Resin composition and method for producing the same, molding material, packaging container, and semiconductor container

Abstract

A resin composition that includes a resin including at least one among a norbornene polymer, a monocyclic cyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and hydrogenated forms thereof and a conductive fibrous filler having an aspect ratio of from 5 to 500.

Description

[Technical Field]

[0001] The present invention relates to a resin composition and a method for producing the same, as well as a molding material, packaging container, and semiconductor container containing the resin composition. [Background technology]

[0002] In recent years, alicyclic structure-containing polymers have attracted attention as raw materials for various resin molded articles because they can exhibit various excellent physical properties such as heat resistance and mechanical strength. For example, Patent Document 1 discloses a resin composition comprising 100 parts by weight of a hydrogenated crystalline cyclic olefin ring-opening polymer having repeating units derived from a polycyclic norbornene monomer having three or more rings, 5 to 100 parts by weight of whiskers with an aspect ratio of 2 to 100, and 5 to 20 parts of a white pigment. According to the resin composition of Patent Document 1, an LED light reflector with excellent heat resistance and light reflectivity can be provided. Furthermore, Patent Document 2 discloses a conductive polymer film comprising a polymer component containing 10 to 100% by mass of a hydrogenated aromatic vinyl-conjugated diene block copolymer, carbon fibers, and conductive fillers other than carbon fibers, wherein the content ratio of carbon fibers and conductive fillers other than carbon fibers is within a predetermined range. The conductive polymer film described in Patent Document 2 has a low volume resistivity and high mechanical strength, making it suitable for use in manufacturing current collectors for electric double-layer capacitors. Furthermore, Patent Document 3 discloses a resin composition containing a cyclic olefin homopolymer having a glass transition temperature within a predetermined range, a fibrous conductive filler, and an elastomer, wherein the elastomer content is within a predetermined range. The resin composition described in Patent Document 3 exhibits excellent mechanical strength, heat resistance, conductivity, and low outgassing when molded into an article. [Prior art documents] [Patent Documents]

[0003] [Patent Document 1] Japanese Patent Publication No. 2015-178580 [Patent Document 2] Japanese Patent Publication No. 2011-68747 [Patent Document 3] Japanese Patent Publication No. 2013-231171 [Overview of the Initiative] [Problems that the invention aims to solve]

[0004] In recent years, resin compositions containing conductive fillers have been required to exhibit excellent cleanliness and minimize particle detachment caused by the conductive fillers when molded products are manufactured. Furthermore, molded products formed using resin compositions containing conductive fillers are also required to have excellent conductivity. However, conventional resin compositions have not been able to achieve a high level of both conductivity and cleanliness in the resulting molded products. Therefore, the present invention aims to provide a resin composition and a method for producing the same that can achieve a high level of both conductivity and cleanliness in the resulting molded article. Furthermore, the present invention aims to provide a molding material, a packaging container, and a semiconductor container that can achieve a high level of both conductivity and cleanliness. [Means for solving the problem]

[0005] The present invention aims to advantageously solve the above problems, and the resin composition of the present invention is characterized by comprising a resin containing at least one of norbornene polymers, monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated versions thereof, and a conductive fibrous filler having an aspect ratio of 5 to 500. In this way, if the resin composition contains a predetermined resin and a conductive fibrous filler having an aspect ratio of 5 to 500, it is possible to achieve a high level of both conductivity and cleanliness in the resulting molded article. The aspect ratio of the conductive fibrous filler can be measured by the method described in the examples of this specification.

[0006] In the resin composition of the present invention, it is preferable that the amount of conductive fibrous filler blended with 100 parts by mass of the resin is 30 parts by mass or more and 240 parts by mass or less. If the amount of conductive fibrous filler blended with 100 parts by mass of the resin satisfies the above range, the conductivity and cleanliness of the resulting molded product can be improved in a well-balanced manner.

[0007] Furthermore, in the resin composition of the present invention, it is preferable that the resin includes a crystalline resin. If the resin includes a crystalline resin, the conductivity of the resulting molded article can be further enhanced, as well as its mechanical strength. Furthermore, the "crystalline" nature of a resin means that its melting point can be detected by measurement according to the differential scanning calorimetry (DSC) method compliant with JIS K7121. The "crystalline" nature of a resin is an inherent property of a polymer with a specific structure, which may result from the stereoregularity of the polymer chains constituting the resin.

[0008] Furthermore, in the resin composition of the present invention, it is preferable that the resin contains a ring-opening polymer of monomers having a norbornene structure or a hydrogenated thereof. If the resin composition contains a ring-opening polymer of monomers having a norbornene structure or a hydrogenated thereof, the amount of outgassing from the resulting molded article can be reduced.

[0009] Furthermore, this invention aims to advantageously solve the above-mentioned problems, and the molding material of the present invention is characterized by containing any of the resin compositions described above. If the molding material contains the resin composition of the present invention, it is possible to achieve a high level of both conductivity and cleanliness in the resulting molded product.

[0010] Furthermore, this invention aims to advantageously solve the above problems, and the packaging container and semiconductor container of the present invention are characterized by being formed by molding any of the resin compositions described above. If the packaging container or semiconductor container is obtained by molding the resin composition of the present invention, such packaging container or semiconductor container will have excellent conductivity and cleanability.

