limit, the physical properties of the resulting molded body can be further improved.

[0015] The vacuum treatment step is preferably carried out at a vacuum degree of −30 kPa or less, more preferably a vacuum degree of −40 kPa or less, even more preferably a vacuum degree of −50 kPa or less, even more preferably a vacuum degree of −60 kPa or less, even more preferably a vacuum degree of −70 kPa or less, and even more preferably a vacuum degree of −80 kPa or less. There is no lower limit to the degree of vacuum in the vacuum treatment step, but it may be, for example, −150 kPa or higher, or −130 kPa or higher. Furthermore, the vacuum treatment step is preferably carried out at a vacuum degree of -150 kPa or more and -30 kPa or less, more preferably at a vacuum degree of -150 kPa or more and -40 kPa or less, even more preferably at a vacuum degree of -150 kPa or more and -50 kPa or less, even more preferably at a vacuum degree of -130 kPa or more and -60 kPa or less, even more preferably at a vacuum degree of -130 kPa or more and -70 kPa or less, and even more preferably at a vacuum degree of -130 kPa or more and -80 kPa or less. By carrying out the vacuum treatment step at a vacuum degree equal to or less than the upper limit, the generation of bubbles in the resulting molded body can be further reduced.

[0016] The vacuum treatment step is carried out for preferably 6 hours or more, more preferably 8 hours or more, even more preferably 10 hours or more, and even more preferably 12 hours or more. There is no upper limit to the time required for the vacuum treatment step, but it may be, for example, 50 hours or less, or 40 hours or less. The vacuum treatment step is preferably carried out for 6 hours to 50 hours, more preferably 8 hours to 50 hours, even more preferably 10 hours to 40 hours, and even more preferably 12 hours to 40 hours. By carrying out the vacuum treatment step for a time equal to or greater than the above lower limit, the generation of bubbles in the resulting molded body can be further reduced.

[0017] (Inert gas treatment process) The inert gas treatment step is a step of removing dissolved oxygen from the cyclic olefin resin composition by drying the cyclic olefin resin composition while heating it in an inert gas environment. The inert gas used in the inert gas treatment step is preferably one or more selected from the group consisting of nitrogen gas, argon gas and helium, more preferably nitrogen gas. The inert gas treatment step can be carried out using, for example, a nitrogen dryer.

[0018] The inert gas treatment step is preferably carried out at an oxygen concentration of 5% or less, more preferably 3% or less, even more preferably 2% or less, and even more preferably 1% or less. There is no lower limit for the oxygen concentration in the inert gas treatment step, but it may be, for example, 0% or more, or 0.01% or more. The inert gas treatment step is preferably carried out at an oxygen concentration of 0% or more and 5% or less, more preferably at an oxygen concentration of 0% or more and 3% or less, even more preferably at an oxygen concentration of 0% or more and 2% or less, and even more preferably at an oxygen concentration of 0.01% or more and 1% or less. Here, the oxygen concentration refers to, for example, the oxygen concentration in a nitrogen dryer. By supplying nitrogen into the nitrogen dryer, the oxygen concentration in the nitrogen dryer can be made equal to or lower than the upper limit value. By ensuring that the oxygen concentration in the inert gas treatment step is equal to or less than the upper limit, oxygen contained in the cyclic olefin resin can be more effectively removed, and the generation of bubbles in the resulting molded article can be more effectively reduced.

[0019] The inert gas treatment step is preferably carried out at a temperature of 50°C or higher and 200°C or lower, more preferably 60°C or higher and 180°C or lower, even more preferably 80°C or higher and 160°C or lower, even more preferably 100°C or higher and 140°C or lower, and even more preferably 110°C or higher and 130°C or lower. By setting the temperature in the inert gas treatment step to be equal to or higher than the above lower limit, the generation of bubbles in the obtained molded body can be further reduced.By setting the temperature in the inert gas treatment step to be equal to or lower than the above upper limit, the physical properties of the obtained molded body can be further improved.

[0020] The inert gas treatment step is carried out for preferably 6 hours or more and 50 hours or less, more preferably 8 hours or more and 45 hours or less, even more preferably 10 hours or more and 40 hours or less, even more preferably 12 hours or more and 35 hours or less, even more preferably 15 hours or more and 30 hours or less, and even more preferably 18 hours or more and 25 hours or less. By carrying out the inert gas treatment step for a time equal to or greater than the above lower limit, the generation of bubbles in the resulting molded body can be further reduced, and by carrying out the inert gas treatment step for a time equal to or less than the above upper limit, the physical properties of the resulting molded body can be further improved.

[0021] Furthermore, in step (1), when the vacuum treatment step is followed by the inert gas treatment step, for example, the cyclic olefin resin composition is subjected to vacuum treatment in a vacuum dryer, and then the pressure inside the vacuum dryer is returned to normal using nitrogen or air, and the cyclic olefin resin composition is then transferred to a nitrogen dryer, and nitrogen is supplied to the nitrogen dryer. In this case, it is preferable to return the pressure inside the vacuum dryer to normal using nitrogen, and more preferably, after returning to normal pressure, the composition is transferred to the nitrogen dryer in an atmosphere with an oxygen concentration of 5% or less. It is also more preferable that nitrogen is supplied into the nitrogen dryer before the cyclic olefin resin composition is transferred thereto.

[0022] (Steps (2) and (3)) Step (2) in the method for producing a cyclic olefin resin molded article of this embodiment is a step of melting the cyclic olefin resin composition that has been subjected to step (1). Step (3) in the method for producing a cyclic olefin resin molded article of this embodiment is a step of injecting the cyclic olefin resin composition melted in step (2) into a mold. Steps (2) and (3) can be carried out, for example, by using an injection molding machine to inject the cyclic olefin resin composition into a mold while it is melted. The temperature at which the cyclic olefin resin composition is melted in the injection molding machine is preferably 150°C or higher and 400°C or lower, more preferably 200°C or higher and 350°C or lower, and even more preferably 230°C or higher and 330°C or lower.

[0023] Furthermore, when steps (2) and (3) are performed on the cyclic olefin resin composition after step (1), for example, the cyclic olefin resin composition after the inert gas treatment step in step (1) can be transported from a nitrogen dryer to an injection molding machine via a resin supply path. The resin supply path from the nitrogen dryer to the injection molding machine is preferably filled with nitrogen to maintain an oxygen concentration of 5% or less. Furthermore, for example, the cyclic olefin resin composition can be stored in a nitrogen dryer before being transferred to an injection molding machine.

[0024] Furthermore, the method for producing a cyclic olefin resin molded product of this embodiment may further include a pelletizing step of kneading the cyclic olefin resin composition in an extruder to form pellets before step (1). That is, the cyclic olefin resin composition of this embodiment can be made into pellets. In the pelletizing step, the cyclic olefin resin composition is 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. The pelletized cyclic olefin resin composition may be dried, for example, with hot air at 80°C or higher.

[0025] <Cyclic olefin resin composition> The cyclic olefin resin composition of the present embodiment preferably contains a cyclic olefin copolymer (A) and an additive (X).

