Cyclic olefin resin composition, molded body

Abstract

A cyclic olefin resin composition comprising a cyclic olefin polymer (A), a diester compound of triglycerol and a fatty acid (B), a monoester compound of diglycerol and a fatty acid or a monoester compound of glycerol and a fatty acid (C) having a molecular weight of 70% or less of the compound (B), the total amount of the compound (B) and the compound (C) being 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).

Description

Technical Field

[0001] This invention relates to cyclic olefin resin compositions and molded articles. Background Technology

[0002] Cyclic olefin polymers are used, for example, in optical lenses such as camera lenses, fθ lenses, and pickup lenses. Cyclic olefin polymers used in such molded optical lenses require properties such as high transparency, excellent dimensional stability, excellent heat resistance, and excellent moisture resistance.

[0003] As an invention relating to cyclic olefin polymers, for example, there is a resin composition comprising diglyceride monooleate or the like in a cyclic olefin polymer as described in Patent Document 1. Patent Document 1 describes a resin composition comprising a polymer in which at least a portion of the repeating structural units comprises an alicyclic structure, and a fatty acid ester of a fatty acid and a polyol having one or more ether groups.

[0004] In addition, Patent Document 2 describes a cyclic olefin resin composition comprising a cyclic olefin polymer (A) and a triglyceride fatty acid ester.

[0005] Patent document 3 discloses a resin composition characterized in that it is a resin composition containing a polymer with an alicyclic structure and a polyglycerol fatty acid ester additive, wherein the polyglycerol fatty acid ester additive is composed of one or more polyglycerol fatty acid ester compounds, and the content of the polyglycerol fatty acid ester additive is 0.2 to 2.0 parts by weight relative to 100 parts by weight of the polymer with an alicyclic structure.

[0006] Existing technical documents

[0007] Patent documents

[0008] Patent Document 1: Japanese Patent Application Publication No. 2015-199939

[0009] Patent Document 2: Japanese Patent Application Publication No. 2018-172665

[0010] Patent Document 3: International Publication No. 2017 / 033968 Summary of the Invention

[0011] The problem that the invention aims to solve

[0012] Cyclic olefin polymers are prone to developing microcracks after high-temperature and high-humidity testing, and these microcracks reduce the optical properties of the molded product. Specifically, microcracks increase the internal haze of the molded body, thus reducing its optical properties as a lens.

[0013] One method to prevent microcrack formation is to add hydrophilic stabilizers to cyclic olefin polymers. By adding hydrophilic stabilizers, the formation of microcracks can be prevented.

[0014] However, according to the research of the inventors, depending on the type of hydrophilic stabilizer, sometimes during molding, dirt originating from the hydrophilic stabilizer adheres to the part of the mold that contacts the molded article and to the mold vent. If dirt adheres to the part of the mold that contacts the molded article, dirt will also adhere to the surface of the molded article. For example, when molding a lens, dirt will adhere to the lens surface, resulting in a decrease in optical properties.

[0015] The present invention was made in view of the above-mentioned problems, and its object is to provide a cyclic olefin resin composition capable of suppressing the generation of microcracks and mold contamination.

[0016] Methods for solving problems

[0017] The inventors conducted repeated and in-depth research to solve the aforementioned problems. Their findings revealed that by combining a specific hydrophilic stabilizer with a monoester of glycerol or diglycerol with a molecular weight lower than that hydrophilic stabilizer, both the generation of microcracks and mold contamination could be resolved, thus completing this invention.

[0018] That is, according to the present invention, a cyclic olefin resin composition, a molded article, and an optical component as shown below are provided. [1]

[0020] A cyclic olefin resin composition comprising:

[0021] Cyclic olefin polymers (A)

[0022] Triglycerides and fatty acid diesters (B), and

[0023] Monoester compounds of diglycerol and fatty acids, or monoester compounds of glycerol and fatty acids (C), with a molecular weight of less than 70% of the above compound (B).

[0024] The total amount of the above compounds (B) and (C) is 0.10 parts by mass and 3 parts by mass or less, relative to 100 parts by mass of the above cyclic olefin polymer (A). [2]

[0026] According to the cyclic olefin resin composition described above [1],

[0027] The aforementioned cyclic olefin polymer (A) comprises at least one selected from cyclic olefin copolymers (A-1) and ring-opening polymers of cyclic olefins (A-2). [3]

[0029] According to the cyclic olefin resin composition described above [2], the cyclic olefin polymer (A) comprises the copolymer (A-1).

[0030] The above-mentioned cyclic olefin copolymer (A-1) has structural unit (a) and structural unit (b).

[0031] Structural unit (a): at least one structural unit derived from an olefin as represented by the following general formula (I).

[0032] Structural unit (b): One or more structural units derived from cyclic olefins selected from the group consisting of repeating units (AA) represented by general formula (II), repeating units (AB) represented by general formula (III), and repeating units (AC) represented by general formula (IV).

[0033] [Chemistry 1]

[0034]

[0035] In the above general formula (I), R 300 A straight-chain or branched hydrocarbon group representing hydrogen atoms or carbon atoms numbering 1 to 29.

[0036] [Chemistry 2]

[0037]

[0038] 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 They can be the same or different from each other, and can be hydrogen atoms, halogen atoms, alkyl groups with 1 to 20 carbon atoms, haloalkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 15 carbon atoms, or aromatic hydrocarbon groups with 6 to 20 carbon atoms. R 75 ~R 78 They can combine to form single or multiple rings.

[0039] [Chemistry 3]

[0040]

[0041] In the above general formula (III), x and d are each independently an integer greater than or equal to 0 or 1. y and z are each independently an integer from 0 to 2. R 81 ~R 99 They can be the same or different from each other, and can be hydrogen atoms, halogen atoms, aliphatic hydrocarbon groups as alkyl groups with 1 to 20 carbon atoms or cycloalkyl groups with 3 to 15 carbon atoms, aromatic hydrocarbon groups or alkoxy groups with 6 to 20 carbon atoms. R89 and R 90 The carbon atom that is bonded to R 93 The bonded carbon atom or R 91 The bonded carbon atoms can be directly bonded or bonded via alkylene groups having 1 to 3 carbon atoms. Additionally, when y = z = 0, R... 92 With R 95 Or R 95 With R 99 They can combine with each other to form monocyclic or polycyclic aromatic rings.

[0042] [Chemistry 4]

[0043]

[0044] In the above general formula (IV), R 100 R 101 They can be the same or different, representing hydrocarbon groups with 1 to 5 hydrogen or carbon atoms. f is 1 ≤ f ≤ 18. [4]

[0046] According to the cyclic olefin resin composition described above [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, wherein the repeating unit (AA) does not contain an aromatic ring.

[0047] The aforementioned cyclic olefins having aromatic rings comprise one or more of 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).