[0011] Furthermore, the present invention aims to advantageously solve the above-mentioned problems, and the method for producing the resin composition of the present invention is characterized by including a mixing step of mixing a conductive fibrous filler material having an aspect ratio of 17 to 500 with the resin to obtain a mixture of conductive fibrous filler having an aspect ratio of 5 to 500 and the resin. According to this method for producing the resin composition of the present invention, the resin composition of the present invention can be produced efficiently. [Effects of the Invention]

[0012] According to the present invention, it is possible to provide a resin composition and a method for producing the same that can achieve a high level of both conductivity and cleanliness in the resulting molded article. Furthermore, according to the present invention, it is possible to provide a molding material, a packaging container, and a semiconductor container that can achieve a high level of both conductivity and cleanliness. [Modes for carrying out the invention]

[0013] Embodiments of the present invention will be described in detail below. Herein, the resin composition of the present invention is used in the manufacture of molding materials, packaging containers, and semiconductor containers of the present invention. Furthermore, the method for manufacturing the resin composition of the present invention allows for the efficient manufacture of the resin composition of the present invention.

[0014] (Resin composition) The resin composition of the present invention is characterized by comprising a resin containing at least one of norbornene polymers, monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated versions thereof, and a conductive fibrous filler having an aspect ratio of 5 to 500. Because the resin composition of the present invention contains a predetermined resin and a conductive fibrous filler having an aspect ratio of 5 to 500, the resulting molded article can achieve a high level of both conductivity and cleanliness.

[0015] <Resin> The resin contained in the resin composition of the present invention includes at least one of a norbornene polymer, a monocyclic cyclic olefin polymer, a cyclic conjugated diene polymer, a vinyl alicyclic hydrocarbon polymer, and hydrogenated products thereof. These resins are preferably not crosslinked.

[0016] Examples of the norbornene polymer and its hydrogenated product include ring-opening polymers of monomers having a norbornene structure and their hydrogenated products; addition polymers of monomers having a norbornene structure and their hydrogenated products. Examples of the ring-opening polymer of a monomer having a norbornene structure include ring-opening homopolymers of one type of monomer having a norbornene structure, ring-opening copolymers of two or more types of monomers having a norbornene structure, and ring-opening copolymers of a monomer having a norbornene structure and any monomer copolymerizable therewith. Further, examples of the addition polymer of a monomer having a norbornene structure include addition homopolymers of one type of monomer having a norbornene structure, addition copolymers of two or more types of monomers having a norbornene structure, and addition copolymers of a monomer having a norbornene structure and any monomer copolymerizable therewith. More specifically, examples of the ring-opening polymer of a monomer having a norbornene structure include polymers obtained by ring-opening polymerization of norbornene-based monomers disclosed in JP-A-2002-321302, such as norbornenes which may have substituents and dicyclopentadienes which may have substituents. Further, for example, examples of the addition polymer of a monomer having a norbornene structure include copolymers obtained by addition polymerization of ethylene to a norbornene-based monomer, and more specifically, random copolymers of a dicyclopentadiene derivative and ethylene.

[0017] As the monocyclic cyclic olefin polymer, for example, addition polymers of monocyclic cyclic olefin monomers such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, and cyclooctene can be used.

[0018] As the cyclic conjugated diene polymer, for example, polymers obtained by 1,2- or 1,4-addition polymerization of cyclic conjugated diene monomers such as cyclopentadiene and cyclohexadiene and their derivatives, and hydrogenated products thereof can be used.

[0019] As the vinyl alicyclic hydrocarbon polymer, for example, polymers of vinyl alicyclic hydrocarbon monomers such as vinylcyclohexene and vinylcyclohexane and their hydrogenated products, and hydrogenated products of the aromatic ring portions of polymers of vinyl aromatic monomers such as styrene, α-methylstyrene, p-methylstyrene, t-butylstyrene, and vinylnaphthalene can be used. In this case, it may be a copolymer such as a random copolymer or a block copolymer of a vinyl alicyclic hydrocarbon polymer or a vinyl aromatic monomer and another monomer copolymerizable with these monomers, and its hydrogenated product. As the block copolymer, there is no particular limitation, such as diblock, triblock, or multi-block or gradient block copolymer with more than that.

[0020] Among them, it is preferable that the resin contains a crystalline resin. If the resin contains a crystalline resin, the conductivity of the obtained molded product can be further enhanced, and the mechanical strength can also be enhanced. Here, when the resin contains a crystalline resin, the proportion of the crystalline resin in the total resin is preferably 50% by mass or more, and may be 100% by mass.

[0021] Also, it is preferable that the resin contains a ring-opening polymer of a monomer having a norbornene structure or its hydrogenated product. If the resin contains a ring-opening polymer of a monomer having a norbornene structure or its hydrogenated product, the amount of outgas from the obtained molded product can be reduced. Here, when the resin contains a ring-opening polymer of a monomer having a norbornene structure or its hydrogenated product, the total content of the ring-opening polymer of the monomer having a norbornene structure and its hydrogenated product in the total resin is preferably 50% by mass or more, and may be 100% by mass.

[0022] Ring-opening polymers of monomers having a norbornene structure or their hydrogenated products may contain, in addition to units derived from monomers having a norbornene structure, units derived from other monomers that are ring-copolymerizable with such units. Examples of such monomers include monocyclic olefin monomers such as cyclohexene, cycloheptene, and cyclooctene. These other monomers that are ring-copolymerizable with monomers having a norbornene structure can be used individually or in combination of two or more. The proportion of units derived from monomers having a norbornene structure in the ring-opening polymer of monomers having a norbornene structure or their hydrogenated products is preferably 70% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and may be 100% by mass.

[0023] Furthermore, it is preferable that the resin contains a ring-opening polymer hydrogenated monomer having a norbornene structure. The hydrogenation rate of such hydrogenated material (the percentage of unsaturated bonds hydrogenated by the hydrogenation reaction) is not particularly limited, but is preferably 98% or more, more preferably 99% or more, based on the total unsaturated bonds contained in the main chain and side chains of the polymer. The higher the hydrogenation rate, the better the heat resistance of the resin.