[0026] (Cyclic olefin copolymer (A)) The cyclic olefin copolymer (A) contained in the cyclic olefin resin composition of this embodiment is a copolymer containing a repeating unit derived from a cyclic olefin as an essential repeating unit.

[0027] [First embodiment] A first embodiment of the cyclic olefin copolymer (A) of this embodiment preferably has at least one olefin-derived repeating unit (a) represented by the following general 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 general formula (II), repeating units (AB) represented by the following general formula (III), and repeating units (AC) represented by the following general formula (IV). When the cyclic olefin copolymer (A) has the repeating unit (a) and the repeating unit (b), the performance balance of the transparency, refractive index, moist heat resistance, and moldability of the molded article can be further improved.

[0028] The above general formulas (I) to (IV) will be explained below.

[0029] [ka]

[0030] In the above general formula (I), preferably, R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0031] The repeating unit represented by the general formula (I) corresponds to an olefin monomer represented by the following general formula (Ia): That is, the olefin monomer represented by the following general formula (Ia) is addition polymerized to form the repeating unit (a) represented by the general formula (I).

[0032] [ka]

[0033] In the above general formula (Ia), preferably, R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. The olefin monomer represented by the general formula (Ia) is preferably one or more selected from the group consisting of ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 3-methyl-1-butene, 3-methyl-1-pentene, 3-ethyl-1-pentene, 4-methyl-1-pentene, 4-methyl-1-hexene, 4,4-dimethyl-1-hexene, 4,4-dimethyl-1-pentene, 4-ethyl-1-hexene, 3-ethyl-1-hexene, 1-octene, 1-decene, 1-dodecene, 1-tetradecene, 1-hexadecene, 1-octadecene, and 1-eicosene. Among these, from the viewpoint of further improving the balance of optical properties and moist heat resistance, the olefin monomer represented by general formula (Ia) is more preferably one or two selected from the group consisting of ethylene and propylene, and more preferably ethylene. Two or more types of olefin monomers represented by the general formula (Ia) may be used, and the olefin monomer may contain at least one type of biomass-derived monomer (ethylene, propylene, α-olefin).

[0034] [ka]

[0035] In the above general formula (II), preferably, 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 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.

[0036] The repeating unit (AA) represented by the general formula (II) corresponds to a cyclic olefin monomer represented by the following general formula (IIa): That is, the cyclic olefin monomer represented by the following general formula (IIa) is addition polymerized to form the repeating unit (AA) represented by the general formula (II).

[0037] [ka]

[0038] In the above general formula (IIa), preferably, u is 0 or 1, v is 0 or a positive integer, more preferably an integer of 0 or more and 2 or less, and even more preferably 0 or 1, 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.

[0039] Specifically, preferred examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; halogenated alkyl groups having 1 to 20 carbon atoms include halogenated versions of the groups listed as alkyl groups having 1 to 20 carbon atoms; cycloalkyl groups having 3 to 15 carbon atoms include cyclohexyl groups; and aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups, as well as aralkyl groups.

[0040] Specific examples of the cyclic olefin monomer represented by general formula (IIa) include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261. The cyclic olefin monomer is obtained from dicyclopentadiene and ethylene. The ethylene may contain repeating units derived from a biomass-derived monomer (ethylene).

[0041] The cyclic olefin monomer represented by the general formula (IIa) is preferably bicyclo[2.2.1]-2-heptene (also called norbornene) and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (also called tetracyclododecene), and more preferably tetracyclododecene. These cyclic olefin monomers have a rigid ring structure, and therefore the elastic modulus of the cyclic olefin copolymer (A) and the molded article can be more easily maintained. Two or more types of cyclic olefin monomers represented by the above general formula (IIa) may be used.

[0042] [ka]

[0043] In the above general formula (III), preferably, x and d are each independently 0 or an integer of 1 or more, more preferably an integer of 0 or more and 2 or less, and even more preferably 0 or 1; y and z are each independently 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 the carbon atom to which R is bonded. 93 or the carbon atom to which R is attached 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] The repeating unit (AB) represented by the general formula (III) corresponds to a cyclic olefin monomer represented by the following general formula (IIIa): That is, the cyclic olefin monomer represented by the following general formula (IIIa) undergoes addition polymerization to form the repeating unit (AB) represented by the general formula (III).

[0045] [ka]

[0046] In the above general formula (IIIa), preferably, x and d each independently represent 0 or an integer of 1 or more, more preferably an integer of 0 or more and 2 or less, and even more preferably 0 or 1; y and z each independently represent 0, 1, or 2; and R 81 ~R 99may 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 the carbon atom to which R is bonded. 93 or the carbon atom to which R is attached 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.

[0047] Specifically, preferred examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; examples of cycloalkyl groups having 3 to 15 carbon atoms include cyclohexyl groups; examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups, and aralkyl groups; and examples of alkoxy groups include methoxy, ethoxy, and propyloxy groups.

[0048] Specific examples of the cyclic olefin monomer represented by general formula (IIIa) include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261.

[0049] Two or more types of cyclic olefin monomers represented by the above general formula (IIIa) may be used.

[0050] [ka]

[0051] In the above general formula (IV), preferably, R100 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 1≦f≦18.

[0052] The repeating unit (AC) represented by the general formula (IV) corresponds to a cyclic olefin monomer represented by the following general formula (IVa): That is, the cyclic olefin monomer represented by the following general formula (IVa) is addition polymerized to form the repeating unit (AC) represented by the general formula (IV).

[0053] [ka]

[0054] In the above general formula (IVa), preferably, 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 1≦f≦18.

[0055] Specific examples of hydrocarbon groups having 1 to 5 carbon atoms include a methyl group, an ethyl group, a propyl group, and an isopropyl group.

[0056] Specific examples of the cyclic olefin monomer represented by general formula (IVa) include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261.

[0057] Two or more types of olefin monomers represented by the above general formula (IVa) may be used.

[0058] In the first embodiment of the cyclic olefin copolymer (A) of this embodiment, by using the above-mentioned olefin monomer represented by the general formula (Ia) or the cyclic olefin monomer represented by the general formula (IIa), (IIIa) or (IVa) as a copolymerization component, the solubility of the cyclic olefin copolymer (A) in a solvent is further improved, resulting in good moldability and an improved product yield.

[0059] Among the cyclic olefin monomers represented by general formula (IIa), (IIIa) or (IVa), the cyclic olefin represented by general formula (IIa) is preferred. It is also preferable to use a cyclic olefin represented by general formula (IIa) and a cyclic olefin represented by general formula (IIIa) or (IVa).

[0060] In a first embodiment of the cyclic olefin copolymer (A) of this embodiment, when the total number of repeating units constituting the cyclic olefin copolymer (A) is taken as 100 mol%, the content of the olefin-derived repeating unit (a) in the cyclic olefin copolymer (A) is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 90 mol% or less, even more preferably 20 mol% or more and 90 mol% or less, even more preferably 30 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, from the viewpoint of further improving the performance balance of the moist heat resistance, mechanical properties, and optical properties of the molded article. The content of the olefin-derived repeating unit (a) is 1 H-NMR or 13 It can be measured by C-NMR.