[0048] [Chemistry 5]

[0049]

[0050] In the above general formula (D-1), n ​​and q are each independently 0, 1, or 2. R 1 ~R 17 Each is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be substituted by a halogen atom other than a fluorine atom, R 10 ~R 17 One of them is a bonding bond. Additionally, when q = 0, R 10 With R 11 R 11 With R 12 R 12 With R 13 R 13 With R 14 R 14 With R 15 R15 With R 10 They can combine to form single or multiple rings. Additionally, when q = 1 or 2, R... 10 With R 11 R 11 With R 17 R 17 With R 12 R 12 With R 13 R 13 With R 14 R 14 With R 15 R 15 With R 16 R 16 With R 16 R 17 With R 17 R 16 With R 10 They can combine with each other to form monocyclic or polycyclic rings. In addition, the monocyclic or polycyclic rings can have double bonds and can be aromatic rings.

[0051] [Chemistry 6]

[0052]

[0053] 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 Each can be independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by a halogen atom other than a fluorine atom. Additionally, when q = 1, R... 28 With R 29 R 29 With R 30 R 30 With R 31 They can combine to form single or multiple rings. Additionally, when q = 2 or 3, R... 28 With R 28 R 28 With R 29 R 29 With R 30 R 30 With R 31 R 31 With R 31 They can combine with each other to form monocyclic or polycyclic rings. The monocyclic or polycyclic rings can have double bonds. In addition, the monocyclic or polycyclic rings can be aromatic rings.

[0054] [Chemistry 7]

[0055]

[0056] In the above general formula (D-3), q is 1, 2, or 3, and R 32 ~R 39 Each can be independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by a halogen atom other than a fluorine atom. Additionally, when q = 1, R... 36 With R 37 R 37 With R 38 R 38 With R 39 They can combine to form single or multiple rings. Additionally, when q = 2 or 3, R... 36 With R 36 R 36 With R 37 R 37 With R 38 R 38 With R 39 R 39 With R 39 They can combine with each other to form monocyclic or polycyclic rings. The monocyclic or polycyclic rings can have double bonds. In addition, the monocyclic or polycyclic rings can be aromatic rings. [5]

[0058] The cyclic olefin resin composition according to any one of [1] to [4] above,

[0059] The molecular weight of the above compound (B) is 300 to 2000. [6]

[0061] The cyclic olefin resin composition according to any one of [1] to [5] above,

[0062] The glass transition temperature of the above-mentioned cyclic olefin polymer (A), as determined by differential scanning calorimetry (DSC), is above 130°C and below 170°C. [7]

[0064] A molded article comprising any one of the cyclic olefin resin compositions described in any one of [1] to [6] above. [8]

[0066] The molded body described above [7] is an optical component.

[0067] Invention Effects

[0068] According to the cyclic olefin resin composition of the present invention, a molded article as an optical component can be obtained, which can suppress the generation of microcracks and mold contamination. Such a molded article has low internal haze and can suppress the increase of internal haze before and after damp heat resistance testing. Therefore, it is primarily suitable for optical applications, such as lenses. Detailed Implementation

[0069] The present invention will now be described based on embodiments. It should be noted that, in this embodiment, unless otherwise specified, "A~B" representing a numerical range means A or more and B or less.

[0070] As described above, according to the present inventors' understanding, depending on the type of hydrophilic stabilizer, during molding, there is a problem that dirt originating from the hydrophilic stabilizer may adhere to the part of the mold that contacts the molded article and the mold venting part.

[0071] The inventors conducted repeated and in-depth research to solve the aforementioned problems. Their findings revealed that by using a specific hydrophilic stabilizer and a monoester of glycerol or diglycerol with a molecular weight lower than the aforementioned hydrophilic stabilizer, both the generation of microcracks and mold contamination could be resolved.

[0072] That is, the cyclic olefin resin composition involved in this embodiment is as follows.

[0073] <Cyclic Olefin Resin Compositions>

[0074] The cyclic olefin resin composition involved in this embodiment includes:

[0075] Cyclic olefin polymers (A)

[0076] Triglycerides and fatty acid diesters (B)

[0077] Monoester compounds of diglycerol and fatty acids, or monoester compounds of glycerol and fatty acids (C), with a molecular weight of less than 70% of the above compound (B).

[0078] The total amount of the above-mentioned compound (B) and compound (C) is 0.10 to 3 parts by mass relative to 100 parts by mass of the above-mentioned polymer (A).

[0079] If the cyclic olefin resin composition according to this embodiment is used, the generation of microcracks and mold contamination can be suppressed. Furthermore, if the molded article is made from the cyclic olefin resin composition according to this embodiment, the internal haze is low, and the increase in internal haze before and after the damp heat resistance test can be reduced. Moreover, since the molded article can maintain transparency before and after the damp heat resistance test, it is also suitable for applications requiring transparency.

[0080] [Cyclic olefin polymers (A)]

[0081] The cyclic olefin polymer (A) involved in this embodiment is a copolymer in which structural units derived from cyclic olefins are required structural units.

[0082] The cyclic olefin polymer (A) preferably comprises at least one selected from cyclic olefin copolymers (A-1) and ring-opening polymers of cyclic olefins (A-2). This allows for further improvement in heat resistance or moldability while maintaining a good balance between the transparency and refractive index of the obtained optical component.

[0083] (Cyclic olefin copolymer (A-1))

[0084] As an example of the cyclic olefin copolymer (A-1) involved in this embodiment, copolymers of ethylene or α-olefins with cyclic olefins can be cited.

[0085] The cyclic olefin compounds constituting the above-mentioned cyclic olefin copolymer (A-1) are not particularly limited, for example, the cyclic olefin monomers described in paragraphs 0037 to 0063 of International Publication No. 2006 / 0118261 can be cited.

[0086] From the viewpoint of further improving the optical properties of the obtained optical component, the cyclic olefin copolymer (A-1) preferably has structural units (a) and (b). Optical properties refer to characteristics such as the transparency and refractive index of the optical component.

[0087] Structural unit (a): at least one structural unit derived from an olefin as represented by the following general formula (I).

[0088] [Chemistry 8]

[0089]

[0090] In the above general formula (I), R 300 A straight-chain or branched hydrocarbon group representing hydrogen atoms or carbon atoms numbering 1 to 29.

[0091] Structural unit (b): at least one structural unit derived from a cyclic olefin selected from the group consisting of repeating units (AA) represented by general formula (II), repeating units (AB) represented by general formula (III), and repeating units (AC) represented by general formula (IV).

[0092] [Chemistry 9]

[0093]

[0094] 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 They can be the same or different from each other, and can be hydrogen atoms, halogen atoms, alkyl groups with 1 to 20 carbon atoms, haloalkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 15 carbon atoms, or aromatic hydrocarbon groups with 6 to 20 carbon atoms. R 75 ~R 78 They can combine to form single or multiple rings.