[0024] Furthermore, a suitable example of a ring-opening polymer of monomers having a norbornene structure or its hydrogenated product is a ring-opening polymer or its hydrogenated product containing monomer units derived from dicyclopentadienes (hereinafter sometimes simply referred to as "dicyclopentadiene-based ring-opening polymers and their hydrogenated products"). These polymers may also contain units derived from other monomers that can be ring-opening copolymerized with dicyclopentadienes.

[0025] For example, dicyclopentadienes that may have substituents and can be used in the preparation of dicyclopentadiene-based ring-opening polymers and their hydrogenated products include dicyclopentadiene, methyldicyclopentadiene, and 5,6-dihydrodicyclopentadiene. Other monomers that can be used in the preparation of dicyclopentadiene-based ring-opening polymers and their hydrogenated products include, without particular limitation, 7,8-benzotricyclo[4.3.0.1 2,5 Deca-3-ene (common name: methanotetrahydrofluorene, also known as 1,4-methano-1,4,4a,9a-tetrahydrofluorene) and its derivatives, tetracyclo[4.4.0.1 2,5 .1 7,10 Examples include norbornenes other than dicyclopentadienes such as dodeca-3-ene (common name: tetracyclododecene) and its derivatives; cyclic olefins; and dienes. The content of dicyclopentadiene, which may have substituents, in the dicyclopentadiene-based ring-opening polymer and its hydrogenated product is not particularly limited. Furthermore, the norbornene-based polymer (1) can be prepared according to conventional methods (see, for example, International Publication No. 2018 / 174029). Moreover, the dicyclopentadiene-based ring-opening polymer and its hydrogenated product are preferably crystalline.

[0026] In particular, the dicyclopentadiene-based ring-opening polymer and its hydrogenated product preferably have syndiotactic stereoregularity. Furthermore, the content of monomer units derived from dicyclopentadienes contained in the dicyclopentadiene-based ring-opening polymer and its hydrogenated product is preferably more than 90% by mass, and more preferably more than 95% by mass, when the total is considered to be 100% by mass.

[0027] The method for preparing dicyclopentadiene-based ring-opening polymers and their hydrogenated products is not particularly limited, and for example, a known method of ring-opening polymerization of the above-mentioned monomers using a metathesis polymerization catalyst can be employed. For example, the method described in Japanese Patent Application Publication No. 2017-149898 can be cited as such.

[0028] The weight-average molecular weight (Mw) of the dicyclopentadiene-based ring-opening polymer is not particularly limited, but is usually 1,000 to 1,000,000, preferably 2,000 to 500,000. By subjecting a ring-opening polymer having such a weight-average molecular weight to a hydrogenation reaction, a hydrogenated dicyclopentadiene-based ring-opening polymer with excellent moldability and other properties can be obtained. The weight-average molecular weight of the dicyclopentadiene-based ring-opening polymer can be adjusted by adjusting the amount of molecular weight adjusting agent used during polymerization.

[0029] The molecular weight distribution (Mw / Mn) of the dicyclopentadiene-based ring-opening polymer is not particularly limited, but is usually 1.0 to 4.0, and preferably 1.5 to 3.5. By subjecting a dicyclopentadiene-based ring-opening polymer having such a molecular weight distribution to a hydrogenation reaction, a hydrogenated dicyclopentadiene-based ring-opening polymer with excellent moldability and other properties can be obtained. The molecular weight distribution of the dicyclopentadiene-based ring-opening polymer can be adjusted by the method of adding monomers and the concentration of monomers during the polymerization reaction. The weight-average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of dicyclopentadiene-based ring-opening polymers are polystyrene-converted values ​​measured by gel permeation chromatography (GPC) using tetrahydrofuran as the developing solvent.

[0030] Among dicyclopentadiene-based ring-opening polymers and their hydrogenated products, dicyclopentadiene-based ring-opening polymer hydrogenated products (hereinafter sometimes referred to as "polymer (α1)") are preferred.

[0031] The melting point of polymer (α1) is preferably 200°C or higher, more preferably 220°C or higher, preferably 350°C or lower, more preferably 320°C or lower, and even more preferably 300°C or lower. A resin composition containing polymer (α1) having a melting point within the above range has good moldability.

[0032] The degree of stereoregularity of polymer (α1) is preferably such that the racemo-dyad ratio is 51% or more, more preferably 60% or more, particularly preferably 65% ​​or more, most preferably 70% or more, preferably 100% or less, more preferably less than 95%, and particularly preferably 90% or less. Polymer (α1) has a higher melting point the higher the racemo-dyad ratio, i.e., the higher the syndiotactic stereoregularity. Furthermore, if the racemo-dyad ratio is less than or equal to the above upper limit, the productivity of polymer (α1) can be increased. The racemo-dyad ratio is as described in the examples of this specification. 13 This can be determined based on 1C-NMR measurements.

[0033] <Conductive fibrous filler> The conductive fibrous filler contained in the resin composition of the present invention is required to have an aspect ratio of 5 or more and 500 or less. Preferably, the aspect ratio of the conductive filler is 7 or more, more preferably 10 or more, preferably 400 or less, more preferably 300 or less, even more preferably 200 or less, and particularly preferably 100 or less. If the aspect ratio of the conductive fibrous filler is above the lower limit, it becomes possible to form a good conductive network between the conductive fibrous fillers in the molded article, and the conductivity of the resulting molded article can be further enhanced. Furthermore, if the aspect ratio of the conductive fibrous filler is below the upper limit, the conductive fibrous filler will be less likely to detach from the molded article, and the cleanliness of the resulting molded article can be further enhanced.

