Cyclic olefin resin composition and molded article

Abstract

This cyclic olefin resin composition contains (A) a cyclic olefin polymer, (B) a diester compound of triglycerin and a fatty acid, and (C) a compound which is a monoester compound of diglycerin and a fatty acid or a monoester compound of glycerin and a fatty acid, and which has a molecular weight that does not exceed 70% of the molecular weight of compound (B). The total amount of compound (B) and compound (C) is 0.10 to 3 parts by mass per 100 parts by mass of polymer (A).

Description

[Technical field]

[0001] The present invention relates to a cyclic olefin resin composition and a molded article. [Background technology]

[0002] Cyclic olefin polymers are used in optical lenses such as imaging lenses, fθ lenses, pickup lenses, etc. Cyclic olefin polymers used in molded articles such as optical lenses are required to have properties such as high transparency, excellent dimensional stability, excellent heat resistance, and excellent moisture resistance.

[0003] An example of an invention relating to a cyclic olefin polymer is a resin composition containing a cyclic olefin polymer and diglycerol monooleate, etc., as described in Patent Document 1. Patent Document 1 describes a resin composition containing a polymer containing an alicyclic structure in at least a portion of the repeating structural units, and a fatty acid ester of a fatty acid and a polyhydric alcohol having one or more ether groups.

[0004] Furthermore, Patent Document 2 describes a cyclic olefin resin composition containing a cyclic olefin polymer (A) and a triglycerol fatty acid ester.

[0005] Patent Document 3 describes a resin composition containing an alicyclic structure-containing polymer and a polyglycerol fatty acid ester-based additive, in which the polyglycerol fatty acid ester-based additive is composed of one or more polyglycerol fatty acid ester compounds, and the content of the polyglycerol fatty acid ester-based additive is 0.2 to 2.0 parts by weight per 100 parts by weight of the alicyclic structure-containing polymer. [Prior art documents] [Patent documents]

[0006] [Patent Document 1] JP 2015-199939 A [Patent Document 2] JP 2018-172665 A [Patent Document 3] International Publication No. 2017 / 033968 Summary of the Invention [Problem to be solved by the invention]

[0007] Cyclic olefin polymers are prone to microcracks after high-temperature, high-humidity tests, and the microcracks that occur degrade the optical properties of the molded article, i.e., the internal haze of the molded article increases due to the microcracks, degrading the optical properties, for example, of the lens.

[0008] One method for preventing the occurrence of microcracks is to add a hydrophilic stabilizer to the cyclic olefin polymer, which can prevent the occurrence of microcracks.

[0009] However, according to the study by the present inventors, it was found that, depending on the type of hydrophilic stabilizer, dirt originating from the hydrophilic stabilizer adheres to the part of the mold that comes into contact with the molded product or to the mold vent part during molding. If dirt adheres to the part of the mold that comes into contact with the molded product, dirt also adheres to the surface of the molded product. For example, when molding a lens, dirt adheres to the lens surface, resulting in a deterioration of optical properties.

[0010] The present invention has been made in consideration of the above problems, and has an object to provide a cyclic olefin resin composition capable of suppressing the occurrence of microcracks and mold staining. [Means for solving the problem]

[0011] The present inventors have conducted extensive research to solve the above problems, and have found that the use of a specific hydrophilic stabilizer in combination with a monoester of glycerin or diglycerin and a fatty acid, which has a lower molecular weight than the hydrophilic stabilizer, can solve both the generation of microcracks and mold staining, thereby completing the present invention.

[0012] That is, according to the present invention, there are provided a cyclic olefin resin composition, a molded article, and an optical member as shown below.

[0013] [1] A cyclic olefin polymer (A), A diester compound of triglycerin and a fatty acid (B), (C) a monoester compound of diglycerin and a fatty acid or a monoester compound of glycerin and a fatty acid, the molecular weight of which is 70% or less of that of the compound (B); Including, The cyclic olefin resin composition, wherein the total amount of the compound (B) and the compound (C) is 0.10 parts by mass or more and 3 parts by mass or less per 100 parts by mass of the cyclic olefin polymer (A). [2] The cyclic olefin resin composition according to the above [1], The cyclic olefin resin composition, wherein the cyclic olefin polymer (A) comprises at least one member selected from the group consisting of a cyclic olefin copolymer (A-1) and a ring-opening polymer of a cyclic olefin (A-2). [3] The cyclic olefin resin composition according to the above [2], wherein the cyclic olefin polymer (A) contains the copolymer (A-1), The cyclic olefin resin composition, wherein the cyclic olefin copolymer (A-1) has a structural unit (a) and a structural unit (b). Structural unit (a): at least one structural unit derived from an olefin represented by the following general formula (I). Structural unit (b): one or more structural units derived from cyclic olefins 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). [ka] In the above general formula (I), R 300represents 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, and w is 0 or 1. 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. 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 an integer of 0 to 2. 81 ~R 99 R 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. 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. 92 and R 95 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 , R101 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. [4] The cyclic olefin resin composition according to the above item [3], wherein the cyclic olefin copolymer (A-1) has a repeating unit (AA) represented by the above general formula (II) and a structural unit (D) derived from a cyclic olefin having an aromatic ring, and the repeating unit (AA) does not contain an aromatic ring; A cyclic olefin resin composition, comprising one or more aromatic ring-containing cyclic olefins selected from the group consisting of compounds represented by general formula (D-1), compounds represented by general formula (D-2), and compounds represented by general formula (D-3). [ka] In the above general formula (D-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. 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. When q=1 or 2, R 10 and R 11 , R 11 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 17 and R 17 , 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. [ka] In the above general formula (D-2), n and m are each independently 0, 1 or 2, and q is 1, 2 or 3. 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. 28 and R 29 , R 29 and R 30 , R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring. When q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R 30 , R 30 and R 31 , R 31 and R 31 may be bonded to each other to form a monocycle or polycycle, the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring. [ka] In the above general formula (D-3), q is 1, 2 or 3; 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. 36and 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. 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. [5] The cyclic olefin resin composition according to any one of the above [1] to [4], The compound (B) has a molecular weight of 300 to 2,000. [6] The cyclic olefin resin composition according to any one of the above [1] to [5], The cyclic olefin resin composition, wherein the cyclic olefin polymer (A) has a glass transition temperature of 130° C. or higher and 170° C. or lower, as measured by a differential scanning calorimeter (DSC). [7] A molded article comprising the cyclic olefin resin composition according to any one of the above [1] to [6]. [8] The molded article according to the above [7], which is an optical component. Effect of the Invention