[0061] When the total number of repeating units constituting the cyclic olefin copolymer (A) is taken as 100 mol%, the content of repeating units (b) derived from cyclic olefin monomers in the cyclic olefin copolymer (A) is preferably 5 mol% or more and 95 mol% or less, more preferably 5 mol% or more and 90 mol% or less, even more preferably 10 mol% or more and 80 mol% or less, even more preferably 10 mol% or more and 70 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, from the viewpoint of further improving the performance balance of the moist heat resistance, mechanical properties, and optical properties of the molded article. The content of the repeating unit (b) derived from a cyclic olefin monomer is 1 H-NMR or 13It can be measured by C-NMR.

[0062] In the first embodiment of the cyclic olefin copolymer (A) of this embodiment, the copolymer type is not particularly limited, and examples thereof include random copolymers, block copolymers, etc. From the viewpoint of further improving the optical properties such as transparency, refractive index, and birefringence of the molded article, the cyclic olefin copolymer (A) of the first embodiment of this embodiment is preferably a random copolymer.

[0063] The cyclic olefin copolymer (A) in the first embodiment of this embodiment is preferably a copolymer of 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, and more preferably, ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene and ethylene with tetracyclo[4.4.0.1 2,5 .1 7,10 The copolymer is one or two selected from the group consisting of random copolymers of 1-3-dodecene and benzonorbornadiene.

[0064] The cyclic olefin copolymer (A) in the first embodiment of this embodiment may be used alone or in combination of two or more.

[0065] The cyclic olefin copolymer (A) in the first embodiment of this embodiment can be produced by appropriately selecting 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.

[0066] [Second embodiment] A second embodiment of the cyclic olefin copolymer (A) of this embodiment preferably has a repeating unit (AA) represented by the following general 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 comprises one or more compounds selected from the group consisting of a compound represented by the following general formula (C-1), a compound represented by the following general formula (C-2), and a compound represented by the following general formula (C-3):

[0067] (Repeating units derived from cyclic olefins (AA)) The repeating unit (AA) is a repeating unit represented by the following general formula (II). When the cyclic olefin copolymer (A) contains the repeating unit (AA), the refractive index of the resulting molded article can be further improved. Furthermore, the repeating unit (AA) preferably does not contain an aromatic ring, which can further improve the moldability of the resulting molded article.

[0068] [ka]

[0069] In the above general formula (II), preferably, 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 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.

[0070] The repeating unit (AA) represented by the general formula (II) corresponds to a cyclic olefin monomer represented by the following general formula (IIa): That is, the cyclic olefin monomer represented by the following general formula (IIa) is addition polymerized to form the repeating unit (AA) represented by the general formula (II).

[0071] [ka]

[0072] In the above general formula (IIa), preferably, u is 0 or 1, v is 0 or a positive integer, more preferably an integer of 0 or more and 2 or less, and even more preferably 0 or 1, 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.

[0073] Specifically, preferred examples of alkyl groups having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; halogenated alkyl groups having 1 to 20 carbon atoms include halogenated versions of the groups listed as alkyl groups having 1 to 20 carbon atoms; and examples of cycloalkyl groups having 3 to 15 carbon atoms include cyclohexyl groups.

[0074] Specific examples of the cyclic olefin monomer represented by general formula (IIa) include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 118261. The cyclic olefin monomer is obtained from dicyclopentadiene and ethylene. The ethylene may contain repeating units derived from a biomass-derived monomer (ethylene).

[0075] The cyclic olefin monomer represented by the general formula (IIa) is preferably bicyclo[2.2.1]-2-heptene (also called norbornene) and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (also called tetracyclododecene), and more preferably tetracyclododecene. These cyclic olefin monomers have a rigid ring structure, and therefore the elastic modulus of the cyclic olefin copolymer (A) and the molded article can be more easily maintained. Two or more types of cyclic olefin monomers represented by the above general formula (IIa) may be used.

[0076] (Repeating unit (C) derived from a cyclic olefin having an aromatic ring) The repeating unit (C) derived from a cyclic olefin having an aromatic ring is a repeating unit derived from a cyclic olefin having an aromatic ring. The aromatic ring-containing cyclic olefin preferably includes one or more compounds selected from the group consisting of compounds represented by the following general formula (C-1), compounds represented by the following general formula (C-2), and compounds represented by the following general formula (C-3): These aromatic ring-containing cyclic olefins may be used alone or in combination of two or more.

[0077] [ka]

[0078] In the above general formula (C-1), preferably, n and q are each independently 0, 1 or 2, more preferably, n is 0 or 1, even more preferably, n is 0, more preferably, q is 0 or 1, even more preferably, q is 0. R 1 ~R 17 are each independently preferably 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 the groups is a bond, and more preferably R 15 is a bond, and more preferably R 1 ~R 17 are each independently 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 , 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 10may 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.

[0079] Preferred examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups; and aromatic hydrocarbon groups such as aralkyl groups. These groups may be substituted with halogen atoms other than fluorine atoms.

[0080] Two or more types of cyclic olefin monomers represented by the above general formula (C-1) may be used.

[0081] The general formula (C-1) preferably contains a cyclic olefin monomer represented by the following general formula (C-1A): Each substituent in the general formula (C-1A) is the same as defined in the general formula (C-1) above.

[0082] [ka]

[0083] [ka]

[0084] In the above general formula (C-2), preferably, n and m are each independently 0, 1, or 2, and q is 1, 2, or 3. More preferably, m is 0 or 1, and even more preferably, m is 1. More preferably, n is 0 or 1, and even more preferably, n is 0. More preferably, q is 1 or 2, and even more preferably, q is 1. R 18 ~R 31are preferably 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. R 18 ~R 31 and are more preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and even more preferably a hydrogen 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, 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, or the monocycle or polycycle may be an aromatic ring.

[0085] Preferred examples of the hydrocarbon group having 1 to 20 carbon atoms include alkyl groups such as methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; cycloalkyl groups such as cyclohexyl groups; aryl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups; and aromatic hydrocarbon groups such as aralkyl groups. These groups may be substituted with halogen atoms other than fluorine atoms.

[0086] Two or more types of cyclic olefin monomers represented by the above general formula (C-2) may be used.

[0087] [ka]

[0088] In the above general formula (C-3), q is preferably 1, 2 or 3, more preferably 1 or 2, and even more preferably 1. R 32 ~R 39 are preferably 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. R 32 ~R 39 and are more preferably each independently a hydrogen atom or a hydrocarbon group having 1 to 20 carbon atoms, and even 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, or the monocycle or polycycle may be an aromatic ring.

[0089] Preferred examples of hydrocarbon groups having 1 to 20 carbon atoms include, independently of one another, alkyl groups having 1 to 20 carbon atoms, cycloalkyl groups having 3 to 15 carbon atoms, and aromatic hydrocarbon groups. More specific examples include methyl, ethyl, propyl, isopropyl, amyl, hexyl, octyl, decyl, dodecyl, and octadecyl groups; examples of cycloalkyl groups having 3 to 15 carbon atoms include cyclohexyl groups; and examples of aromatic hydrocarbon groups having 6 to 20 carbon atoms include aryl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl groups, as well as aralkyl groups. These groups may be substituted with halogen atoms other than fluorine atoms.