[0034] As conductive fibrous fillers, any material can be used without particular limitation, as long as its aspect ratio meets the above range. For example, conductive fibrous fillers include carbon fibers such as PAN (polyacrylonitrile) carbon fibers and pitch carbon fibers; metal oxide fibers such as tin oxide, indium oxide, alumina, and zinc oxide; and metal fibers such as steel, stainless steel, tungsten, and copper. Among these, pitch carbon fibers and metal oxide fibers are preferred. Here, pitch carbon fibers include isotropic pitch carbon fibers and mesophase pitch carbon fibers, but isotropic pitch carbon fibers can be suitably used.

[0035] <Amount of conductive fibrous filler> The amount of conductive fibrous filler blended in the resin composition is preferably 30 parts by mass or more, more preferably 40 parts by mass or more, preferably 240 parts by mass or less, more preferably 200 parts by mass or less, even more preferably 100 parts by mass or less, and particularly preferably 70 parts by mass or less, per 100 parts by mass of resin. If the amount of conductive fibrous filler blended is above the lower limit, the conductivity and strength of the resulting molded article can be increased. If the amount of conductive fibrous filler blended is below the upper limit, the amount of conductive fibrous filler that detaches from the molded article can be reduced, further improving the cleanliness of the resulting molded article.

[0036] <Other ingredients> The resin composition of the present invention may optionally contain other components such as additives. Examples of additives include antioxidants, nucleating agents, waxes, ultraviolet absorbers, light stabilizers, near-infrared absorbers, colorants such as dyes and pigments, plasticizers, antistatic agents, and fluorescent whitening agents. The content of these additives can be appropriately determined depending on the purpose.

[0037] (Method for manufacturing resin compositions) The resin composition can be prepared by mixing the above-mentioned resin, a conductive fibrous filler, and optionally used additives. The mixing method is not particularly limited and includes, for example, melt mixing using a single-screw kneader or a twin-screw kneader, or dry blending using a mixer. If necessary, a solvent capable of dissolving the resin may be used during mixing.

[0038] More specifically, when mixing a resin with a conductive fibrous filler as a material (hereinafter sometimes referred to as "conductive fibrous filler material"), it is preferable to mix a conductive fibrous filler material with an aspect ratio of 17 to 500 with the resin to obtain a mixture of conductive fibrous filler and resin with an aspect ratio of 5 to 500. By using a conductive fibrous filler material having an aspect ratio within the above range and controlling the mixing conditions (e.g., mixing temperature and rotation speed) during mixing with the resin, the aspect ratio of the conductive fibrous filler in the resulting mixture can be controlled to the above predetermined range, thereby enabling the efficient production of the resin composition of the present invention.

[0039] Furthermore, if the aspect ratio of the conductive fibrous filler material (i.e., the aspect ratio before mixing) is A1 and the aspect ratio of the conductive fibrous filler (i.e., the aspect ratio after mixing) is A2, it is preferable that the maintenance of the aspect ratio before and after mixing: A2 / A1 is 0.60 or higher, and more preferably 0.70 or higher. By mixing under conditions such that the value of A2 / A1 is equal to or greater than the above lower limit, the deterioration of the conductive fibrous filler material during the manufacturing process of the resin composition can be suppressed, and the lifespan of the resulting resin composition and its molding material can be extended. The upper limit of the maintenance of the aspect ratio is not particularly limited, but it is usually 1.00 or lower.

[0040] (molding material) The molding material of the present invention is characterized by containing the resin composition of the present invention described above. Because the molding material of the present invention contains the resin composition of the present invention, it is possible to achieve a high level of both conductivity and cleanliness. The shape of the molding material is not particularly limited, and examples include a sheet or a plate. A molding material in the form of a sheet or a plate can be suitably used for press molding and can be suitably used to provide a molded product with excellent conductivity and cleanliness.

[0041] (packaging container) The packaging container of the present invention is characterized by containing the resin composition of the present invention described above. Because the packaging container of the present invention contains the resin composition of the present invention, it is possible to achieve a high level of both conductivity and cleanliness. For this reason, the packaging container of the invention is suitable as a packaging container for electronic equipment components. The packaging container of the present invention can be manufactured by molding the resin composition of the present invention or the molding material of the present invention according to a molding method suitable for the desired shape.

[0042] (semiconductor container) The semiconductor container of the present invention is characterized by containing the resin composition of the present invention described above. Because the semiconductor container of the present invention contains the resin composition of the present invention, it is possible to achieve a high level of both conductivity and cleanliness. The semiconductor container may be, for example, a FOUP (Front Opening Unified Pod), FOSB (Front Opening Shipping Box), wafer tray, wafer carrier, handles that can be attached to these trays or carriers, carrier tape, dicing tape, wafer cassette, and housing used in semiconductor manufacturing processes. The semiconductor container of the present invention can be manufactured by molding the resin composition of the present invention or the molding material of the present invention according to a molding method suitable for the shape of the target semiconductor container. More specifically, for example, the semiconductor container can be molded according to a melt molding method. Examples of melt molding methods include injection molding, blow molding, and injection blow molding. These methods can be appropriately selected according to the target container shape, etc. Among these, injection molding is preferred. [Examples]

[0043] The present invention will be described in detail below based on examples, but the present invention is not limited to these examples. In the following description, "%" and "parts" representing quantities refer to mass unless otherwise specified. In addition, in a polymer produced by copolymerizing multiple types of monomers, the proportion of a monomer unit formed by polymerizing a certain monomer in the polymer is usually equal to the ratio of that certain monomer to the total monomers used in the polymerization of the polymer (starting ratio), unless otherwise specified. In the examples and comparative examples, various physical properties were measured according to the following methods.