[0014] According to the cyclic olefin resin composition of the present invention, a molded article that can be an optical part that can suppress the occurrence of microcracks and mold stains can be obtained. Such a molded article has low internal haze and can suppress the increase in internal haze before and after moist heat resistance test. Therefore, it can be mainly used for optical applications and lenses. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0015] 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.

[0016] As described above, according to the findings of the present inventors, depending on the type of hydrophilic stabilizer, there is a problem in that during molding, dirt originating from the hydrophilic stabilizer adheres to the parts of the mold that come into contact with the molded product or to the mold vent parts.

[0017] The present inventors have conducted extensive research to solve the above problems, and have found that the occurrence of microcracks and mold staining can be both solved by using a specific hydrophilic stabilizer in combination with a monoester of glycerin or diglycerin and a fatty acid, which has a lower molecular weight than the hydrophilic stabilizer.

[0018] That is, the cyclic olefin resin composition according to this embodiment is as follows.

[0019] <Cyclic olefin resin composition> The cyclic olefin resin composition according to the present embodiment comprises: A cyclic olefin polymer (A), A diester compound of triglycerin and a fatty acid (B), (C) a monoester compound of diglycerin and a fatty acid or a monoester compound of glycerin and a fatty acid, the molecular weight of which is 70% or less of that of the compound (B); Including, The total amount of the compound (B) and the compound (C) is 0.10 parts by mass or more and 3 parts by mass or less with respect to 100 parts by mass of the polymer (A).

[0020] The cyclic olefin resin composition according to the present embodiment can suppress the occurrence of microcracks and mold stains. In addition, the molded article of the cyclic olefin resin composition according to the present embodiment has low internal haze and can reduce the increase in internal haze before and after a moist heat resistance test. Furthermore, the molded article can maintain transparency before and after a moist heat resistance test, so it can be suitably used for applications that require transparency.

[0021] [Cyclic olefin polymer (A)] The cyclic olefin polymer (A) according to this embodiment is a copolymer having a structural unit derived from a cyclic olefin as an essential constituent unit.

[0022] The cyclic olefin polymer (A) preferably contains at least one selected from the group consisting of a cyclic olefin copolymer (A-1) and a ring-opening polymer of a cyclic olefin (A-2). The resulting optical component can have a good balance between transparency and refractive index while further improving heat resistance and moldability.

[0023] (Cyclic Olefin Copolymer (A-1)) The cyclic olefin copolymer (A-1) according to this embodiment may be, for example, a copolymer of ethylene or an α-olefin with a cyclic olefin. The cyclic olefin compound constituting the cyclic olefin copolymer (A-1) is not particularly limited, but examples thereof include the cyclic olefin monomers described in paragraphs 0037 to 0063 of WO 2006 / 0118261.

[0024] The cyclic olefin copolymer (A-1) preferably has the structural unit (a) and the structural unit (b) from the viewpoint of further improving the optical properties of the obtained optical component. The optical properties refer to the properties of the optical component such as transparency and refractive index.

[0025] Structural unit (a): at least one structural unit derived from an olefin represented by the following general formula (I).

[0026] [ka]

[0027] 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.

[0028] Structural unit (b): at least one structural unit derived from a cyclic olefin 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).

[0029] [ka]

[0030] In the above general formula (II), u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. 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. 75 ~R 78 may be bonded to each other to form a monocyclic or polycyclic ring.

[0031] [ka]

[0032] 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 an integer of 0 to 2. 81 ~R 99R 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. 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. 92 and R 95 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 general formula (IV), R 100 , 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.

[0035] The olefin monomer, which is one of the copolymerization raw materials of the cyclic olefin copolymer (A-1) according to the present embodiment, undergoes addition polymerization to form the constitutional unit represented by the above general formula (I). Specifically, the olefin monomer represented by the following general formula (Ia) corresponding to the above general formula (I) is used.

[0036] [ka]

[0037] In the above general formula (Ia), R 300 represents a hydrogen atom or a linear or branched hydrocarbon group having 1 to 29 carbon atoms.

[0038] Examples of the olefin monomer represented by the general 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 optical components having better heat resistance, mechanical properties, and optical properties, among these, ethylene and propylene are preferred, and ethylene is particularly preferred. Two or more types of olefin monomers represented by the general formula (Ia) may be used.