[0090] Two or more types of cyclic olefin monomers represented by the above general formula (C-3) may be used.

[0091] Among these, the cyclic olefin monomer having an aromatic ring preferably includes one or more selected from the group consisting of benzonorbornadiene, indenenorbornene, and methylphenylnorbornene.

[0092] In a second embodiment of the cyclic olefin copolymer (A) of this embodiment, when all of the repeating units constituting the cyclic olefin copolymer (A) are taken as 100 mol%, the content of the repeating unit (AA) in the cyclic olefin copolymer (A) is preferably 5 mol% or more and 95 mol% or less, more preferably 10 mol% or more and 95 mol% or less, even more preferably 20 mol% or more and 95 mol% or less, even more preferably 30 mol% or more and 95 mol% or less, even more preferably 40 mol% or more and 95 mol% or less, and even more preferably 50 mol% or more and 95 mol% or less, from the viewpoint of further improving the performance balance of the moist heat resistance, mechanical properties, and optical properties of the molded article. The content of repeating units (AA) is 1 H-NMR or 13 It can be measured by C-NMR.

[0093] In a second embodiment of the cyclic olefin copolymer (A) of this embodiment, when all of the repeating units constituting the cyclic olefin copolymer (A) are taken as 100 mol%, the content of the repeating unit (C) in the cyclic olefin copolymer (A) is preferably 5 mol% or more and 95 mol% or less, more preferably 5 mol% or more and 90 mol% or less, even more preferably 5 mol% or more and 80 mol% or less, even more preferably 5 mol% or more and 70 mol% or less, even more preferably 5 mol% or more and 60 mol% or less, and even more preferably 5 mol% or more and 50 mol% or less, from the viewpoint of further improving the performance balance of the moist heat resistance, mechanical properties, and optical properties of the molded article. The content of the repeating unit (C) is 1 H-NMR or 13 It can be measured by C-NMR.

[0094] In the second embodiment of the cyclic olefin copolymer (A) of this embodiment, the copolymer type is not particularly limited, and examples thereof include random copolymers, block copolymers, etc. From the viewpoint of further improving the performance balance between transparency and moist heat resistance in the molded article, the cyclic olefin copolymer (A) of the second embodiment of this embodiment is preferably a random copolymer.

[0095] In the second embodiment of this embodiment, the cyclic olefin copolymer (A) may be used alone or in combination of two or more.

[0096] The cyclic olefin copolymer (A) according to the second embodiment of this embodiment can be produced by appropriately selecting the conditions according to the methods described in, for example, JP 60-168708 A, JP 61-120816 A, JP 61-115912 A, JP 61-115916 A, JP 61-271308 A, JP 61-272216 A, JP 62-252406 A, JP 62-252407 A, JP 2007-314806 A, JP 2010-241932 A, etc. In addition, as the cyclic olefin copolymer (A) according to the second embodiment, for example, 5013L-10 (manufactured by POLYPLASTICS Co., Ltd.) can be used.

[0097] The glass transition temperature of the cyclic olefin resin composition of the present embodiment is preferably 100°C or higher, 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, from the viewpoint of further improving the heat resistance of the molded article, and is preferably 170°C or lower, from the viewpoint of further improving the moldability. The glass transition temperature (Tg) can be measured using a differential scanning calorimeter from the endothermic curve obtained by heating a cyclic olefin resin composition in a nitrogen atmosphere from room temperature to 250°C at a heating rate of 10°C / min, holding the temperature for 5 minutes, then cooling the composition to -20°C at a heating rate of 10°C / min, holding the temperature for 5 minutes, and then heating the composition to 250°C at a heating rate of 10°C / min.

[0098] The content of the cyclic olefin copolymer (A) in the cyclic olefin resin composition of this embodiment, when the total amount of the cyclic olefin resin composition is taken as 100% by mass, is preferably 50% by mass or more, more preferably 70% by mass or more, even more preferably 80% by mass or more, even more preferably 90% by mass or more, even more preferably 95% by mass or more, even more preferably 98% by mass or more, even more preferably 99% by mass or more, and is, for example, less than 100% by mass, from the viewpoint of further improving the performance balance between moldability and optical properties.

[0099] (Additive (X)) The additive (X) may be any additive that is usually added to a thermoplastic resin, and preferably, one or more selected from the group consisting of hydrophilic agents, nucleating agents, antioxidants, hydrophilic stabilizers (or water-absorbing stabilizers), hydrochloric acid absorbers, heat stabilizers, light stabilizers, ultraviolet absorbers, lubricants, antistatic agents, flame retardants, pigments, dyes, dispersants, copper inhibitors, neutralizing agents, foaming agents, plasticizers, anti-foaming agents, crosslinking agents, flow improvers such as peroxides, weld strength improvers, and mold release improvers (mold release agents). Among these, from the viewpoint of further improving optical performance, the additive (X) preferably contains a hydrophilic agent.

[0100] (hydrophilic agent) The hydrophilic agent preferably includes a fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups. The ether group of the polyhydric alcohol does not include an ether group in the ester group. Among these, the hydrophilic agent more preferably includes a fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups. When the cyclic olefin resin composition contains a fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups, deterioration of the optical performance of the molded article under high-temperature and high-humidity conditions can be further suppressed. The reason for this is not clear, but the following is thought to be the reason. First, the fatty acid ester has hydrophilic functional groups such as hydroxyl groups, ether groups, and carbonyl groups. Therefore, even when molded under high-temperature, high-humidity conditions, it is presumed that water absorbed within the optical component is dispersed, and water aggregation, which causes deterioration of optical performance, is suppressed. As a result of suppressing water aggregation, which causes deterioration of optical performance, it is thought that deterioration of optical performance under high-temperature, high-humidity conditions is suppressed.

[0101] The polyhydric alcohol having one or more ether groups preferably includes one or more selected from the group consisting of diglycerin, triglycerin, tetraglycerin, and sorbitan, and more preferably includes one or more selected from the group consisting of diglycerin and triglycerin. In this embodiment, the fatty acid ester is preferably a glycerin fatty acid ester, and more preferably includes one or more selected from the group consisting of diglycerin fatty acid esters and triglycerin fatty acid esters. The diglycerin fatty acid ester is a fatty acid in which at least one of the four hydroxyl groups contained in diglycerin is esterified with a fatty acid. The triglycerin fatty acid ester is a fatty acid in which at least one of the five hydroxyl groups contained in triglycerin is esterified with a fatty acid.

[0102] The fatty acid preferably includes one or more selected from the group consisting of saturated fatty acids such as butanoic acid, pentanoic acid, hexanoic acid, heptanoic acid, octanoic acid, nonanoic acid, capric acid, lauric acid, myristic acid, palmitic acid, and stearic acid; monounsaturated fatty acids such as crotonic acid, myristoleic acid, palmitoleic acid, sapienic acid, oleic acid, elaidic acid, gadoleic acid, and eicosenoic acid; diunsaturated fatty acids such as linoleic acid, eicosadienoic acid, and docosadienoic acid; triunsaturated fatty acids such as linolenic acid, pinolenic acid, eleostearic acid, and eicosatrienoic acid; and tetraunsaturated fatty acids such as stearidonic acid, arachidonic acid, and eicosatetraenoic acid.