[0044] (Aspect ratio of conductive fibrous filler material (aspect ratio before mixing)) The conductive filler material to be used was collected and used as a measurement sample. The surface of the measurement sample was observed using a microscope (Keyence Corporation, Digital Microscope VHX-5000), and the aspect ratio was calculated by dividing the major axis of the identified fibrous filler by its minor axis. Three observation samples were used, and the average of the aspect ratios obtained from three randomly selected samples was defined as the "aspect ratio of the conductive fibrous filler material." The "major axis" of the fibrous filler material was defined as the diameter of a circle circumscribing the fibrous filler material.

[0045] (Aspect ratio of conductive fibrous filler (aspect ratio after mixing)) The resin compositions prepared in the examples and comparative examples were dried at 120°C for 4 hours to obtain dried resin compositions. The obtained dried resin compositions were placed in a small injection molding machine (DSM Xplore, Micro Injection Molding Machine 10cc) and injection molding was performed under the conditions of a molding temperature of 290°C, an injection pressure of 0.7 MPa, and a mold temperature of 80°C to produce molded products with a thickness of 30 × 60 × 3 mm. The surface of the obtained molded products was observed using a microscope (Keyence, Digital Microscope VHX-5000), and the aspect ratio was calculated by dividing the major axis of the identified fibrous filler by its minor axis. Three observation samples were used, and the average of the aspect ratios obtained from three randomly selected samples was defined as the "aspect ratio of conductive fibrous filler." Furthermore, the aspect ratio of the conductive fibrous filler in the (dried) resin composition before molding, i.e., the aspect ratio of the conductive fibrous filler in the molded product as observed on the surface, may be substantially the same. Also, the "major axis" of the fibrous filler was defined as the diameter of a circle circumscribing the fibrous filler.

[0046] (Molecular weight of ring-opened polymers) The ring-opening polymers prepared in Examples 1-5, 7-9, and Comparative Examples 1-3 were used as samples for measurement. The molecular weight (weight-average molecular weight and number-average molecular weight) of the ring-opening polymers was determined as polystyrene equivalent values ​​using a gel permeation chromatography (GPC) system HLC-8320 (Tosoh Corporation) with an H-type column (Tosoh Corporation) at a temperature of 40°C and tetrahydrofuran as the solvent.

[0047] (Hydrogenation rate of ring-opening polymer hydrogenated products) Using orthodichlorobenzene-d4 as the solvent, 1 ¹H-NMR measurements were performed to determine the hydrogenation rate when the ring-opened polymers prepared in Examples 1-5, 7-9, and Comparative Examples 1-3 were hydrogenated.

[0048] (Glass transition temperature and melting point of ring-opening polymer hydrogenated products) The ring-opening polymer hydrogenated materials prepared in Examples 1-5, 7-9, and Comparative Examples 1-3 were used as measurement samples. The obtained measurement samples were heated to 320°C under a nitrogen atmosphere, and then rapidly cooled to room temperature using liquid nitrogen at a cooling rate of -10°C / min. The glass transition temperature and melting point of the ring-opening polymer hydrogenated materials were determined by increasing the temperature at 10°C / min using a differential scanning calorimeter (DSC).

[0049] (Ratio of racemo-dyad in ring-opening polymer hydrogenated products) The ring-opening polymer hydrogenated products prepared in Examples 1-5, 7-9 and Comparative Examples 1-3 were used as measurement samples. Using orthodichlorobenzene-d4 / 1,2,4-trichlorobenzene (TCB)-d3 (mixing ratio (by mass) 1 / 2) as the solvent, the inverse-gated decoupling method was applied at 200°C. 13 13C-NMR measurements were performed to determine the proportion of racemo-dyads. Specifically, using the 127.5 ppm peak of orthodichlorobenzene-d4 as the reference shift, the proportion of racemo-dyads was determined based on the intensity ratio of the 43.35 ppm signal from meso-dyads and the 43.43 ppm signal from racemo-dyads.

[0050] (Cleanliness) The cleanliness of molded articles obtained using the resin compositions obtained in the examples and comparative examples was evaluated by particle count. For molded articles obtained according to the manufacturing method described in the section on (aspect ratio of conductive fibrous filler), the surface was washed with ultrapure water. The washed molded articles were left in a Class 10000 cleanroom for 168 hours. After that, the surface of the molded articles was washed with ultrapure water, and the amount of particles in the washing water was measured with a particle counter. A molded product was determined to be clean if the particle count was 10,000 particles / ml or less.

[0051] (conductive) The conductivity of molded articles obtained using the resin compositions obtained in the examples and comparative examples was evaluated by the surface resistivity of the molded articles. The resin compositions obtained in the examples and comparative examples were dried at 120°C for 4 hours to obtain dried resin compositions. The obtained dried resin compositions were placed in an injection molding machine (FANUC S-2000i) and injection molding was performed under conditions of a molding temperature of 290°C and a mold temperature of 80°C to produce disc-shaped molded articles with a diameter of 50 mm and a thickness of 3 mm. The surface resistivity of the molded articles thus obtained was measured using an insulation meter (Kawaguchi Electric Works R-503). Surface resistivity is 1 × 10 10 A value of Ω or less was considered to indicate excellent conductivity. The lower limit of the surface resistivity measurement is not particularly limited, but for example, 1 × 10⁻⁶ 2 It could be Omega.