[0039] When the total of the structural units constituting the cyclic olefin copolymer (A-1) according to this embodiment is taken as 100 mol %, the proportion of the olefin-derived structural unit (a) is preferably 5 mol % or more and 95 mol % or less, more preferably 20 mol % or more and 90 mol % or less, even more preferably 40 mol % or more and 80 mol % or less, and particularly preferably 50 mol % or more and 70 mol % or less. The proportion of olefin-derived structural units (a) is: 13 It can be measured by C-NMR.

[0040] The cyclic olefin monomer, which is one of the copolymerization raw materials of the cyclic olefin copolymer (A-1) according to this embodiment, undergoes addition polymerization to form the structural unit (b) derived from the cyclic olefin represented by the above general formula (II), the above general formula (III) or the above general formula (IV). Specifically, the cyclic olefin monomer represented by the general formula (IIa), (IIIa) and (IVa) corresponding to the above general formula (II), the above general formula (III) and the above general formula (IV), respectively, is used.

[0041] [ka]

[0042] In the above general formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer of 0 or more and 2 or less, 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.

[0043] [ka]

[0044] In the above general formula (IIIa), x and d each independently represent an integer of 0 or 1 or more, preferably an integer of 0 or more and 2 or less, more preferably 0 or 1; y and z each independently represent 0, 1, or 2; 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 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.

[0045] [ka]

[0046] In the above general formula (IVa), R 100 , 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.

[0047] By using the olefin monomer represented by the above-mentioned general formula (Ia) or the cyclic olefin monomer represented by the general formula (IIa), (IIIa) or (IVa) as the copolymerization component, the solubility of the cyclic olefin copolymer (A-1) in a solvent is further improved, resulting in good moldability and improved product yield.

[0048] Specific examples of the cyclic olefin monomer represented by the general formula (IIa), (IIIa) or (IVa) that can be used include the compounds described in paragraphs 0037 to 0063 of WO 2006 / 0118261.

[0049] 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, 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.

[0050] Among the cyclic olefin monomers represented by the general formula (IIa), (IIIa) or (IVa), the cyclic olefin monomer represented by the general formula (IIa) is preferred.

[0051] Examples of the cyclic olefin monomer represented by the above general formula (IIa) include bicyclo[2.2.1]-2-heptene (also called norbornene), tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (also called tetracyclododecene) is preferably used, and tetracyclo[4.4.0.1 2,5 .1 7,10 It is more preferable to use ]-3-dodecene. These cyclic olefins have a rigid ring structure, and therefore have the advantage that the elastic modulus of the copolymer and the optical component can be easily maintained.

[0052] When the total of the structural units constituting the cyclic olefin copolymer (A-1) according to this embodiment is taken as 100 mol %, the proportion of the structural unit (b) derived from the cyclic olefin 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 20 mol % or more and 60 mol % or less, and particularly preferably 30 mol % or more and 50 mol % or less.

[0053] The copolymerization type of the cyclic olefin copolymer (A-1) according to this embodiment is not particularly limited, but can be, for example, random copolymer, block copolymer, etc. In this embodiment, it is preferable to use a random copolymer as the cyclic olefin copolymer (A-1) according to this embodiment, since it has excellent optical properties such as transparency, refractive index and birefringence, and can obtain high-precision optical components.

[0054] The cyclic olefin copolymer (A-1) according to the present embodiment is a copolymer of ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 A random copolymer of ethylene and bicyclo[2.2.1]-2-heptene is preferred, and a random copolymer of ethylene and tetracyclo[4.4.0.1 2,5.1 7,10 A random copolymer with 1-dodecene is more preferred.

[0055] The copolymer (A-1) according to this embodiment may be used alone or in combination of two or more kinds.

[0056] The copolymer (A-1) according to this embodiment 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, and the like.

[0057] It is preferred that the cyclic olefin copolymer (A-1) has a repeating unit (AA) represented by the above general formula (II) and a structural unit (D) derived from a cyclic olefin having an aromatic ring, the repeating unit (AA) does not contain an aromatic ring, and the cyclic olefin having an aromatic ring contains one or more compounds selected from the group consisting of a compound represented by the following formula (D-1), a compound represented by the following formula (D-2), and a compound represented by the following formula (D-3).

[0058] [ka]

[0059] In the above (D-1), n ​​and q are each independently 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. Also, when q=0, R 10 and R 11 , R 11 and R 12 , R 12 and R 13 , R13 and R 14 , R 14 and R 15 , R 15 and R 10 may be bonded to each other to form a monocyclic or polycyclic ring. When q=1 or 2, R 10 and R 11 , R 11 and R 17 , R 17 and R 17 , R 17 and R 12 , R 12 and R 13 , R 13 and R 14 , R 14 and R 15 , R 15 and R 16 , R 16 and R 16 , R 16 and R 10 may be bonded to each other to form a monocycle or polycycle, and the monocycle or polycycle may have a double bond, or the monocycle or polycycle may be an aromatic ring.

[0060] [ka]

[0061] In the above formula (D-2), n and m are each independently 0, 1 or 2, and q is 1, 2 or 3. 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. 28 and R 29 , R 29 and R 30 , R 30 and R 31 may be bonded to each other to form a monocyclic or polycyclic ring. When q=2 or 3, R 28 and R 28 , R 28 and R 29 , R 29 and R30 , R 30 and R 31 , R 31 and R 31 may be bonded to each other to form a monocycle or polycycle, the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring.

[0062] [ka]

[0063] In the above formula (D-3), q is 1, 2 or 3; 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. 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. 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.