[0103] The diglycerin fatty acid ester is preferably one or more selected from the group consisting of saturated diglycerin fatty acid esters such as diglycerin monocaprylate, diglycerin dicaprylate, diglycerin monocaprate, diglycerin dicaprate, diglycerin monolaurate, diglycerin dilaurate, diglycerin monomyristate, diglycerin dimyristate, diglycerin monopalmitate, diglycerin dipalmitate, diglycerin monostearate, diglycerin distearate, diglycerin monobehenate, and diglycerin dibehenate; unsaturated diglycerin fatty acid esters such as diglycerin monooleate and diglycerin dioleate; and the like. One or more selected from these can be used in combination. In this embodiment, the diglycerin fatty acid ester is preferably an ester of diglycerin and a saturated or unsaturated fatty acid having 12 to 18 carbon atoms selected from the above.

[0104] The triglycerin fatty acid ester is preferably triglycerin monocaprylate, triglycerin dicaprylate, triglycerin tricaprylate, triglycerin monocaprate, triglycerin dicaprate, triglycerin tricaprate, triglycerin monolaurate, triglycerin dilaurate, triglycerin trilaurate, triglycerin monomyristate, triglycerin dimyristate, triglycerin trimyristate, triglycerin monopalmitate, triglycerin dipalmitate, triglycerin The fatty acid esters may include one or more selected from the group consisting of saturated triglycerin fatty acid esters such as triglycerin tripalmyrate, triglycerin monostearate, triglycerin distearate, triglycerin tristearate, triglycerin monobehenate, triglycerin dibehenate, and triglycerin tribehenate; unsaturated triglycerin fatty acid esters such as triglycerin monooleate, triglycerin dioleate, and triglycerin trioleate; and the like, and one or more selected from these may be used in combination.

[0105] The glycerin fatty acid ester according to this embodiment preferably comprises an ester of triglycerin or diglycerin with a saturated or unsaturated fatty acid having from 8 to 24 carbon atoms, and more preferably comprises an ester of triglycerin or diglycerin with a saturated or unsaturated fatty acid having from 12 to 18 carbon atoms.

[0106] Examples of the glycerin fatty acid ester according to this embodiment include a monoester alone, a mixture of a monoester and a diester, or a mixture of a monoester, a diester and a triester.

[0107] (antioxidant) As the antioxidant, a phenol-based antioxidant, a sulfur-based antioxidant, a phosphorus-based antioxidant, or the like can be used. The phenolic antioxidant is preferably 2,6-di-tert-butyl-p-cresol, stearyl (3,3-dimethyl-4-hydroxybenzyl) thioglycolate, stearyl-β-(4-hydroxy-3,5-di-tert-butylphenol) propionate, distearyl-3,5-di-tert-butyl-4-hydroxybenzylphosphonate, 2,4,6-tris(3',5'-di-tert-butyl-4'-hydroxybenzylthio)-1,3,5-triazine, distearyl (4-hydroxy-3-methyl-5- tert-butylbenzyl)malonate, 2,2'methylenebis(4-methyl-6-tert-butylphenol), 4,4'-methylenebis(2,6-di-tert-butylphenol), 2,2'-methylenebis[6-(1-methylcyclohexyl)p-cresol], bis[3,5-bis[4-hydroxy-3-tert-butylphenyl)butylic acid]glycol ester, 4,4'-butylidenebis(6-tert-butyl-m-cresol), 1,1,3-tris(2-methyl-4-hydroxy-5-tert-butylphenyl) nyl)butane, bis[2-tert-butyl-4-methyl-6-(2-hydroxy-3-tert-butyl-5-methylbenzyl)phenyl]terephthalate, 1,3,5-tris(2,6-dimethyl-3-hydroxy-4-tert-butyl)benzyl isocyanurate, 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-2,4,6-trimethylbenzene, tetrakis[methylene-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate]methane, pentaerythritol-tetrakis Phenols such as bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)isocyanurate, 1,3,5-tris[(3,5-di-tert-butyl-4-hydroxyphenyl)propionyloxyethyl]isocyanurate, 2-octylthio-4,6-di(4-hydroxy-3,5-di-tert-butyl)phenoxy-1,3,5-triazine, 4,4'-thiobis(6-tert-butyl-m-cresol) and 4,The polymer may include one or more selected from the group consisting of polyhydric phenol carbonate oligoesters such as carbonate oligoesters of 4'-butylidenebis(2-tert-butyl-5-methylphenol) (e.g., degree of polymerization 2 to 10).

[0108] The sulfur-based antioxidant preferably includes one or more selected from the group consisting of dialkylthiodipropionates such as dilauryl, dimyristyl, and distearyl, and esters of alkylthiopropionic acids such as butyl, octyl, lauryl, and stearyl with polyhydric alcohols (for example, glycerin, trimethylolethane, trimethylolpropane, pentaerythritol, and trishydroxyethyl isocyanurate) (for example, pentaerythritol tetralaurylthiopropionate).

[0109] The phosphorus-based antioxidant is preferably trioctyl phosphite, trilauryl phosphite, tridecyl phosphite, octyl-diphenyl phosphite, tris(2,4-di-tert-butylphenyl) phosphite, triphenyl phosphite, tris(butoxyethyl) phosphite, tris(nonylphenyl) phosphite, distearyl pentaerythritol diphosphite, tetra(tridecyl)-1,1,3-tris(2-methyl-5-tert-butyl-4-hydroxyphenyl)butanol, Tanethene diphosphite, tetra(C12-C15 mixed alkyl)-4,4'-isopropylidene diphenyl diphosphite, tetra(tridecyl)-4,4'-butylidenebis(3-methyl-6-tert-butylphenol) diphosphite, tris(3,5-di-tert-butyl-4-hydroxyphenyl)phosphite, tris(mono- and di-mixed nonylphenyl)phosphite, hydrogenated-4,4'-isopropylidene diphenol polyphosphite, bis(octylphenyl)bis[4,4'-butylidenebis (3-methyl-6-tert-butylphenol)]·1,6-hexanediol diphosphite, phenyl·4,4'-isopropylidenediphenol·pentaerythritol diphosphite, bis(2,4-di-tert-butylphenyl)pentaerythritol diphosphite, bis(2,6-di-tert-butyl-4-methylphenyl)pentaerythritol diphosphite, tris[4,4'isopropylidenebis(2-tert-butylphenol)]phosphite, phenyl·diisodecylphosphite The compound contains one or more compounds selected from the group consisting of tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite, di(nonylphenyl)pentaerythritol diphosphite, tris(1,3-di-stearoyloxyisopropyl)phosphite, 4,4'-isopropylidenebis(2-tert-butylphenol)-di(nonylphenyl)phosphite, 9,10-di-hydro-9-oxa-9-oxa-10-phosphaphenanthrene-10-oxide, and tetrakis(2,4-di-tert-butylphenyl)-4,4'-biphenylene diphosphonite.