[0052] (Outgassing volume) The resin compositions prepared in the examples and comparative examples were dried at 120°C for 4 hours to obtain dried resin compositions. A sample container made of a glass tube with an inner diameter of 4 mm containing the obtained dried composition was connected to a gas collection tube cooled with liquid nitrogen. The sample container was then heated at 180°C for 30 minutes in a stream of high-purity helium (helium purity of 99.99995% by volume or higher), and the gas released from the sample was continuously collected by the gas collection tube. The collected gas was subjected to thermal desorption gas chromatography-mass spectrometry using n-decane as an internal standard, and the amount of gas released from the sample was calculated as an n-decane equivalent value. An outgassing amount of 50 ppm or less was judged to be sufficiently low. The following equipment and analytical conditions were used in this analysis. [Heat-based desorption] Equipment: Gerstel TDS A2 Sample heating conditions: 180°C, 30 minutes Helium gas flow rate: 30 ml / min Gas collection tube: A 1mm diameter tube filled with glass wool. Temperature of gas collection tube: -130°C (during gas collection), 280°C (during gas release) [Gas chromatography] Equipment: Agilent 6890N Column: Agilent HP-5ms (0.25 × 30 m, df = 0.25 μm) Carrier gas flow rate: 1 ml / min Column pressure: NONE (Flow control) Heating profile: The temperature was maintained at 40°C for 3 minutes, then increased to 280°C at a rate of 10°C / min, and held at 280°C for 10 minutes. [Mass spectrometer] Equipment: Agilent 5973N

[0053] (strength) The strength of molded articles obtained using the resin compositions obtained in the examples and comparative examples was evaluated by the flexural modulus of the molded article. The resin compositions obtained in the examples and comparative examples were dried at 120°C for 4 hours to obtain dried resin compositions. The obtained dried resin compositions were placed in a small injection molding machine (DSM Xplore, Micro Injection Moulding Machine 10cc) and injection molding was performed under the conditions of a molding temperature of 290°C, an injection pressure of 0.7 MPa, and a mold temperature of 80°C to produce test specimens for measuring the flexural modulus with a thickness of 80 × 10 × 4 mm. Using the obtained test specimens, a bending test was performed at a test speed of 2 mm / min in accordance with JIS K7171 using an Autograph (product name "AGS-5kNJ·TCR2", Shimadzu Corporation) to measure the flexural modulus. A bending modulus of elasticity of 100 MPa or higher was determined to indicate sufficiently high strength.