[0064] The hydrocarbon groups having 1 to 20 carbon atoms of (D-1) to (D-3) each independently include, for example, an alkyl group having 1 to 20 carbon atoms, a cycloalkyl group having 3 to 15 carbon atoms, and an aromatic ring hydrocarbon group. More specifically, the alkyl group includes 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. The cycloalkyl group includes a cyclohexyl group. The aromatic hydrocarbon group includes 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.

[0065] Such a cyclic olefin copolymer (A-1) can further suppress the generation of haze before and after a moist heat resistance test, and can further suppress the contamination of the inside of a mold during continuous molding.

[0066] When the total structural units of the cyclic olefin copolymer (A-1) according to this embodiment are taken as 100 mol%, the content of the repeating unit (AA) represented by general formula (II) and the structural unit (D) derived from a cyclic olefin having an aromatic ring 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 80 mol% or less, still more preferably 30 mol% or more and 80 mol% or less, and even more preferably 40 mol% or more and 78 mol% or less. In this embodiment, the contents of the repeating unit (AA) and the structural unit (D) are, for example, 1 H-NMR or 13 It can be measured by C-NMR.

[0067] (Ring-opening polymer of cyclic olefin (A-2)) As the cyclic olefin polymer (A), a ring-opening polymer (A-2) of a cyclic olefin can be used. Examples of the ring-opening polymer (A-2) of a cyclic olefin include a ring-opening polymer of a norbornene-based monomer, a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with the norbornene-based monomer, and hydrogenated products thereof.

[0068] Examples of norbornene monomers include bicyclo[2.2.1]hept-2-ene (common name: norbornene) and its derivatives (those having a substituent on the ring), tricyclo[4.3.0 1,6 .1 2,5 ]Deca-3,7-diene (commonly known as dicyclopentadiene) and its derivatives, 7,8-benzotricyclo[4.3.0.1 2,5 ]dec-3-ene (commonly known as methanotetrahydrofluorene: 1,4-methano-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene (common name: tetracyclododecene) and its derivatives, etc. The substituents on the rings of these derivatives include alkyl groups, alkylene groups, vinyl groups, alkoxycarbonyl groups, and alkylidene groups. The derivatives may have one or more substituents. Examples of derivatives having a substituent on the ring include 8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene, 8-ethylidene-tetracyclo[4.4.0.1 2,5 .1 7,10 ]dodec-3-ene and the like. These norbornene monomers may be used alone or in combination of two or more.

[0069] A ring-opening polymer of a norbornene-based monomer, or a ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization therewith, can be obtained by polymerizing the monomer components in the presence of a known ring-opening polymerization catalyst. Examples of the ring-opening polymerization catalyst that can be used include catalysts consisting of a halide of a metal such as ruthenium or osmium, a nitrate or an acetylacetone compound, and a reducing agent; and catalysts consisting of a halide of a metal such as titanium, zirconium, tungsten, or molybdenum, or an acetylacetone compound, and an organoaluminum compound. Examples of other monomers capable of undergoing ring-opening copolymerization with norbornene monomers include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

[0070] A hydrogenated ring-opening polymer of a norbornene-based monomer or a hydrogenated ring-opening polymer of a norbornene-based monomer and another monomer capable of ring-opening copolymerization with the norbornene-based monomer can usually be obtained by adding a known hydrogenation catalyst containing a transition metal such as nickel or palladium to a polymerization solution of the ring-opening polymer and hydrogenating the carbon-carbon unsaturated bonds.

[0071] The ring-opened polymer (A-2) of cyclic olefin according to this embodiment can be produced by appropriately selecting the conditions according to the methods described in, for example, JP-A-60-26024, JP-A-9-268250, JP-A-63-145324, JP-A-2001-72839, and the like.

[0072] The ring-opening polymer (A-2) of cyclic olefin according to this embodiment may be used alone or in combination of two or more kinds.

[0073] The content of the cyclic olefin copolymer (A) according to this embodiment in the resin composition is preferably 80% by mass or more and 99% by mass or less, more preferably 90% by mass or more and 99% by mass or less, and even more preferably 95% by mass or more and 99% by mass or less.

[0074] The glass transition temperature (Tg) of the cyclic olefin copolymer (A) according to the present embodiment is preferably in the range of 130° C. to 170° C. When the glass transition temperature (Tg) of the cyclic olefin copolymer (A) is in the above range, sufficient heat resistance and good moldability can be obtained when used as an optical component that requires heat resistance, such as an in-vehicle camera lens or a camera lens for a mobile device.

[0075] The glass transition temperature (Tg) of the cyclic olefin copolymer (A) according to the present embodiment can be measured using a differential scanning calorimeter (DSC).For example, using RDC220 manufactured by SII Nano Technology Co., Ltd., the glass transition temperature can be measured by increasing the temperature from room temperature to 200°C at a heating rate of 10°C / min under a nitrogen atmosphere, then holding for 5 minutes, then lowering the temperature to 30°C at a heating rate of 10°C / min, then holding for 5 minutes, and then raising the temperature to 200°C at a heating rate of 10°C / min.

[0076] [Diester compound of triglycerin and fatty acid (B)] The diester compound (B) according to the present embodiment is a diester compound of triglycerin and a fatty acid. There is no particular limitation as long as it is a diester compound of triglycerin and a fatty acid, but the molecular weight of the diester compound (B) is preferably 300 to 2000, more preferably 400 to 1500, even more preferably 500 to 1000, and even more preferably 700 to 900. Here, when the diester compound (B) contains two or more kinds of diester compounds, the above molecular weight of the diester compound (B) means the molecular weight of the diester compound (B) having the highest content (hereinafter, the "highest content" is also referred to as the "main component"). In this case, an ester compound of triglycerin and a fatty acid, which is a mixture of a monoester compound of triglycerin and a fatty acid or a triester compound of triglycerin and a fatty acid, may be used as long as it contains a diester compound (B) of triglycerin and a fatty acid as the main component.