[0110] Further, as other antioxidants, 6-hydroxychroman derivatives such as various α, β, γ and δ tocopherols or mixtures thereof, 2,5-dimethyl-substituted, 2,5,8-trimethyl-substituted and 2,5,7,8-tetramethyl-substituted 2-(4-methyl-pent-3-enyl)-6-hydroxychroman, 2,2,7-trimethyl-5-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-7-tert-butyl-6-hydroxychroman, 2,2,5-trimethyl-6-tert-butyl-6-hydroxychroman, 2,2-dimethyl-5-tert-butyl-6-hydroxychroman, etc. can also be used.

[0111] (hydrochloric acid absorber) In addition, hydrochloric acid absorbents include: General formula: M x Al y (OH) 2x+3y-2z (A) z aH2O (wherein M is Mg, Ca or Zn, A is an anion other than a hydroxyl group, x, y and z are positive numbers, and a is 0 or a positive number), preferably MgAl(OH) 16 CO3·4H2O, Mg6Al2(OH) 20 CO3·5H2O, Mg5Al2(OH) 14 CO3·4H2O, Mg 10 Al2(OH) 22 (CO3)2·4H2O, Mg6Al2(OH) 16 HPO4·4H2O, Ca6Al2(OH) 16 CO3·4H2O, Zn6Al2(OH) 16 CO3·4H2O, Zn6Al2(OH) 16 SO4·4H2O, Mg6Al2(OH) 16 SO3·4H2O, Mg6Al2(OH) 12 One or more selected from the group consisting of CO3·3H2O and the like can be used.

[0112] (light stabilizer) Preferred examples of the light stabilizer include hydroxybenzophenones such as 2-hydroxy-4-methoxybenzophenone, 2-hydroxy-4-n-octoxybenzophenone-2,2'-di-hydroxy-4-methoxybenzophenone, and 2,4-dihydroxybenzophenone; 2-(2'-hydroxy-3'-tert-butyl-5'-methylphenyl)-5-chlorobenzotriazole; 2-(2'-hydroxy-3',5'-di-tert-butylphenyl)-5-chlorobenzotriazole; benzotriazoles such as 2-(2'-hydroxy-3',5'-di-tert-amylphenyl)benzotriazole, benzoates such as phenyl salicylate, p-tert-butylphenyl salicylate, 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate, and hexadecyl-3,5-di-tert-butyl-4-hydroxybenzoate, 2,2'-thiobis(4-tert-octylphenyl)benzotriazole, nickel compounds such as (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester nickel salt, [2,2'-thiobis(4-tert-octylphenolate)]-n-butylamine nickel, and (3,5-di-tert-butyl-4-hydroxybenzyl)phosphonic acid monoethyl ester nickel salt; substituted acrylonitriles such as methyl α-cyano-β-methyl-β-(p-methoxyphenyl)acrylate; and N'-2-ethylphenyl-N-ethoxy-5-tert-butylphenyl oxalic acid diamide and N-2-ethylphenyl-N'-2-ethoxyphenyl oxalic acid diamide. The compound includes one or more compounds selected from the group consisting of oxalic acid dianilides such as acid diamides, bis(2,2,6,6-tetramethyl-4-piperidine) sebaciate, poly[{(6-(1,1,3,3-tetramethylbutyl)imino}-1,3,5-triazine-2,4-diyl{4-(2,2,6,6-tetramethylpiperidyl)imino}hexamethylene], and hindered amine compounds such as a condensate of 2-(4-hydroxy-2,2,6,6-tetramethyl-1-piperidyl)ethanol and dimethyl succinate.

[0113] (lubricant) The lubricant preferably contains one or more selected from the group consisting of aliphatic hydrocarbons such as paraffin wax, polyethylene wax, and polypropylene wax; higher fatty acids such as capric acids, lauric acid, myristic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, and behenic acid, or metal salts thereof (for example, lithium salts, calcium salts, sodium salts, magnesium salts, and potassium salts); aliphatic alcohols such as palmityl alcohol, cetyl alcohol, and stearyl alcohol; aliphatic amides such as caproic amide, caprylic acid amide, capric acid amide, lauric acid amide, myristic acid amide, palmitic acid amide, and stearic acid amide; esters of aliphatic acids and alcohols; and fluorine compounds such as fluoroalkylcarboxylic acids or metal salts thereof and fluoroalkylsulfonic acid metal salts.

[0114] (hydrophilic stabilizer (or water-absorbing stabilizer)) The hydrophilic stabilizer (or water-absorbing stabilizer) preferably includes polyhydric alcohols described in JP-A-9-241484, polyhydric alcohols described in JP-A-2001-26718, and sorbitol derivatives described in JP-A-2001-26682. These are preferably used because they have excellent transparency and can produce resin compositions with little loss of transparency under high-temperature, high-humidity conditions. In particular, with highly hydrophobic resins such as cyclic olefin resins, if trace amounts of moisture are incorporated during molding, cracks may occur around the water molecules when the molded product is used. The resin composition of a cyclic olefin resin and a hydrophilic stabilizer obtained by the manufacturing method of this embodiment can minimize such cracking and is extremely useful.

[0115] The polyhydric alcohol used as the hydrophilic stabilizer has a molecular weight of 2000 or less, and the ratio of the number of carbon atoms to the number of hydroxyl groups in the same molecule is preferably 1.5 to 30, more preferably 3 to 20, and even more preferably 6 to 20, and includes those with 6 or more carbon atoms. If the ratio and number of carbon atoms are within this range, the compatibility with the cyclic olefin resin is good and there is no risk of foaming during melt-kneading, which may adversely affect transparency. The range of the number of carbon atoms is preferably 6 to 100, and more preferably 6 to 60.

[0116] The polyhydric alcohol preferably includes one in which at least one hydroxyl group in the molecule is bonded to a primary carbon atom. Polyhydric alcohols also include those having an ether bond, a thioether bond, an alicyclic hydrocarbon group, or an aromatic hydrocarbon group in the molecule, and are preferably aliphatic polyhydric alcohols. However, those having an ester group are not included. The polyhydric alcohol is preferably one or more selected from the group consisting of 3,7,11,15-tetramethyl-1,2,3-trihydroxyhexadecane, dihydroxyoctane, trihydroxyoctane, tetrahydroxyoctane, dihydroxynonane, trihydroxynonane, tetrahydroxynonane, pentahydroxynonane, hexahydroxynonane, dihydroxytriacontane, trihydroxytriacontane, and eicosahydroxytriacontane. Among these, 3,7,11,15-tetramethyl-1,2,3-trihydroxyhexadecane is more preferred.

[0117] Specific examples of polyhydric alcohols include 1,2-hexadecanediol, 2,3-heptadecanediol, 1,3-octadecanediol, and 1,2-decyltetradecanediol. The sorbitol derivatives used in this embodiment are compounds represented by the following general formulas (Ia) to (Ie).