[0054] (Example 1) <Preparation of crystalline norbornene-based ring-opening polymer hydrogenated products> In a metal pressure-resistant reaction vessel with its interior purged with nitrogen, 154.5 parts of cyclohexane (an organic solvent), 42.8 parts of a cyclohexane solution (70% concentration) of dicyclopentadiene (endo-isomer content of 99% or more) (30 parts as dicyclopentadiene), and 1.9 parts of 1-hexene (a molecular weight modifier) ​​were added, and the entire mixture was heated to 53°C. Meanwhile, 0.014 parts of tetrachlorotungstenphenylimide (tetrahydrofuran) complex, a metal compound used as a ring-opening polymerization catalyst, were dissolved in 0.70 parts of toluene (an organic solvent) to obtain a solution. To this solution, 0.061 parts of an n-hexane solution (19% concentration) of diethylaluminum ethoxide, an organometallic reducing agent used as a ring-opening polymerization catalyst, were added, and the mixture was stirred for 10 minutes to prepare a ring-opening polymerization catalyst solution. This ring-opening polymerization catalyst solution was added to the reactor, and the ring-opening polymerization reaction was carried out at 53°C for 4 hours to obtain a solution containing the dicyclopentadiene ring-opening polymer. To 200 parts of the solution containing the obtained dicyclopentadiene ring-opening polymer, 0.037 parts of 1,2-ethanediol were added as a stopping agent, and the mixture was stirred at 60°C for 1 hour to stop the polymerization reaction. Then, 1 part of a hydrotalcite-like compound (product name "Kyoword® 2000", manufactured by Kyowa Chemical Industry Co., Ltd.), an adsorbent, was added, and the mixture was heated to 60°C and stirred for 1 hour. 0.4 parts of a filtration aid (product name "Radiolite® #1500", manufactured by Showa Chemical Industry Co., Ltd.) were added, and the adsorbent was filtered off using a PP pleated cartridge filter (product name "TCP-HX", manufactured by ADVANTEC Toyo Co., Ltd.) to obtain a solution containing the dicyclopentadiene ring-opening polymer. When the molecular weight of the dicyclopentadiene ring-opening polymer was measured using a portion of this solution, the weight-average molecular weight (Mw) was 28,100, the number-average molecular weight (Mn) was 8,750, and the molecular weight distribution (Mw / Mn) was 3.21. To 200 parts of a solution containing the obtained dicyclopentadiene ring-opening polymer (polymer content 30 parts), 100 parts of cyclohexane and 0.0043 parts of chlorohydridecarbonyltris(triphenylphosphine)ruthenium were added, and a hydrogenation reaction was carried out at a hydrogen pressure of 6 MPa and 180°C for 4 hours. The reaction solution was a slurry liquid with solid content precipitated. The reaction mixture was separated from the solids by centrifugation, and the solids were dried under reduced pressure at 60°C for 24 hours to obtain 28.5 parts of hydrogenated dicyclopentadiene ring-opening polymer. The hydrogenation rate of unsaturated bonds in the hydrogenation reaction was over 99%, the glass transition temperature of the hydrogenated dicyclopentadiene ring-opening polymer was 98°C, and the melting point was 262°C. Furthermore, the racemo-dyad ratio was 89%. To 100 parts of pellets made of the crystalline norbornene-based ring-opening polymer hydrogenated as described above, 42 parts of isotropic pitch-based carbon fiber (manufactured by Osaka Gas Chemical Co., Ltd., Donacarbomilled SC-2415, fiber diameter: 13 μm, fiber length: 0.22 mm) with an aspect ratio A1 of 17 was added as a conductive fibrous filler material to obtain a mixture. This mixture was kneaded using a twin-screw extruder (manufactured by Toshiba Machine Co., Ltd., TEM35B) at a resin temperature of 280°C and a screw rotation speed of 100 rpm, extruded into strands, water-cooled, and then cut with a pelletizer to obtain 140 parts of resin composition pellets. The aspect ratio A2 of the conductive fibrous filler in the resin composition was measured according to the above and was found to be 15. The aspect ratio retention A2 / A1 before and after mixing was 0.88. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0055] (Example 2) In the preparation of the resin composition, a resin composition was obtained in the same manner as in Example 1, except that the conductive fibrous filler was replaced with 66 parts of isotropic pitch carbon fiber (manufactured by Osaka Gas Chemical Co., Ltd., Donacarbomilled S-246, fiber diameter: 13 μm, fiber length: 1 mm) with an aspect ratio A1 of 77. The aspect ratio A2 of the conductive fibrous filler in the resin composition was measured according to the above and was found to be 58. The aspect ratio retention A2 / A1 before and after mixing was 0.75. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0056] (Example 3) In the preparation of the resin composition, a resin composition was obtained in the same manner as in Example 1, except that the conductive fibrous filler was replaced with 42 parts of isotropic pitch carbon fiber (manufactured by Osaka Gas Chemical Co., Ltd., Donacarbomilled S-246, fiber diameter: 13 μm, fiber length: 1 mm) with an aspect ratio A1 of 77. The aspect ratio A2 of the conductive fibrous filler in the resin composition was measured according to the above and was found to be 58. The aspect ratio retention rate A2 / A1 before and after mixing was 0.75. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0057] (Example 4) In the preparation of the resin composition, a resin composition was obtained in the same manner as in Example 1, except that the conductive fibrous filler was replaced with 42 parts of isotropic pitch carbon fiber (manufactured by Osaka Gas Chemical Co., Ltd., DonaCarboChop S-232, fiber diameter: 13 μm, fiber: 5.5 mm) having an aspect ratio A1 of 423. The aspect ratio A2 of the conductive fibrous filler in the resin composition was measured according to the above and was found to be 360. The aspect ratio retention A2 / A1 before and after mixing was 0.85. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0058] (Example 5) A resin composition was obtained in the same manner as in Example 1, except that an amorphous norbornene-based ring-opening polymer hydrogenated resin (amorphous norbornene-based ring-opening polymer hydrogenated resin) prepared as described below was used as the resin. The aspect ratio A2 of the conductive fibrous filler in the resin composition was measured according to the above and was found to be 15. The aspect ratio retention A2 / A1 before and after mixing was 0.88. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1. <Amorphous norbornene-based ring-opening polymer hydrogenated products> In a nitrogen atmosphere, 0.82 parts of 1-hexene, 0.15 parts of dibutyl ether, and 0.30 parts of triisobutylaluminum were placed in a reactor at room temperature and mixed with 500 parts of dehydrated cyclohexane. After that, while maintaining the temperature at 45°C, 76 parts of dicyclopentadiene (DCPD), and 2,5 .1 7,10 70 parts of 8-methyl-tetracyclo[4.4.0.1 2,7 .1 1 0,13 dodeca-3-ene (TCD), 54 parts of tetracyclo[7.4.0.0 2,7 .1 1 0,13 trideca-2,4,6,11-tetraene (MTF), and 80 parts of tungsten hexachloride (0.7% toluene solution) were continuously added in parallel over 2 hours for polymerization. Next, 1.06 parts of butyl glycidyl ether and 0.52 parts of isopropyl alcohol were added to the polymerization solution to inactivate the polymerization catalyst and stop the polymerization reaction. When the reaction solution containing the obtained ring-opening polymer was analyzed by gas chromatography, the polymerization conversion rate of each monomer was 99.5%. Next, 270 parts of cyclohexane were added to 100 parts of the reaction solution containing the obtained ring-opening polymer, and further 5 parts of a diatomaceous earth-supported nickel catalyst (nickel loading rate: 58% by mass, pore volume: 0.25 ml / g, specific surface area: 180 m 2 / g) as a hydrogenation catalyst were added. The mixture was pressurized to 5 MPa with hydrogen and heated to 200°C with stirring, followed by reacting for 8 hours to obtain a reaction solution containing a hydrogenated product of the DCPD / TCD / MTF ring-opening copolymer. The hydrogenation catalyst was removed by filtration. Then, using a cylindrical concentration dryer (manufactured by Hitachi, Ltd.), at a temperature of 270°C and a pressure of 1 kPa or less, cyclohexane as a solvent and other volatile components were removed from the solution. Next, the hydrogenated product was extruded in a strand form from an extruder in a molten state and pelletized after cooling to obtain pellets. The Mw of this pelletized hydrogenated ring-opening polymer was 34,000, the hydrogenation rate was 99% or more, and the glass transition temperature was 135°C. Also, the melting point of the hydrogenated ring-opening polymer was not observed, and it was found to be amorphous.