[0095] [Chemistry 10]

[0096]

[0097] In the above general formula (III), x and d are each independently an integer greater than or equal to 0 or 1. y and z are each independently an integer from 0 to 2. R 81 ~R 99 They can be the same or different from each other, and can be hydrogen atoms, halogen atoms, aliphatic hydrocarbon groups as alkyl groups with 1 to 20 carbon atoms or cycloalkyl groups with 3 to 15 carbon atoms, aromatic hydrocarbon groups or alkoxy groups with 6 to 20 carbon atoms. R 89 and R 90 The carbon atom that is bonded to R 93 The bonded carbon atom or R 91 The bonded carbon atoms can be directly bonded or bonded via alkylene groups having 1 to 3 carbon atoms. Additionally, when y = z = 0, R... 92 With R 95 Or R 95 With R 99 They can combine with each other to form monocyclic or polycyclic aromatic rings.

[0098] [Chemistry 11]

[0099]

[0100] In the above general formula (IV), R 100 R 101 They can be the same or different, representing hydrocarbon groups with 1 to 5 hydrogen or carbon atoms. f is 1 ≤ f ≤ 18.

[0101] The olefin monomer used as one of the copolymerization raw materials for the cyclic olefin copolymer (A-1) according to this embodiment is a monomer that undergoes addition polymerization to form the structural unit represented by the above general formula (I). Specifically, an olefin monomer represented by the following general formula (Ia), which corresponds to the above general formula (I), can be used.

[0102] [Chemistry 12]

[0103]

[0104] In the above general formula (Ia), R 300 A straight-chain or branched hydrocarbon group representing 1 to 29 hydrogen or carbon atoms.

[0105] Examples of olefin monomers represented by the above 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 with superior heat resistance, mechanical properties, and optical properties, ethylene and propylene are preferred, with ethylene being particularly preferred. Two or more olefin monomers represented by the above general formula (Ia) may be used.

[0106] When the total structural unit constituting the cyclic olefin copolymer (A-1) of this embodiment is set to 100 mol%, the proportion of structural unit (a) derived from olefin 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.

[0107] It should be noted that the proportion of structural units (a) derived from olefins can be determined by... 13 The measurements were performed using C-NMR.

[0108] The cyclic olefin monomer, one of the copolymer raw materials for the cyclic olefin copolymer (A-1) according to this embodiment, is a monomer derived from a cyclic olefin and formed by addition polymerization to form the structural unit (b) represented by the above-described general formula (II), general formula (III), or general formula (IV). Specifically, cyclic olefin monomers represented by general formulas (IIa), (IIIa), and (IVa), which correspond to the above-described general formulas (II), (III), and (IV), respectively, are used.

[0109] [Chemistry 13]

[0110]

[0111] In the above general formula (IIa), u is 0 or 1, v is 0 or a positive integer, preferably an integer between 0 and 2, more preferably 0 or 1, w is 0 or 1, and R 61 ~R 78 and R a1 and R b1They can be the same or different, and can be hydrogen atoms, halogen atoms, alkyl groups with 1 to 20 carbon atoms, haloalkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 15 carbon atoms, or aromatic hydrocarbon groups with 6 to 20 carbon atoms, R 75 ~R 78 They can combine to form single or multiple rings.

[0112] [Chemistry 14]

[0113]

[0114] In the above general formula (IIIa), x and d are each independently an integer greater than or equal to 0 or 1, preferably an integer greater than or equal to 0 and less than or equal to 2, more preferably 0 or 1, y and z are each independently 0, 1 or 2, and R 81 ~R 99 They can be the same or different, and can be hydrogen atoms, halogen atoms, alkyl groups with 1 to 20 carbon atoms or cycloalkyl groups with 3 to 15 carbon atoms, aliphatic hydrocarbon groups with 6 to 20 carbon atoms, aromatic hydrocarbon groups or alkoxy groups, R 89 and R 90 The carbon atom that is bonded to R 93 The bonded carbon atom or R 91 The bonded carbon atoms can be directly bonded or bonded via alkylene groups having 1 to 3 carbon atoms. Additionally, when y = z = 0, R... 95 With R 92 Or R 95 With R 99 They can combine with each other to form monocyclic or polycyclic aromatic rings.

[0115] [Chemistry 15]

[0116]

[0117] In the above general formula (IVa), R 100 R 101 They can be the same or different, representing hydrocarbon groups with 1 to 5 hydrogen or carbon atoms, where f is 1 ≤ f ≤ 18.

[0118] As a copolymer component, by using olefin monomers represented by the above general formula (Ia), cyclic olefin monomers represented by general formulas (IIa), (IIIa) or (IVa), the solubility of the cyclic olefin copolymer (A-1) in the solvent is further improved, the molding properties are improved, and the yield of the product is increased.

[0119] For specific examples of cyclic olefin monomers represented by general formulas (IIa), (IIIa) or (IVa), compounds described in paragraphs 0037 to 0063 of International Publication No. 2006 / 0118261 may be used.

[0120] Specifically, examples include bicyclic 2-heptene derivatives (bicyclic hept-2-ene derivatives), tricyclic 3-decene derivatives, tricyclic 3-undecene derivatives, tetracyclic 3-dodecene derivatives, pentacyclic 4-pentadecaene derivatives, pentacyclic pentadecadiene derivatives, pentacyclic 3-pentadecaene derivatives, pentacyclic 4-hexadecene derivatives, pentacyclic 3-hexadecene derivatives, hexacyclic 4-heptadecene derivatives, and heptacyclic 5-eicosene derivatives. Compounds, heptacyclic-4-eicosene derivatives, heptacyclic-5-docosene derivatives, octacyclic-5-docosene derivatives, nonacyclic-5-pentacyclic derivatives, nonacyclic-6-hexacyclic derivatives, cyclopentadiene-acenaphthene adducts, 1,4-methylene-1,4,4a,9a-tetrahydrofluorene derivatives, 1,4-methylene-1,4,4a,5,10,10a-hexahydroanthracene derivatives, and cycloalkylene derivatives with 3 to 20 carbon atoms.

[0121] Among the cyclic olefin monomers represented by general formula (IIa), (IIIa) or (IVa), the cyclic olefin represented by general formula (IIa) is preferred.

[0122] As the cyclic olefin monomer represented by the above general formula (IIa), bicyclo[2.2.1]-2-heptene (also known as norbornene) and tetracyclo[4.4.0.1]-2-heptene are preferred. 2,5 .1 7,10 ]-3-Dodecene (also known as tetracyclic dodecene), more preferably tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene. These cyclic olefins have a rigid ring structure, thus having the advantage that the elastic modulus of copolymers and optical components is easily maintained.

[0123] When the total structural unit constituting the cyclic olefin copolymer (A-1) of this embodiment is set to 100 mol%, the proportion of structural unit (b) derived from 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.

[0124] The copolymerization type of the cyclic olefin copolymer (A-1) involved in this embodiment is not particularly limited, and examples include random copolymers and block copolymers. In this embodiment, from the perspective of obtaining optical components with excellent optical properties such as transparency, refractive index and birefringence, and high precision, a random copolymer is preferably used as the cyclic olefin copolymer (A-1) involved in this embodiment.