[0118] [ka]

[0119] In the above general formula (Ia), each R and R' may be the same or different and is any one of an alkyl group having 1 to 8 carbon atoms, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms, and m and n each independently are an integer of 0 to 3.

[0120] The compound represented by the above general formula (Ia) is preferably 1,3,2,4-dibenzylidene sorbitol, 1,3-benzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-benzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, 1,3-p-methylbenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-benzylidene sorbitol, -methylbenzylidene sorbitol, 1,3,2,4-di(p-methylbenzylidene)sorbitol, 1,3,2,4-di(p-ethylbenzylidene)sorbitol, 1,3,2,4-di(pn-propylbenzylidene)sorbitol, 1,3,2,4-di(pi-propylbenzylidene)sorbitol, 1,3,2,4-di(pn-butylbenzylidene)sorbitol, 1,3,2,4-di(ps-butylbenzylidene)sorbitol, 1,3,2,4-di(pt-butylbenzylidene)sorbitol, 1,3,2,4-di(2' ,4'-dimethylbenzylidene)sorbitol, 1,3,2,4-di(p-methoxybenzylidene)sorbitol, 1,3,2,4-di(p-ethoxybenzylidene)sorbitol, 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-benzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3-p-chlorobenzylidene-2,4-p-ethylbenzylidene sorbitol, 1,3-p-methylbenzylidene Examples include 1,3-benzylidene-2,4-p-chlorobenzylidene sorbitol, 1,3-p-ethylbenzylidene-2,4-p-chlorobenzylidene sorbitol and 1,3,2,4-di(p-chlorobenzylidene)sorbitol and mixtures of two or more thereof, in particular 1,3,2,4-dibenzylidene sorbitol, 1,3,2,4-di(p-methylbenzylidene)sorbitol, 1,3,2,4-di(p-ethylbenzylidene)sorbitol, 1,3-p-chlorobenzylidene-2,4-p-methylbenzylidene sorbitol, 1,3,2,Contains one or more selected from the group consisting of 4-di(p-chlorobenzylidene)sorbitol and mixtures of two or more thereof.

[0121] The sorbitol derivative preferably includes a compound represented by the following general formula (Y).

[0122] [ka]

[0123] In the above general formula (Y), R and R' may be the same or different and represent a methyl group or an ethyl group.

[0124] [ka]

[0125] In the above general formula (Ib), each R may be the same or different and is any of an alkyl group having 1 to 8 carbon atoms, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms, and m is an integer of 0 to 3.

[0126] The compound represented by the general formula (Ib) above preferably includes one or more compounds selected from the group consisting of 2,4-benzylidene sorbitol, 2,4-pn-propylbenzylidene sorbitol, 2,4-pi-propylbenzylidene sorbitol, 2,4-pn-butylbenzylidene sorbitol, 2,4-ps-butylbenzylidene sorbitol, 2,4-pt-butylbenzylidene sorbitol, 2,4-(2',4'-dimethylbenzylidene)sorbitol, 2,4-p-methoxybenzylidene sorbitol, 2,4-p-ethoxybenzylidene sorbitol, 2,4-p-chlorobenzylidene sorbitol, and mixtures of two or more thereof.

[0127] [ka]

[0128] In the above general formula (Ic), each R may be the same or different and is any of an alkyl group having 1 to 8 carbon atoms, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms, and n is an integer of 0 to 3.

[0129] The compound represented by the general formula (Ic) preferably includes one or more compounds selected from the group consisting of 1,3-benzylidene sorbitol, 1,3-pn-propylbenzylidene sorbitol, 1,3-pi-propylbenzylidene sorbitol, 1,3-pn-butylbenzylidene sorbitol, 1,3-ps-butylbenzylidene sorbitol, 1,3-pt-butylbenzylidene sorbitol, 1,3-(2',4'-dimethylbenzylidene)sorbitol, 1,3-p-methoxybenzylidene sorbitol, 1,3-p-ethoxybenzylidene sorbitol, 1,3-p-chlorobenzylidene sorbitol, and mixtures of two or more thereof.

[0130] [ka]

[0131] In the above general formula (1-d), R 1 ~R 4 is an aliphatic acyl group having 10 to 30 carbon atoms or a hydrogen atom.

[0132] The compound represented by the general formula (Id) above preferably includes one or more compounds selected from the group consisting of 1,5-sorbitan monostearate, 1,5-sorbitan distearate, 1,5-sorbitan tristearate, 1,5-sorbitan monolaurate, 1,5-sorbitan dilaurate, 1,5-sorbitan trilaurate, 1,5-sorbitan monopalmitate, 1,5-sorbitan dipalmitate, 1,5-sorbitan tripalmitate, and mixtures of two or more of these compounds.

[0133] [ka]

[0134] In the above general formula (Ie), R 5 ~R 8 is an aliphatic acyl group having 10 to 30 carbon atoms or a hydrogen atom.

[0135] The compound represented by the general formula (Ie) above preferably includes one or more compounds selected from the group consisting of 1,4-sorbitan monostearate, 1,4-sorbitan distearate, 1,4-sorbitan tristearate, 1,4-sorbitan monolaurate, 1,4-sorbitan dilaurate, 1,4-sorbitan trilaurate, 1,4-sorbitan monopalmitate, 1,4-sorbitan dipalmitate, 1,4-sorbitan tripalmitate, and mixtures of two or more of these compounds.

[0136] The sorbitol derivative preferably includes one or more selected from the group consisting of benzylidene sorbitol derivatives represented by the general formulas (Ia) to (Ic), and more preferably includes a dibenzylidene sorbitol derivative represented by the general formula (Ia). The sorbitol derivatives represented by the general formulas (Ia) to (Ie) may be used singly or in combination of two or more. In this embodiment, from the viewpoint of further improving dispersibility, the sorbitol derivative may be used in combination with a fatty acid, such as a fatty acid having 10 to 30 carbon atoms.

[0137] The content of the additive (X) in the cyclic olefin resin composition of this embodiment is preferably 0.0001 to 10 parts by mass, more preferably 0.001 to 10 parts by mass, even more preferably 0.01 to 8 parts by mass, even more preferably 0.05 to 5 parts by mass, even more preferably 0.1 to 3 parts by mass, even more preferably 0.3 to 2 parts by mass, even more preferably 0.5 to 1.5 parts by mass, and even more preferably 0.8 to 1.2 parts by mass, relative to 100 parts by mass of the cyclic olefin copolymer (A).

[0138] <Molded body and optical member> The cyclic olefin resin molded article of this embodiment can be used in various shapes such as lens, sphere, rod, plate, column, cylinder, tube, fiber, film or sheet.

[0139] The cyclic olefin resin molded article of this embodiment is preferably an optical member. Optical components are components used in optical devices and the like, and are particularly suitable for use in optical components requiring 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, light converging lenses for head-up displays, light diffusing lenses for head-up displays, and lenses for various optical devices such as cameras for personal computers, mobile phones, smartphone cameras, cameras for tablet devices, cameras for mobile devices, digital cameras, and cameras for medical devices. Other uses include automotive interior panels, automotive lamp lenses, automotive inner lenses, automotive lens protective covers, and automotive light guides.