[0077] An example of such a compound (B) is preferably at least one selected from the group consisting of triglycerol dioleate and triglycerol distearate, more preferably triglycerol dioleate.

[0078] [Monoester compound of diglycerin and fatty acid or monoester compound of glycerin and fatty acid (C)] The monoester compound (C) according to the present embodiment is a monoester compound of diglycerin and a fatty acid or a monoester compound of glycerin and a fatty acid. The molecular weight of the monoester compound (C) is lower than that of the diester compound (B), typically 70% or less, more preferably 65% ​​or less, and even more preferably 60% or less of that of the diester compound (B). The specific range of the molecular weight is preferably 100-500, more preferably 200-480, and further preferably 300-450. Here, when the monoester compound (C) contains two or more kinds of monoester compounds, the above molecular weight of the monoester compound (C) means the molecular weight of the main component monoester compound (C).

[0079] The total amount of the diester compound (B) and the monoester compound (C) is 0.10 parts by mass or more and 3 parts by mass or less, more preferably 0.15 parts by mass or more and 2.5 parts by mass or less, even more preferably 0.18 parts by mass or more and 2 parts by mass or less, even more preferably 0.20 parts by mass or more and 1.5 parts by mass or less, even more preferably 0.25 parts by mass or more and 1.2 parts by mass or less, even more preferably 0.30 parts by mass or more and 1.0 parts by mass or less, even more preferably 0.35 parts by mass or more and 0.80 parts by mass or less, based on 100 parts by mass of the cyclic olefin polymer (A). In this way, both the occurrence of microcracks and mold stains can be suppressed.

[0080] The mass ratio of the diester compound (B) to the monoester compound (C) is not particularly limited, but is preferably diester compound (B):monoester compound (C)=1:4 to 4:1, more preferably diester compound (B):monoester compound (C)=1:3 to 3:1, and even more preferably diester compound (B):monoester compound (C)=1:2.5 to 2.5:1.

[0081] The content of the diester compound (B) in the cyclic olefin resin composition according to this embodiment is preferably from 0.01 to 1.5 parts by mass, more preferably from 0.05 to 1.0 parts by mass, even more preferably from 0.08 to 0.80 parts by mass, even more preferably from 0.10 to 0.60 parts by mass, even more preferably from 0.10 to 0.40 parts by mass, and even more preferably from 0.10 to 0.30 parts by mass, relative to 100 parts by mass of the cyclic olefin polymer (A).

[0082] In addition, the content of the ester compound of triglycerin and fatty acid (a mixture of a diester compound (B) of triglycerin and fatty acid, a monoester compound of triglycerin and fatty acid, and a triester compound of triglycerin and fatty acid) in the cyclic olefin resin composition according to this embodiment is preferably from 0.05 to 2.5 parts by mass, more preferably from 0.10 to 2.0 parts by mass, even more preferably from 0.15 to 1.5 parts by mass, even more preferably from 0.20 to 1.0 parts by mass, and even more preferably from 0.25 to 0.80 parts by mass, relative to 100 parts by mass of the cyclic olefin polymer (A).

[0083] The content of the monoester compound (C) in the cyclic olefin resin composition according to this embodiment is preferably from 0.05 to 2.0 parts by mass, more preferably from 0.10 to 1.5 parts by mass, even more preferably from 0.15 to 1.0 parts by mass, even more preferably from 0.20 to 0.80 parts by mass, even more preferably from 0.20 to 0.60 parts by mass, and even more preferably from 0.25 to 0.55 parts by mass, relative to 100 parts by mass of the cyclic olefin polymer (A).

[0084] By using the above diester compound (B) in combination with a monoester compound (C) having a lower molecular weight than the diester compound (B) and formed from glycerin or diglycerin and a fatty acid, it is possible to simultaneously suppress both the occurrence of microcracks and mold fouling. This is believed to be because the molecular weight of the monoester compound (C) is lower than that of the diester compound (B), and therefore the volatility of the monoester compound (C) is higher than that of the diester compound (B).

[0085] A specific example of such a monoester compound (C) is preferably at least one selected from the group consisting of diglycerol monooleate and glycerol monostearate, but is not limited thereto.

[0086] The total content of the cyclic olefin polymer (A), the diester compound (B) and the monoester compound (C) in the cyclic olefin resin composition is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and particularly preferably 95% by mass or more, based on 100% by mass of the entire cyclic olefin resin composition. By being equal to or more than the lower limit, the optical performance can be further improved. The upper limit of the total content is not particularly limited, but is preferably 100% by mass or less, and more preferably 98% by mass or less.

[0087] [Other ingredients] The cyclic olefin resin composition according to the present embodiment may contain, as necessary, weather resistance stabilizers, heat resistance stabilizers, antioxidants, metal deactivators, hydrochloric acid absorbers, antistatic agents, flame retardants, slip agents, antiblocking agents, antifogging agents, lubricants, natural oils, synthetic oils, waxes, organic or inorganic fillers, and the like, within the range that does not impair the object of the present embodiment, and the blending ratios of the fillers are appropriate.