[0059] (Example 6) A resin composition was obtained in the same manner as in Example 1, except that an addition polymer of monomers having a norbornene structure (a random copolymer of a dicyclopentadiene derivative and ethylene; manufactured by Mitsui Chemicals, Inc., Apel® 6013T; amorphous) was used as the resin. The aspect ratio A2 of the conductive fibrous filler in the resin composition was measured according to the above and was found to be 15. The aspect ratio retention A2 / A1 before and after mixing was 0.88. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0060] (Example 7) A resin composition was obtained in the same manner as in Example 4, except that the amount of conductive fibrous filler was changed to 200 parts. The aspect ratio A2 of the conductive fibrous filler in the resin composition was measured according to the above and was found to be 360. The aspect ratio retention rate A2 / A1 before and after mixing was 0.85. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0061] (Example 8) In the preparation of the resin composition, a resin composition was obtained in the same manner as in Example 1, except that the conductive fibrous filler was replaced with 42 parts of tin oxide fibers (manufactured by Ishihara Sangyo Co., Ltd., FS-10P, fiber diameter: 0.01~0.02 μm, fiber length: 0.2~2 μm) with an aspect ratio A1 of 25. The aspect ratio A2 of the conductive fibrous filler in the resin composition was measured according to the above and was found to be 18. The aspect ratio retention A2 / A1 before and after mixing was 0.72. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0062] (Example 9) A resin composition was obtained in the same manner as in Example 1, except that a resin composition was used in which 50 parts by mass each of crystalline norbornene-based ring-opening polymer hydrogenated material prepared in Example 1 and amorphous norbornene-based ring-opening polymer hydrogenated material prepared in Example 5 were mixed. The mixing was performed at the time of compounding the conductive fibrous filler. The aspect ratio A2 of the conductive fibrous filler in the resin composition was measured according to the above and was found to be 15. The aspect ratio retention A2 / A1 before and after mixing was 0.88. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0063] (Comparative Example 1) In the preparation of the resin composition, a resin composition was obtained in the same manner as in Example 1, except that conductive fibrous fillers were not included and were replaced with 10 parts of titanium oxide whiskers with an aspect ratio of 191 (manufactured by Ishihara Sangyo Co., Ltd., FTL-300, fiber diameter: 0.27 μm, fiber length: 5.15 μm). Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0064] (Comparative Example 2) In the preparation of the resin composition, a resin composition was obtained in the same manner as in Example 1, except that 42 parts of carbon fiber with an aspect ratio of 857 (manufactured by Mitsubishi Rayon, Pyrophil® Chopped Fiber TR06UB4E) was added instead of a conductive fibrous filler with a predetermined aspect ratio. When the aspect ratio of the conductive fibrous filler in the resin composition was measured according to the above, it was found to be 610. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0065] (Comparative Example 3) In the preparation of the resin composition, a resin composition was obtained in the same manner as in Example 1, except that 13 parts of carbon fibers with an aspect ratio of 857 (manufactured by Nippon Polymer Co., Ltd., "EPU-LCL", fiber diameter: 7.0 μm, fiber length: 6.0 mm) were added instead of conductive fibrous fillers with a predetermined aspect ratio. When the aspect ratio of the conductive fibrous filler in the resin composition was measured according to the above, it was found to be 620. Furthermore, various attributes were evaluated using the obtained resin composition according to the above procedure. The results are shown in Table 1.

[0066] [Table 1]

[0067] Table 1 shows that the resin compositions according to Examples 1 to 9, which include a predetermined resin and a conductive fibrous filler with an aspect ratio of 5 to 500, were able to achieve a high level of both conductivity and cleanliness in the resulting molded articles. On the other hand, in Comparative Example 1, which did not contain the specified conductive fibrous filler, the conductivity of the resulting molded product could not be improved. Furthermore, in Comparative Examples 2 and 3, which incorporated conductive fibrous fillers with an aspect ratio larger than that of the present invention, a large amount of particles detached from the resulting molded product, indicating that the cleanliness of the molded product could not be improved. [Industrial applicability]

[0068] According to the present invention, it is possible to provide a resin composition and a method for producing the same that can achieve a high level of both conductivity and cleanliness in the resulting molded article. Furthermore, according to the present invention, it is possible to provide a molding material, a packaging container, and a semiconductor container that can achieve a high level of both conductivity and cleanliness.

Claims

1. A resin comprising at least one of norbornene polymers, monocyclic cyclic olefin polymers, cyclic conjugated diene polymers, vinyl alicyclic hydrocarbon polymers, and hydrogenated versions thereof, It includes a conductive fibrous filler having an aspect ratio of 5 or more and 500 or less, and further, The aforementioned resin includes a crystalline resin, and The conductive fibrous filler is either or at least one of polyacrylonitrile-based carbon fibers and pitch-based carbon fibers. Resin composition.

2. The resin composition according to claim 1, wherein the amount of conductive fibrous filler blended with 100 parts by mass of the resin is 30 parts by mass or more and 240 parts by mass or less.

3. The resin composition according to claim 1 or 2.

4. The resin composition according to any one of claims 1 to 3, wherein the resin comprises a ring-opening polymer of monomers having a norbornene structure or a hydrogenated product thereof.

5. A molding material comprising the resin composition according to any one of claims 1 to 4.

6. A packaging container formed by molding a resin composition according to any one of claims 1 to 4.

7. A semiconductor container formed by molding a resin composition according to any one of claims 1 to 4.

8. A method for producing a resin composition according to any one of claims 1 to 4, comprising a mixing step of mixing a conductive fibrous filler material having an aspect ratio of 17 or more and 500 or less with the resin to obtain a mixture of a conductive fibrous filler having an aspect ratio of 5 or more and 500 or less with the resin.

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