[0140] Although the embodiments of the present invention have been described above, these are merely examples of the present invention, and various other configurations can also be adopted. Furthermore, the present invention is not limited to the above-described embodiment, and modifications and improvements within the scope of achieving the object of the present invention are included in the present invention. [Example]

[0141] The present invention will be described in more detail below based on examples, but the present invention is not limited to these examples.

[0142] (Catalyst Preparation) Ethyl aluminum sesquichloride (C2H5)3Al2Cl3 was diluted with cyclohexane to prepare an organoaluminum compound catalyst solution.

[0143] (polymerization) In a stirred polymerization reactor, 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 The copolymerization of ethylene with 3-dodecene was carried out to obtain a cyclic olefin copolymer solution. Here, ethylene was fed into the polymerization reactor together with hydrogen gas.

[0144] (decalcification) Water and an aqueous solution of sodium hydroxide were added to the resulting cyclic olefin copolymer solution to terminate the polymerization reaction and remove the catalyst residues present in the cyclic olefin copolymer solution (decalcification). Pentaerythritol-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] was added as a phenolic antioxidant to the decalcified cyclic olefin copolymer solution, and the mixture was mixed in a stirring tank for 1 hour.

[0145] (Desolvation) The cyclic olefin copolymer solution containing the stabilizer was heated to 180°C, and the solvent and unreacted monomers were removed to obtain the molten cyclic olefin copolymer (ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene) was obtained. The glass transition temperature Tg of the resulting cyclic olefin copolymer was evaluated and found to be 155°C.

[0146] (Extrusion) 100 parts by mass of the obtained cyclic olefin copolymer and 0.9 parts by mass of distilled diglycerin fatty acid ester (Rikemal DO-100, manufactured by Riken Vitamin Co., Ltd.) were kneaded and pelletized, and the obtained pellets were dried with hot air at a temperature of 100°C for 4 hours to obtain a cyclic olefin resin composition.

[0147] (vacuum drying) The obtained cyclic olefin resin composition was dried at 23° C. and −85 kPa for 12 hours in a vacuum dryer (LCV-243, manufactured by Espec Corporation), after which the pressure inside the vacuum dryer was returned to normal pressure with air.

[0148] (Nitrogen drying) The vacuum-dried cyclic olefin resin composition was immediately placed in a continuous nitrogen dryer (DO-10N, manufactured by Kawata Co., Ltd.) and dried at 120° C. and an oxygen concentration of 1% for 20 hours.

[0149] (melt and injection molding) The nitrogen-dried cyclic olefin resin composition was transferred to an injection molding machine, and after melting the cyclic olefin resin composition, injection molding was carried out under the conditions below to produce lenses with optical surfaces measuring 59 mm x 50 mm x 7 mm thick. Lens sampling was carried out once every hour, and molding was carried out continuously for 7 days. Injection molding machine: SE-75EV, manufactured by Sumitomo Heavy Industries Mold: φ59VR model lens Cylinder temperature: 260℃ Back pressure: 30kgf / cm 2 Screw rotation speed: 30 rpm

[0150] (Lens observation) The obtained lenses were observed in bright field using a stereo microscope (SMZ-1000, manufactured by Nikon Corporation), and the defect rate (%) due to bubbles was calculated according to the following criteria: The defect rate (%) was calculated as the average value for all lenses (24 x 7 = 168 lenses) sampled once every hour for 7 days. (standard) A (Good): When observed under a microscope, there are no bubbles with a maximum diameter of 20 μm or more that can be visually determined. B (Poor): When observed under a microscope, there is one or more bubbles with a maximum diameter of 20 μm or more that can be visually determined.

[0151] [Comparative Example 1] The evaluation was carried out in the same manner as in Example 1, except that the vacuum drying treatment was not carried out.

[0152] [Table 1]

Claims

1. A method for producing a cyclic olefin resin molded product, comprising: Step (1) includes a step of subjecting a cyclic olefin resin composition to a vacuum treatment and a step of subjecting the composition to an inert gas treatment; a step (2) of melting the cyclic olefin resin composition; and (3) a step of injecting the molten cyclic olefin resin composition into a mold, in this order.

2. The method for producing a cyclic olefin resin molded article according to claim 1 , wherein in the step (1), the inert gas treatment step is carried out after the vacuum treatment step.

3. The method for producing a cyclic olefin resin molded article according to claim 1 or 2, wherein the inert gas treatment is carried out at an oxygen concentration of 5% or less.

4. The method for producing a cyclic olefin resin molded article according to any one of claims 1 to 3, wherein the vacuum treatment is carried out at 10°C or higher.

5. The method for producing a cyclic olefin resin molded article according to any one of claims 1 to 4, wherein the vacuum treatment step is carried out at a vacuum degree of -30 kPa or less.

6. The method for producing a cyclic olefin resin molded article according to any one of claims 1 to 5, wherein the vacuum treatment is carried out for 6 hours or more.

7. The method for producing a cyclic olefin resin molded article according to any one of claims 1 to 6, wherein the inert gas treatment is carried out at 50°C or higher.

8. The method for producing a cyclic olefin resin molded article according to any one of claims 1 to 7, wherein the inert gas treatment step is carried out for 6 hours or more.

9. The method for producing a cyclic olefin resin molded article according to any one of claims 1 to 8, wherein the cyclic olefin resin composition comprises a cyclic olefin copolymer (A) and an additive (X).

10. The method for producing a cycloolefin resin molded article according to claim 9 , wherein the additive (X) comprises a hydrophilic agent.

11. The cyclic olefin copolymer (A) is At least one olefin-derived repeating unit (a) represented by the following general formula (I); a repeating unit (b) derived from at least one cyclic olefin monomer selected from the group consisting of a repeating unit (AA) represented by the following general formula (II), a repeating unit (AB) represented by the following general formula (III), and a repeating unit (AC) represented by the following general formula (IV); The method for producing a cycloolefin resin molded article according to claim 9 or 10, comprising: 【Chemistry 1】 (In the above general formula (I), R ３００ represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms. 【Chemistry 2】 (In the above general 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.) 【Transformation 3】 (In the above general formula (III), x and d each independently represent an integer of 0 or 1 or more, y and z each independently represent 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 4】 (In the above general 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 1≦f≦18.

12. The cyclic olefin copolymer (A) is A repeating unit (AA) represented by the following general formula (II), and having a repeating unit (C) derived from a cyclic olefin having an aromatic ring, the repeating unit (AA) does not contain an aromatic ring, The method for producing a cyclic olefin-based resin molded product according to claim 9 or 10, wherein the cyclic olefin having an aromatic ring comprises one or more compounds selected from the group consisting of a compound represented by the following general formula (C-1), a compound represented by the following general formula (C-2), and a compound represented by the following general formula (C-3): 【Transformation 5】 (In the above general 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.) 【Transformation 6】 (In the above 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. 【Transformation 7】 (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 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. 【Transformation 8】 (In the above 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.

13. The method for producing a cyclic olefin resin molded article according to any one of claims 1 to 12, wherein the cyclic olefin resin molded article is an optical element.

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