[0125] As the cyclic olefin copolymer (A-1) involved in this embodiment, it is preferably ethylene and tetracyclo[4.4.0.1] 2, 5 .1 7,10 Random copolymers of 1-3-dodecene and random copolymers of ethylene with bicyclo[2.2.1]-2-heptene, more preferably random copolymers of ethylene with tetracyclo[4.4.0.1]-3-dodecene. 2,5 .1 7,10 Random copolymer of 3-dodecene.

[0126] The copolymer (A-1) involved in this embodiment can be used alone or in combination of two or more.

[0127] The copolymer (A-1) involved in this embodiment can be manufactured, for example, by selecting appropriate conditions according to the methods disclosed in Japanese Patent Application Publication Nos. 60-168708, 61-120816, 61-115912, 61-115916, 61-271308, 61-272216, 62-252406, and 62-252407.

[0128] 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, wherein the repeating unit (AA) does not contain an aromatic ring, and the cyclic olefin having an aromatic ring preferably comprises one or more of the compounds selected from the group consisting of the compounds represented by the following formula (D-1), the following formula (D-2), and the following formula (D-3).

[0129] [Chemistry 16]

[0130]

[0131] In (D-1) above, n and q are each independently 0, 1, or 2. R 1 ~R 17 Each is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be substituted by a halogen atom other than a fluorine atom, R 10 ~R 17 One of them is a bonding bond. Additionally, when q = 0, R 10 With R 11 R 11 With R 12 R 12 With R 13 R 13 With R 14 R14 With R 15 R 15 With R 10 They can combine to form single or multiple rings. Additionally, R... when q = 1 or 2... 10 With R 11 R 11 With R 17 R 17 With R 17 R 17 With R 12 R 12 With R 13 R 13 With R 14 R 14 With R 15 R 15 With R 16 R 16 With R 16 R 16 With R 10 They can combine with each other to form monocyclic or polycyclic rings. In addition, the monocyclic or polycyclic rings can have double bonds and can be aromatic rings.

[0132] [Chemistry 17]

[0133]

[0134] In the above equation (D-2), n and m are each independently 0, 1, or 2, and q is 1, 2, or 3. 18 ~R 31 Each can be independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by a halogen atom other than a fluorine atom. Additionally, when q = 1, R... 28 With R 29 R 29 With R 30 R 30 With R 31 They can combine to form single or multiple rings. Additionally, when q = 2 or 3, R... 28 With R 28 R 28 With R 29 R 29 With R 30 R 30 With R 31 R 31 With R 31 They can combine with each other to form monocyclic or polycyclic rings. The monocyclic or polycyclic rings can have double bonds. In addition, the monocyclic or polycyclic rings can be aromatic rings.

[0135] [Chemistry 18]

[0136]

[0137] In the above formula (D-3), q is 1, 2, or 3, and R 32 ~R 39 Each can be independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by a halogen atom other than a fluorine atom. Additionally, when q = 1, R... 36 With R 37 R 37 With R 38 R 38 With R 39 They can combine to form single or multiple rings. Additionally, when q = 2 or 3, R... 36 With R 36 R 36 With R 37 R 37 With R 38 R 38 With R 39 R 39 With R 39 They can combine with each other to form monocyclic or polycyclic rings. The monocyclic or polycyclic rings can have double bonds. In addition, the monocyclic or polycyclic rings can be aromatic rings.

[0138] Furthermore, examples of hydrocarbon groups with 1 to 20 carbon atoms (D-1) to (D-3) include alkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 15 carbon atoms, and aromatic cyclic hydrocarbon groups. More specifically, examples of alkyl groups include methyl, ethyl, propyl, isopropyl, pentyl, hexyl, octyl, decyl, dodecyl, and octadecyl. Examples of cycloalkyl groups include cyclohexyl. Examples of aromatic hydrocarbon groups include aryl or aralkyl groups such as phenyl, tolyl, naphthyl, benzyl, and phenylethyl. These hydrocarbon groups can also be substituted with halogen atoms other than fluorine atoms.

[0139] If it is a cyclic olefin copolymer (A-1), the generation of haze before and after the damp heat resistance test can be further suppressed. In addition, it can further suppress contamination inside the mold caused by continuous molding.

[0140] When the total structural units of the cyclic olefin copolymer (A-1) according to this embodiment are set to 100 mol%, the content of repeating units (AA) represented by general formula (II) and structural units (D) derived from cyclic olefins having aromatic rings 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, even more preferably 30 mol% or more and 80 mol% or less, and even more preferably 40 mol% or more and 78 mol% or less.

[0141] In this embodiment, the content of repeating units (AA) and structural units (D) can be determined, for example, by means of... 1 H-NMR or 13 The determination was performed using C-NMR.

[0142] (Ring-opening polymers of cyclic olefins (A-2))

[0143] Alternatively, as a cyclic olefin polymer (A), an open-ring polymer of cyclic olefins (A-2) can be used.

[0144] Examples of ring-opening polymers of cyclic olefins (A-2) include, for example, ring-opening polymers of norbornene monomers, ring-opening polymers of norbornene monomers and other monomers capable of ring-opening copolymerization with the norbornene monomers, and their hydrides.

[0145] Examples of norbornene monomers include, for example, bicyclic [2.2.1]hept-2-ene (common name: norbornene) and its derivatives (derivatives with substituents on the ring), tricyclic [4.3.0]... 1,6 .1 2,5 [Dec-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 methylene tetrahydrofluorene: also called 1,4-methylene-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclic [4.4.0.1] 2,5 .1 7,10 ]-3-Dodecene (common name: tetracyclic dodecene) and its derivatives, etc.

[0146] Examples of substituents that replace the ring in these derivatives include alkyl, alkylene, vinyl, alkoxycarbonyl, and alkylidene groups. It should be noted that one or more substituents are permissible. An example of such derivatives with substituents on the ring is 8-methoxycarbonyl-tetracyclo[4.4.0.1]. 2,5 .1 7,10 [Dodecyl-3-ene, 8-methyl-8-methoxycarbonyl-tetracyclo[4.4.0.1]] 2,5 .1 7,10 [Dodecyl-3-ene, 8-ethide-tetracyclo[4.4.0.1]] 2,5 .1 7,10 Dodecyl-3-ene, etc.

[0147] These norbornene monomers can be used individually or in combination of two or more.

[0148] Ring-opening polymers of norbornene monomers, or ring-opening polymers of norbornene monomers and other monomers capable of ring-opening copolymerization with the norbornene monomer, can be obtained by polymerizing the monomer components in the presence of a known ring-opening polymerization catalyst.

[0149] As ring-opening polymerization catalysts, for example, catalysts composed of halides of metals such as ruthenium and osmium, nitrates or acetylacetone compounds and reducing agents can be used; catalysts composed of halides of metals such as titanium, zirconium, tungsten, and molybdenum or acetylacetone compounds and organoaluminum compounds can also be used.