[0088] The cyclic olefin resin composition according to the present embodiment can be preferably made into a molded article. The method of molding the cyclic olefin resin composition 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, 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 is preferred from the viewpoint of moldability and productivity. In addition, 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 in the range of usually 150°C to 400°C, preferably 200°C to 350°C, more preferably 230°C to 330°C.

[0089] The cyclic olefin resin composition according to the present embodiment can be obtained by, for example, a method of melt-kneading the cyclic olefin polymer (A) and other components added as required using a known kneading device such as an extruder and a Banbury mixer; a method of dissolving the cyclic olefin polymer (A) and other components added as required in a common solvent and then evaporating the solvent; a method of adding a solution of the cyclic olefin polymer (A) and other components added as required in a poor solvent to precipitate; etc. The diester compound (B) and the monoester compound (C) can be added before or during the melt-kneading using a kneading device such as an extruder and a Banbury mixer.

[0090] The resulting molded product is then annealed for 2 to 8 hours at a temperature in the range of (glass transition temperature (Tg) of the cyclic olefin polymer (A)-40)°C to (glass transition temperature (Tg) of the cyclic olefin polymer (A)-5)°C, to obtain an optical component. The annealing treatment relaxes the molecules of the cyclic olefin polymer (A) in the molded product, reducing the free volume. This makes it difficult for a change in specific gravity (change in volume) to occur even when the product is heated. Here, if the annealing conditions are made strict, the molded body will deform and will not return to its original shape, so it is preferable to carry out the annealing treatment under the above conditions within a range in which the molded body does not deform. In other words, it is preferable to carry out the annealing treatment at a temperature and for a time period in which the molded body does not deform.

[0091] The optical member obtained in the above manner has excellent resistance to moist heat. Therefore, the increase in internal haze before and after the moist heat resistance test can be suppressed, and the optical member can be preferably used mainly for optical applications and lenses. In addition, the optical member can maintain transparency before and after the moist heat resistance test, and therefore can be preferably used for applications requiring transparency.

[0092] 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

[0093] 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.

[0094] [Example 1] <Polymerization of Cyclic Olefin Copolymer (A-1)> (Catalyst Adjustment) VO(OC2H5)Cl2 was diluted with cyclohexane to prepare a cyclohexane solution of vanadium catalyst with a vanadium concentration of 6.7 mmol / L. Ethyl aluminum sesquichloride (Al(C2H5) 1.5 Cl 1.5 ) was diluted with cyclohexane to prepare a cyclohexane solution of an organoaluminum compound catalyst having an aluminum concentration of 107 mmol / L.

[0095] (polymerization) A stirred polymerization vessel (inner diameter 500 mm, reaction volume 100 L) was used to continuously polymerize ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 A copolymerization reaction with 1,2-diphenylmethane was carried out. Cyclohexane was used as the polymerization solvent. When carrying out this polymerization reaction, the cyclohexane solution of the vanadium catalyst prepared by the above method was fed into the polymerization vessel so that the vanadium catalyst concentration relative to cyclohexane in the polymerization vessel was 0.6 mmol / L. Furthermore, ethylaluminum sesquichloride, an organoaluminum compound, was fed into the polymerization vessel so that the mass ratio of aluminum to vanadium (Al / V) was 18.0. The polymerization temperature was set to 8°C, and the polymerization pressure was set to 1.8 kg / cm. 2 G is copolymerized successively with ethylene and tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene copolymer (ethylene-tetracyclo[4.4.0.1 2,5 .1 7,10 ]-3-dodecene copolymer) was obtained.

[0096] (Decalcification) Ethylene-tetracyclo[4.4.0.1 2,5 .1 7,10 The polymerization reaction was terminated by adding water and a 25% NaOH solution as a pH adjuster to the ethylene-tetracyclo[4.4.0.1 2,5 .1 7,10 The catalyst residue present in the 4-dodecene copolymer was removed (decalcified) to obtain a polymer solution A. The above demineralization treatment was performed on ethylene tetracyclo[4.4.0.1 2,5 .1 7,10 To a cyclohexane solution of 1-dodecene copolymer (polymer solution A, polymer concentration 7.7% by mass), pentaerythrityl-tetrakis[3-(3,5-di-t-butyl-4-hydroxyphenyl)propionate] was added as a stabilizer in an amount of 0.4 parts by mass per 100 parts by mass of the copolymer, and then the mixture was diluted to an effective volume of 1.0 cm 3 The mixture was mixed for 1 hour using a stirring tank.

[0097] (Desolvation) 20kg / cm as heat source 2 A cyclohexane solution of the copolymer with a concentration of 5% by mass was supplied at a rate of 150 kg / H to a double-tube humidifier (outer tube diameter 2B, inner tube diameter 3 / 4B, length 21 m) using G water vapor and heated to 180°C. 25kg / cm as heat source 2 Using a double-tube flash dryer (outer tube diameter 2B, inner tube diameter 3 / 4B, length 27m) using G steam and a flash hopper (volume 200L), most of the unreacted monomers were removed from the cyclohexane solution of the copolymer that had undergone the heating step together with the polymerization solvent cyclohexane to obtain a flash-dried molten cyclic olefin random copolymer (resin A). The glass transition temperature (Tg) of resin A measured with a differential scanning calorimeter was 161°C.

[0098] <Ester compound of triglycerin and fatty acid> (B-1): A triglycerin fatty acid ester compound containing 40 mass% triglycerin diolate (molecular weight 769, diester compound (B) of triglycerin and fatty acid) as the main component, 20 mass% monoester compound of triglycerin and fatty acid, 36 mass% triester compound of triglycerin and fatty acid, and 4 mass% triglycerin was used.