[0150] Other monomers that can undergo ring-opening copolymerization with norbornene monomers include, for example, monocyclic cyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene.

[0151] Hydrogenates of ring-opening polymers of norbornene monomers, and hydrides of ring-opening polymers of norbornene monomers and other monomers capable of ring-opening copolymerization with the norbornene monomers, can generally be obtained by adding a known hydrogenation catalyst containing transition metals such as nickel and palladium to the polymerization solution of the aforementioned ring-opening polymers to hydrogenate the carbon-carbon unsaturated bonds.

[0152] The ring-opening polymer of the cyclic olefin involved in this embodiment (A-2) can be manufactured, for example, by selecting appropriate conditions according to the methods of Japanese Patent Application Publication No. 60-26024, Japanese Patent Application Publication No. 9-268250, Japanese Patent Application Publication No. 63-145324, Japanese Patent Application Publication No. 2001-72839, etc.

[0153] The ring-opening polymer of the cyclic olefin involved in this embodiment (A-2) can be used alone or in combination of two or more.

[0154] The content of the cyclic olefin copolymer (A) involved in this embodiment is preferably 80% by mass or more and 99% by mass or less in the resin composition, 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.

[0155] The glass transition temperature (Tg) of the cyclic olefin copolymer (A) involved in this embodiment is preferably in the range of 130°C to 170°C. If the glass transition temperature (Tg) of the cyclic olefin copolymer (A) is in the above range, sufficient heat resistance can be obtained when it is used as an optical component requiring heat resistance, such as a lens for an automotive camera or a lens for a portable device camera, and good moldability can also be obtained.

[0156] The glass transition temperature (Tg) of the cyclic olefin copolymer (A) involved in this embodiment can be determined using a differential scanning calorimeter (DSC). For example, an RDC220 manufactured by SIInanotechnology can be used. Under a nitrogen atmosphere, the temperature is increased from room temperature to 200°C at a heating rate of 10°C / min, held for 5 minutes, then decreased to 30°C at a cooling rate of 10°C / min, held for 5 minutes, and then increased to 200°C at a heating rate of 10°C / min. The glass transition temperature is then measured.

[0157] [Triglycerides and fatty acid diesters (B)]

[0158] The diester compound (B) involved in this embodiment is a diester compound of triglycerides and fatty acids. There is no particular limitation as long as it is a diester compound of triglycerides and fatty acids. 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.

[0159] Here, when diester compound (B) contains two or more diester compounds, the molecular weight of diester compound (B) mentioned above refers to the molecular weight of the diester compound (B) with the highest content (hereinafter, "highest content" will also be referred to as "main component").

[0160] At this point, as long as the main component is a diester compound (B) containing triglycerides and fatty acids, a mixture of monoester compounds of triglycerides and fatty acids, and triester compounds of triglycerides and fatty acids, i.e., ester compounds of triglycerides and fatty acids, can also be used.

[0161] As an example of such a compound (B), it is preferably at least one selected from the group consisting of triglyceride dioleate and triglyceride distearate, more preferably triglyceride dioleate.

[0162] [Diglycerides of fatty acids or monoesters of glycerol and fatty acids (C)]

[0163] The monoester compound (C) involved in this embodiment is a monoester compound of diglycerol and fatty acid or a monoester compound of glycerol and fatty acid. The molecular weight of the monoester compound (C) is lower than that of the diester compound (B) described above, typically 70% or less, more preferably 65% ​​or less, and even more preferably 60% or less.

[0164] The specific range of molecular weight is preferably 100 to 500, more preferably 200 to 480, and even more preferably 300 to 450.

[0165] Here, when the monoester compound (C) contains two or more monoester compounds, the above-mentioned molecular weight of the monoester compound (C) refers to the molecular weight of the main component monoester compound (C).

[0166] Furthermore, relative to 100 parts by mass of the aforementioned cyclic olefin polymer (A), the combined amount of the aforementioned diester compound (B) and the aforementioned monoester compound (C) is 0.10 parts by mass to 3 parts by mass, more preferably 0.15 parts by mass to 2.5 parts by mass, even more preferably 0.18 parts by mass to 2 parts by mass, even more preferably 0.20 parts by mass to 1.5 parts by mass, even more preferably 0.25 parts by mass to 1.2 parts by mass, even more preferably 0.30 parts by mass to 1.0 part by mass, and even more preferably 0.35 parts by mass to 0.80 parts by mass. If these ranges are set, both the generation of microcracks and the generation of mold contamination can be suppressed.

[0167] Furthermore, the mass ratio of the diester compound (B) to the monoester compound (C) is not particularly limited, but preferably it is 1:4 to 4:1, more preferably it is 1:3 to 3:1, and even more preferably it is 1:2.5 to 2.5:1.

[0168] Furthermore, the content of the diester compound (B) in the cyclic olefin resin composition according to this embodiment is preferably 0.01 parts by mass or more and 1.5 parts by mass or less relative to 100 parts by mass of the cyclic olefin polymer (A), more preferably 0.05 parts by mass or more and 1.0 parts by mass or less, even more preferably 0.08 parts by mass or more and 0.80 parts by mass or less, even more preferably 0.10 parts by mass or more and 0.60 parts by mass or less, even more preferably 0.10 parts by mass or more and 0.40 parts by mass or less, and even more preferably 0.10 parts by mass or more and 0.30 parts by mass or less.

[0169] Furthermore, the content of triglyceride and fatty acid ester compounds (a mixture of triglyceride and fatty acid diester compounds (B), triglyceride and fatty acid monoester compounds, and triglyceride and fatty acid triester compounds) in the cyclic olefin resin composition according to this embodiment is preferably 0.05 parts by mass or more and 2.5 parts by mass or less, more preferably 0.10 parts by mass or more and 2.0 parts by mass or less, even more preferably 0.15 parts by mass or more and 1.5 parts by mass or less, even more preferably 0.20 parts by mass or more and 1.0 parts by mass or less, and even more preferably 0.25 parts by mass or more and 0.80 parts by mass or less, relative to 100 parts by mass of the cyclic olefin polymer (A).

[0170] Furthermore, the content of the monoester compound (C) in the cyclic olefin resin composition according to this embodiment is preferably 0.05 parts by mass or more and 2.0 parts by mass or less relative to 100 parts by mass of the cyclic olefin polymer (A), more preferably 0.10 parts by mass or more and 1.5 parts by mass or less, even more preferably 0.15 parts by mass or more and 1.0 parts by mass or less, even more preferably 0.20 parts by mass or more and 0.80 parts by mass or less, even more preferably 0.20 parts by mass or more and 0.60 parts by mass or less, and even more preferably 0.25 parts by mass or more and 0.55 parts by mass or less.

[0171] By combining the aforementioned diester compound (B) with a monoester compound (C) of glycerol or diglycerol with fatty acids of a lower molecular weight than the aforementioned diester compound (B), it is possible to simultaneously suppress both the generation of microcracks and mold contamination.

[0172] It is believed that this is 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).

[0173] As a specific example of such a monoester compound (C), at least one selected from the group consisting of diglyceride monooleate and glyceride monostearate may be preferred, but not limited thereto.

[0174] When the total content of the cyclic olefin resin composition is set to 100% by mass, 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. By achieving the above lower limit or above, the optical properties can be further improved.

[0175] In addition, there is no particular limit to the upper limit of the total content, but it is preferably 100% by mass or less, and more preferably 98% by mass or less.

[0176] [Other ingredients]

[0177] The cyclic olefin resin composition involved in this embodiment may be combined with weather stabilizers, heat stabilizers, antioxidants, metal deactivators, hydrochloric acid absorbers, antistatic agents, flame retardants, slip agents, anti-blocking agents, anti-fogging agents, lubricants, natural oils, synthetic oils, waxes, organic or inorganic fillers, etc., as needed without impairing the purpose of this embodiment, and the proportions of these additives shall be appropriate.

[0178] The cyclic olefin resin composition involved in this embodiment can preferably be formed into a molded article. There are no particular limitations on the method for molding the cyclic olefin resin composition to obtain the molded article, and known methods can be used. Depending on its application and shape, for example, extrusion molding, injection molding, blow molding, blow molding, extrusion blow molding, injection blow molding, compression molding, vacuum molding, powder slush molding, calendering, foam molding, etc., can be applied. Among these, injection molding is preferred from the viewpoint of moldability and productivity. Furthermore, the molding conditions are appropriately selected according to the intended use or the molding method; for example, the resin temperature during injection molding is typically selected within the range of 150°C to 400°C, preferably 200°C to 350°C, and more preferably 230°C to 330°C.

[0179] The cyclic olefin resin composition according to this embodiment can be obtained, for example, by the following methods: a method of melt-blending the cyclic olefin polymer (A) and other components to be added as needed using a known mixing apparatus such as an extruder and a Banbury mixer; a method of dissolving the cyclic olefin polymer (A) and other components to be added as needed in a common solvent and then evaporating the solvent; a method of precipitation by adding a solution of the cyclic olefin polymer (A) and other components to be added as needed to a poor solvent, etc. It should be noted that when the diester compound (B) and the monoester compound (C) are melt-blended in a mixing apparatus such as an extruder and a Banbury mixer, they can be added before or during the blending process.

[0180] Next, the obtained molded body is annealed for 2 to 8 hours in a 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, thereby obtaining an optical component. Through the above annealing treatment, the molecules of the cyclic olefin polymer (A) in the molded body are relaxed, and the free volume is reduced. Therefore, even with heat treatment, it is difficult for a change in specific gravity (volume change) to occur.

[0181] Here, if the annealing conditions are too stringent, the molded body will deform and become irrecoverable. Therefore, it is preferable to perform the annealing under the aforementioned conditions within a range that prevents deformation of the molded body. That is, it is preferable to perform the annealing at a temperature and time that does not cause deformation of the molded body.

[0182] The optical components obtained through the above operation exhibit excellent resistance to damp heat. Therefore, the increase in internal haze before and after the damp heat test can be suppressed, making them suitable primarily for optical applications and lenses. Furthermore, since transparency is maintained before and after the damp heat test, they are also suitable for applications requiring transparency.

[0183] The embodiments of the present invention have been described above, but these are merely examples of the present invention, and various configurations other than those described above are also possible.

[0184] Furthermore, the present invention is not limited to the above-described embodiments, and variations and improvements that can achieve the objectives of the present invention are also included in the present invention.

[0185] Example

[0186] Hereinafter, this embodiment will be described in detail with reference to the embodiments and other examples. It should be noted that this embodiment is not limited to the descriptions in these embodiments.

[0187] [Example 1]

[0188] <Polymerization of Cyclic Olefin Copolymer (A-1)>

[0189] (Catalyst modulation)

[0190] VO(OC2H5)Cl2 was diluted with cyclohexane to prepare a cyclohexane solution of vanadium catalyst with a concentration of 6.7 mmol / L. Ethyl sesquichloride (Al(C2H5)) was then diluted with cyclohexane. 1.5 Cl 1.5 The cyclohexane solution of the organoaluminum compound catalyst was diluted and prepared to a concentration of 107 mmol / L.

[0191] (polymerization)

[0192] The reaction of ethylene with tetracyclo[4.4.0.1] was carried out continuously using a stirred polymerizer (500 mm inner diameter, 100 L reaction volume). 2,5 .1 7,10 The copolymerization of 3-dodecene was carried out. Cyclohexane was used as the polymerization solvent. During the polymerization reaction, a cyclohexane solution of vanadium catalyst prepared by the above method was supplied to the polymerizer such that the concentration of vanadium catalyst relative to cyclohexane in the polymerizer was 0.6 mmol / L.

[0193] Additionally, ethyl sesquichloride, an organoaluminum compound, is supplied to the polymerizer in such a way that the mass ratio of aluminum to vanadium (Al / V) is 18.0. The polymerization temperature is set to 8°C and the polymerization pressure to 1.8 kg / cm². 2 G undergoes a continuous copolymerization reaction to obtain ethylene and tetracyclo[4.4.0.1] 2,5 .1 7,10 A copolymer of 3-dodecene (ethylene-tetracyclo[4.4.0.1]) 2, 5 .1 7,10 ]-3-dodecene copolymer).

[0194] (deashing)

[0195] Ethylene-tetracyclo[4.4.0.1] removed from the polymerizer 2,5 .1 7,10 Adding water and a 25% by mass NaOH solution as a pH adjuster to the 3-dodecene copolymer solution stopped the polymerization reaction. Additionally, the ethylene-tetracyclo[4.4.0.1] component... 2,5 .1 7,10 The catalyst residue in the 3-dodecene copolymer is removed (deashed) to obtain polymer solution A.

[0196] After the above deashing treatment, ethylene-tetracyclo[4.4.0.1] 2,5 .1 7,10 In a cyclohexane solution of 3-dodecene copolymer (polymer solution A, polymer concentration 7.7% by mass), pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate] as a stabilizer was added to make it 0.4 parts by mass relative to 100 parts by mass of the copolymer, and the effective volume was temporarily used to 1.0 cm. 3 Mix in the mixing tank for 1 hour.

[0197] (Desolventization)

[0198] After using 20kg / cm 2 In a dual-tube humidifier (outer tube diameter 2B, inner tube diameter 3 / 4B, length 21m) using water vapor as a heat source, a cyclohexane solution of the above copolymer with a concentration of 5% by mass is supplied at a rate of 150 kg / H and heated to 180°C.