[0099] <Ester compound of diglycerin and fatty acid or ester compound of glycerin and fatty acid> (C-1): A glycerin fatty acid ester compound was used that contained 99% by mass of glycerin monostearate (molecular weight 359, monoester compound (C) of glycerin and fatty acid) as the main component and 1% by mass of a diester compound of glycerin and fatty acid.

[0100] (C-2): A diglycerin fatty acid ester compound containing 87% by mass of diglycerin monooleate (molecular weight 430, monoester compound (C) of diglycerin and fatty acid) as the main component, 8% by mass of a diester compound of diglycerin and fatty acid, and 5% by mass of diglycerin was used.

[0101] <Diglycerol and fatty acid ester compound (D) having a molecular weight exceeding 70% of that of the compound (B)> The main component used was a diglycerin fatty acid ester compound containing 45 mass% diglycerin dioleate (molecular weight 695, a diester compound of diglycerin and fatty acid), 33 mass% monoester compound of diglycerin and fatty acid, and 22 mass% diglycerin, fatty acid and triester compound.

[0102] (Extrusion) Using a vented twin-screw kneading extruder, the above-mentioned molten resin A was charged from the resin charging section of the extruder, and then, in order to remove volatiles, while sucking from the vent section through a trap with a vacuum pump, 0.70 parts by mass of triglycerin fatty acid ester compound (B-1) was added to the cylinder section downstream of the vent section (of which, the amount of the diester compound (B) of triglycerin and fatty acid was 0.28 parts by mass) per 100 parts by mass of resin A, and 0.50 parts by mass of glycerin fatty acid ester compound (C-1) was added to the cylinder section downstream of the vent section (of which, the amount of the monoester compound (C) of glycerin and fatty acid was 0.495 parts by mass), and kneaded downstream of the vent section of the extruder. At this time, the extruder conditions were adjusted so that the difference between the maximum and minimum values ​​of the resin temperature in the extruder diverter section was within 3 ° C.

[0103] Next, the kneaded mixture was pelletized by an underwater pelletizer attached to the outlet of the extruder, and the obtained pellets were dried with hot air at 100° C. for 4 hours. Furthermore, about 3 to 5 times the amount of resin calculated from the average residence time in the polymerization vessel was poured out for washing, and then a sample was collected to obtain a resin composition containing resin A. In order to prevent the inclusion of iron atoms (Fe), stainless steel piping and polymerization vessel were used in the polymer production equipment.

[0104] [Example 2] A resin composition was produced in the same manner as in Example 1, except that 0.32 parts by mass of triglycerin fatty acid ester compound (B-1) was added per 100 parts by mass of resin A (of which, the amount of diester compound (B) of triglycerin and fatty acid was 0.13 parts by mass), and 0.32 parts by mass of diglycerin fatty acid ester compound (C-2) was added per 100 parts by mass of resin A (of which, the amount of monoester compound (C) of diglycerin and fatty acid was 0.28 parts by mass) instead of glycerin fatty acid ester compound (C-1).

[0105] [Comparative Example 1] A resin composition was produced in the same manner as in Example 1, except that the glycerin fatty acid ester compound (C-1) was not added.

[0106] [Comparative Example 2] A resin composition was produced in the same manner as in Example 1, except that 0.32 parts by mass of triglycerin fatty acid ester compound (B-1) was added relative to 100 parts by mass of resin A (of which, the amount of diester compound (B) of triglycerin and fatty acid was 0.13 parts by mass), and 0.32 parts by mass of diglycerin and fatty acid ester compound (D) was added relative to 100 parts by mass of resin A (of which, the amount of diester compound of diglycerin and fatty acid was 0.14 parts by mass) instead of glycerin fatty acid ester compound (C-1).

[0107] [Comparative Example 3] A resin composition was produced in the same manner as in Example 1, except that 3.0 parts by mass of triglycerin fatty acid ester compound (B-1) was added relative to 100 parts by mass of resin A (of which, the amount of diester compound (B) of triglycerin and fatty acid was 1.2 parts by mass), and 3.5 parts by mass of glycerin fatty acid ester compound (C-1) was added relative to 100 parts by mass of resin A (of which, the amount of monoester compound (C) of glycerin and fatty acid was 3.47 parts by mass).

[0108] [Comparative Example 4] Triglycerin fatty acid ester compound (B-1) was used in an amount of 0.05 parts by mass (of which the amount of diester compound (B) of triglycerin and fatty acid was 0.02 parts by mass) per 100 parts by mass of resin A, and glycerin fatty acid ester compound (C-1) was used in an amount of 0.03 parts by mass (of which the amount of monoester compound (C) of glycerin and fatty acid was 0. 0 A resin composition was produced in the same manner as in Example 1, except that 297 parts by mass of the tertiary amine compound was added.