[0199] Utilizing 25kg / cm 2 A dual-tube flash dryer (outer tube diameter 2B, inner tube diameter 3 / 4B, length 27m) and a flash hopper (volume 200L) using steam as a heat source remove cyclohexane, the polymerization solvent, along with most of the unreacted monomers, from the cyclohexane solution of the copolymer that has undergone the above heating process, thereby obtaining a molten cyclic olefin random copolymer (resin A) after flash drying. The glass transition temperature (Tg) of resin A, measured by differential scanning calorimetry, is 161°C.

[0200] <Ester compounds of triglycerides and fatty acids>

[0201] (B-1): The following triglyceride fatty acid ester compounds are used: triglyceride dioleate (molecular weight 769, triglyceride and fatty acid diester compound (B)) containing 40% by mass as the main component, 20% by mass of triglyceride and fatty acid monoester compound, 36% by mass of triglyceride and fatty acid triester compound, and 4% by mass of triglyceride.

[0202] <Ester compounds of diglycerol and fatty acids or ester compounds of glycerol and fatty acids>

[0203] (C-1): Use the following glycerol fatty acid ester compound, namely, 99% by mass of glycerol monostearate (molecular weight 359, monoester compound of glycerol and fatty acids (C)) as the main component, and 1% by mass of glycerol and fatty acid diester compound.

[0204] (C-2): The following diglyceride fatty acid ester compounds are used: diglyceride monooleate (molecular weight 430, monoester compound of diglyceride and fatty acid (C)) containing 87% by mass as the main component, diglyceride and fatty acid diester compound (C) containing 8% by mass as the main component, and diglyceride monooleate compound (C) containing 8% by mass as the main component, and diglyceride monooleate compound (C) containing 5% by mass as the main component.

[0205] <An ester compound (D) of diglycerides and fatty acids with a molecular weight exceeding 70% of that of compound (B) above>

[0206] The following diglyceride fatty acid ester compounds are used: diglyceride dioleate (molecular weight 695, a diester compound of diglyceride and fatty acid) containing 45% by mass as the main component, monoester compound of diglyceride and fatty acid containing 33% by mass, and triester compound of diglyceride and fatty acid containing 22% by mass.

[0207] (Extrusion)

[0208] Using a twin-screw extruder with a vent, molten resin A is charged into the resin loading section of the extruder. To remove volatiles, the resin is drawn out from the vent section via a trap using a vacuum pump. Simultaneously, in the barrel section downstream of the vent section, 0.70 parts by mass of triglyceride fatty acid ester compound (B-1) (containing 0.28 parts by mass of triglyceride and fatty acid diester compound (B)) and 0.50 parts by mass of glycerol fatty acid ester compound (C-1) (containing 0.495 parts by mass of glycerol and fatty acid monoester compound (C)) relative to 100 parts by mass of resin A are added, and the mixture is compounded in the extruder downstream of the vent section. At this time, the extruder conditions are adjusted so that the difference between the maximum and minimum resin temperature in the extruder distributor section is within 3°C.

[0209] Next, the compound is granulated using an underwater pelletizer installed at the extruder outlet, and the resulting pellets are dried with hot air at 100°C for 4 hours.

[0210] Further washing is performed by introducing approximately 3 to 5 times the amount of resin calculated based on the average residence time within the polymerizer, followed by sample collection to obtain a resin composition containing resin A. To suppress the incorporation of iron atoms (Fe), stainless steel piping and polymerizers are used in the polymer manufacturing equipment.

[0211] [Example 2]

[0212] The resin composition was prepared by adding 0.32 parts by weight of triglyceride fatty acid ester compound (B-1) (in which the amount of triglyceride and fatty acid diester compound (B) is 0.13 parts by weight) relative to 100 parts by weight of resin A, instead of glyceride fatty acid ester compound (C-1), and adding 0.32 parts by weight of diglyceride fatty acid ester compound (C-2) (in which the amount of diglyceride and fatty acid monoester compound (C) is 0.28 parts by weight) relative to 100 parts by weight of resin A. Otherwise, the same procedure as in Example 1 was followed.

[0213] [Comparative Example 1]

[0214] The resin composition was prepared in the same manner as in Example 1, except that no glycerol fatty acid ester compound (C-1) was added.

[0215] [Comparative Example 2]

[0216] The resin composition was prepared by adding 0.32 parts by weight of triglyceride fatty acid ester compound (B-1) (wherein the amount of triglyceride and fatty acid diester compound (B) is 0.13 parts by weight) relative to 100 parts by weight of resin A, and by adding 0.32 parts by weight of diglyceride and fatty acid ester compound (D) (wherein the amount of diglyceride and fatty acid diester compound is 0.14 parts by weight) instead of glyceride fatty acid ester compound (C-1). Otherwise, the process was the same as in Example 1.

[0217] [Comparative Example 3]

[0218] The resin composition was prepared by adding 3.0 parts by weight of triglyceride fatty acid ester compound (B-1) (in which the amount of triglyceride and fatty acid diester compound (B) is 1.2 parts by weight) relative to resin A100 parts by weight, and 3.5 parts by weight of glycerol fatty acid ester compound (C-1) (in which the amount of glycerol and fatty acid monoester compound (C) is 3.47 parts by weight) relative to resin A100 parts by weight, otherwise, the same procedure as in Example 1 was followed.

[0219] [Comparative Example 4]

[0220] The resin composition was prepared by adding 0.05 parts by weight of triglyceride fatty acid ester compound (B-1) (in which the amount of triglyceride and fatty acid diester compound (B) is 0.02 parts by weight) relative to resin A100 parts by weight, and 0.03 parts by weight of glycerol fatty acid ester compound (C-1) (in which the amount of glycerol and fatty acid monoester compound (C) is 0.0297 parts by weight) relative to resin A100 parts by weight, otherwise, the same procedure as in Example 1 was followed.

[0221] <Evaluation>

[0222] (Internal fog)

[0223] The obtained resin composition was injection molded using an injection molding machine (FANUC ROBOSHOT S2000i-30α) at ​​a barrel temperature of 275°C and a mold temperature of 120°C to form a test piece with an optical surface measuring 35mm × 65mm × 3mm in thickness.

[0224] For the internal haze of the test piece, benzyl alcohol was used, and the determination was performed based on JIS K-7136, and the evaluation was based on the following criteria.

[0225] 0.5% or less: ◎

[0226] More than 0.5% but less than 1.0%: 〇

[0227] More than 1.0%: ×

[0228] (Resistance to damp heat)

[0229] The test piece prepared for the internal haze measurement was placed in an atmosphere of 85°C and 85% relative humidity for 48 hours. Then, it was removed and placed in an atmosphere of 23°C and 50% relative humidity for 48 hours, after which the internal haze was measured.

[0230] The change in internal haze from the internal haze before the damp heat test (hereinafter, Δ represents internal haze) is measured and evaluated based on the following criteria.

[0231] 0.5% or less: ◎

[0232] More than 0.5% but less than 1.0%: 〇

[0233] More than 1.0%: ×

[0234] (Mold contamination)

[0235] Using a mold and an injection molding machine (FANUC ROBOSHOT α30iA) to form a flat lens with a diameter of 6.0 mm and a thickness of 0.5 mm, the resin compositions obtained in Examples 1, 2 and Comparative Example 1 were continuously injection molded at a barrel temperature of 285°C and a mold temperature of 122°C. The number of shots required to generate dirt on the lens surface was evaluated based on the following criteria.

[0236] More than 12,000 times: ◎

[0237] More than 10,000 times but less than 12,000 times: 0

[0238] Less than 10,000 times: ×

[0239] The evaluation was conducted through microscopic observation.

[0240] [Table 1]

[0241]

[0242] [Table 2]

[0243]

[0244] Examples 1 and 2 exhibit low internal haze and can suppress the generation of internal haze before and after the damp heat resistance test, thus suppressing the formation of microcracks. Furthermore, compared with Comparative Example 1, Examples 1 and 2 also show reduced mold contamination.

[0245] In addition, compared with Comparative Examples 2 to 4, Examples 1 and 2 have lower internal haze, or can suppress the generation of internal haze before and after the damp heat resistance test, and can suppress the generation of microcracks.

[0246] This application claims priority based on Japanese Patent Application No. 2021-048392, filed on March 23, 2021, the entire contents of which are incorporated herein by reference.

Claims

1. A cyclic olefin resin composition comprising: Cyclic olefin polymers (A) Triglycerides and fatty acid diesters (B), and A monoester compound of diglycerol and fatty acid or a monoester compound of glycerol and fatty acid (C) having a molecular weight of less than 70% of the diester compound (B). Relative to 100 parts by weight of the cyclic olefin polymer (A), the combined amount of the diester compound (B) and the monoester compound (C) is 0.10 parts by weight or more and 3 parts by weight or less. The mass ratio of the diester compound (B) to the monoester compound (C) is 1:4 to 4:

1. The molecular weight of the diester compound (B) is 500 to 1000.

2. The cyclic olefin resin composition according to claim 1, The cyclic olefin polymer (A) comprises at least one selected from cyclic olefin addition polymers (A-1) and cyclic olefin ring-opening polymers (A-2).

3. The cyclic olefin resin composition according to claim 2, The cyclic olefin polymer (A) comprises the cyclic olefin addition polymer (A-1). The cyclic olefin addition polymer (A-1) has structural unit (a) and 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 repeating units (AA) represented by general formula (II), repeating units (AB) represented by general formula (III), and repeating units (AC) represented by general formula (IV). [Chemistry 1] In the general formula (I), R 300 A hydrocarbon group representing hydrogen atoms or 1 to 29 carbon atoms, either straight-chain or branched. [Chemistry 2] In the 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 They can be the same or different, and can be hydrogen atoms, halogen atoms, alkyl groups with 1 to 20 carbon atoms, haloalkyl groups with 1 to 20 carbon atoms, cycloalkyl groups with 3 to 15 carbon atoms, or aromatic hydrocarbon groups with 6 to 20 carbon atoms, R 75 ~R 78 They can combine to form single or multiple rings. [Chemistry 3] In the general formula (III), x and d are each independently an integer greater than or equal to 0 or 1, y and z are each independently an integer from 0 to 2, and R 81 ~R 99 They can be the same or different, consisting of hydrogen atoms, halogen atoms, aliphatic hydrocarbon groups as alkyl groups with 1 to 20 carbon atoms or cycloalkyl groups with 3 to 15 carbon atoms, aromatic hydrocarbon groups or alkoxy groups with 6 to 20 carbon atoms, R 89 and R 90 The carbon atom that is bonded to R 93 The bonded carbon atom or R 91 The bonded carbon atoms can be directly bonded or bonded via alkylene groups having 1 to 3 carbon atoms. Additionally, when y = z = 0, R... 92 With R 95 Or R 95 With R 99 They can combine with each other to form monocyclic or polycyclic aromatic rings. [Chemistry 4] In the general formula (IV), R 100 R 101 They can be the same or different, representing hydrocarbon groups with 1 to 5 hydrogen or carbon atoms, where f is 1 ≤ f ≤ 18.

4. The cyclic olefin resin composition according to claim 3, The cyclic olefin addition polymer (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, wherein 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 compounds represented by general formula (D-1), compounds represented by general formula (D-2), and compounds represented by general formula (D-3). [Chemistry 5] In the general formula (D-1), n ​​and q are each independently 0, 1, or 2, and R 1 ~R 17 Each is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be substituted by a halogen atom other than a fluorine atom, R 10 ~R 17 One of them is a bonding bond; in addition, when q = 0, R 10 With R 11 R 11 With R 12 R 12 With R 13 R 13 With R 14 R 14 With R 15 R 15 With R 10 They can combine to form single or multiple rings. Furthermore, when q = 1 or 2, R... 10 With R 11 R 11 With R 17 R 17 With R 12 R 12 With R 13 R 13 With R 14 R 14 With R 15 R 15 With R 16 R 16 With R 16 R 17 With R 17 R 16 With R 10 They can combine with each other to form monocyclic or polycyclic rings. Furthermore, the monocyclic or polycyclic rings can have double bonds, and they can be aromatic rings. [Chemistry 6] In the general formula (D-2), n and m are each independently 0, 1, or 2, q is 1, 2, or 3, and R 18 ~R 31 Each is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by a halogen atom other than a fluorine atom. Furthermore, when q = 1, R 28 With R 29 R 29 With R 30 R 30 With R 31 They can combine to form single or multiple rings. Additionally, when q = 2 or 3, R... 28 With R 28 R 28 With R 29 R 29 With R 30 R 30 With R 31 R 31 With R 31 They can combine with each other to form monocyclic or polycyclic rings, which may have double bonds, and may also be aromatic rings. [Chemistry 7] In the general formula (D-3), q is 1, 2, or 3, and R 32 ~R 39 Each is independently a hydrogen atom, a halogen atom other than a fluorine atom, or a hydrocarbon group with 1 to 20 carbon atoms that can be replaced by a halogen atom other than a fluorine atom. Additionally, when q = 1, R... 36 With R 37 R 37 With R 38 R 38 With R 39 They can combine to form single or multiple rings. Additionally, when q = 2 or 3, R... 36 With R 36 R 36 With R 37 R 37 With R 38 R 38 With R 39 R 39 With R 39 They can combine with each other to form a single ring or multiple rings, and the single ring or multiple rings can have double bonds. In addition, the single ring or multiple rings can be aromatic rings.

5. The cyclic olefin resin composition according to any one of claims 1 to 4, The glass transition temperature of the cyclic olefin polymer (A), as determined by differential scanning calorimetry (DSC), is above 130°C and below 170°C.

6. A molded article comprising the cyclic olefin resin composition according to any one of claims 1 to 5.

7. The molded body according to claim 6, wherein it is an optical component.

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