[0109] <Evaluation> (Internal Haze) Using an injection molding machine (ROBOSHOT S2000i-30α manufactured by Fanuc Corporation), the obtained resin composition was injection molded at a cylinder temperature of 275°C and a mold temperature of 120°C to mold a test piece having an optical surface and dimensions of 35 mm x 65 mm x 3 mm thick. The internal haze of the test piece was measured using benzyl alcohol in accordance with JIS K-7136, and was evaluated according to the following criteria. 0.5% or less: ◎ More than 0.5% and less than 1.0%:〇 More than 1.0%: ×

[0110] (Moisture and heat resistance) The test pieces prepared for the internal haze measurement were left in an atmosphere at a temperature of 85° C. and a relative humidity of 85% for 48 hours, then taken out into an atmosphere at a temperature of 23° C. and a relative humidity of 50%, and the internal haze was measured after 48 hours. The amount of change (hereinafter, Δ internal haze) obtained by subtracting the internal haze before the moist heat resistance test from the internal haze after the moist heat resistance test was measured and evaluated based on the following criteria. 0.5% or less: ◎ More than 0.5% and less than 1.0%:〇 More than 1.0%: ×

[0111] (Mold dirt) The resin compositions obtained in Examples 1 and 2 and Comparative Example 1 were continuously injection molded using a mold for forming a flat lens having a lens portion with a diameter of 6.0 mm and a lens portion with a thickness of 0.5 mm, under conditions of a cylinder temperature of 285°C and a mold temperature of 122°C, and the results were evaluated based on the number of shots at which stains occurred on the lens surface, and were evaluated based on the following criteria. Over 12000Shot:◎ More than 10000 shots and less than 12000 shots:〇 10000Shot or less: × The evaluation was carried out by microscopic observation.

[0112] [Table 1]

[0113] [Table 2]

[0114] In Examples 1 and 2, the internal haze was low, and the generation of internal haze before and after the moist heat resistance test was suppressed, and the generation of microcracks was suppressed. Furthermore, in Examples 1 and 2, the mold fouling was also reduced compared to Comparative Example 1. Moreover, in comparison with Comparative Examples 2 to 4, Examples 1 and 2 had low internal haze or were able to suppress the generation of internal haze before and after the moist heat resistance test, and were able to suppress the generation of microcracks.

[0115] This application claims priority based on Japanese Patent Application No. 2021-048392, filed on March 23, 2021, the disclosure of which is incorporated herein in its entirety.

Claims

1. A cyclic olefin polymer (A), (B) a diester compound of triglycerin and a fatty acid; (C) a monoester compound of diglycerin and a fatty acid or a monoester compound of glycerin and a fatty acid, the molecular weight of which is 70% or less of that of the diester compound (B); Including, the total amount of the diester compound (B) and the monoester compound (C) is 0.10 parts by mass or more and 3 parts by mass or less based on 100 parts by mass of the cyclic olefin polymer (A), A cyclic olefin resin composition, wherein a mass ratio of the diester compound (B) to the monoester compound (C) is diester compound (B):monoester compound (C)=1:4 to 4:

1.

2. The cyclic olefin resin composition according to claim 1, The cyclic olefin resin composition, wherein the cyclic olefin polymer (A) comprises at least one member selected from the group consisting of a cyclic olefin copolymer (A-1) and a ring-opening polymer of a cyclic olefin (A-2).

3. The cyclic olefin resin composition according to claim 2, the cyclic olefin polymer (A) contains the copolymer (A-1), The cyclic olefin resin composition, wherein the cyclic olefin copolymer (A-1) has a structural unit (a) and a structural unit (b). Structural unit (a): At least one structural unit derived from an olefin represented by the following general formula (I). Structural unit (b): one or more structural units derived from cyclic olefins 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): 【Chemistry 1】 In the 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 general formula (II), u is 0 or 1, v is 0 or a positive integer, and w is 0 or 1. 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. ７５ ~R ７８ may be bonded to each other to form a monocyclic or polycyclic ring. 【Chemistry 3】 In the general formula (III), x and d each independently represent an integer of 0 or 1 or more. y and z each independently represent an integer of 0 to 2. 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. 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. ９２ and R ９５ Or R ９５ and R ９９ may be bonded to each other to form a monocyclic or polycyclic aromatic ring. 【Chemistry 4】 In the general formula (IV), R １００ , R １０１ may be the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 5 carbon atoms, and f is 1≦f≦18.

4. The cyclic olefin resin composition according to claim 3, the cyclic olefin copolymer (A-1) has a repeating unit (AA) represented by the general formula (II) and a structural unit (D) derived from a cyclic olefin having an aromatic ring, the repeating unit (AA) does not contain an aromatic ring, The cyclic olefin having an aromatic ring comprises one or more compounds selected from the group consisting of a compound represented by general formula (D-1), a compound represented by general formula (D-2), and a compound represented by general formula (D-3). 【Chemistry 5】 In the general formula (D-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 the bonds is a bond. When q=0, R １０ and R １１ , R １１ and R １２ , R １２ and R １３ , R １３ and R １４ , R １４ and R １５ , R １５ and R １０ may be bonded to each other to form a monocyclic or polycyclic ring. １０ and R １１ , R １１ 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 １７ and R １７ , R １６ and R １０ may be bonded to each other to form a monocycle or polycycle, the monocycle or polycycle may have a double bond, and the monocycle or polycycle may be an aromatic ring. 【Chemistry 6】 In the general formula (D-2), n and m each independently represent 0, 1, or 2, and q represents 1, 2, or 3. 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. 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. 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. 【Chemistry 7】 In the general formula (D-3), q is 1, 2 or 3; 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. 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. 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.

5. The cyclic olefin resin composition according to any one of claims 1 to 4, The diester compound (B) has a molecular weight of 300 to 2,000.

6. The cyclic olefin resin composition according to any one of claims 1 to 5, The cyclic olefin resin composition, wherein the cyclic olefin polymer (A) has a glass transition temperature of 130° C. or higher and 170° C. or lower, as measured by a differential scanning calorimeter (DSC).

7. A molded article comprising the cyclic olefin resin composition according to any one of claims 1 to 6.

8. The molded article according to claim 7 , which is an optical component.

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