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WO2025204544A1 - Composition de résine, son procédé de production, et corps moulé - Google Patents

Composition de résine, son procédé de production, et corps moulé

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Publication number
WO2025204544A1
WO2025204544A1 PCT/JP2025/007557 JP2025007557W WO2025204544A1 WO 2025204544 A1 WO2025204544 A1 WO 2025204544A1 JP 2025007557 W JP2025007557 W JP 2025007557W WO 2025204544 A1 WO2025204544 A1 WO 2025204544A1
Authority
WO
WIPO (PCT)
Prior art keywords
ring
norbornene
opening polymer
resin composition
polymer
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Pending
Application number
PCT/JP2025/007557
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English (en)
Japanese (ja)
Inventor
直也 源
剛 平田
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Zeon Corp
Original Assignee
Zeon Corp
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Filing date
Publication date
Application filed by Zeon Corp filed Critical Zeon Corp
Publication of WO2025204544A1 publication Critical patent/WO2025204544A1/fr
Pending legal-status Critical Current
Anticipated expiration legal-status Critical

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
    • C08G61/00—Macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain of the macromolecule
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L45/00—Compositions of homopolymers or copolymers of compounds having no unsaturated aliphatic radicals in side chain, and having one or more carbon-to-carbon double bonds in a carbocyclic or in a heterocyclic ring system; Compositions of derivatives of such polymers
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08L—COMPOSITIONS OF MACROMOLECULAR COMPOUNDS
    • C08L65/00—Compositions of macromolecular compounds obtained by reactions forming a carbon-to-carbon link in the main chain; Compositions of derivatives of such polymers

Definitions

  • the present invention relates to a resin composition, a method for producing the same, and a molded article.
  • a polymer (hydrogenated norbornene-based ring-opening polymer) obtained by hydrogenating a ring-opening polymer obtained by ring-opening polymerization of a monomer composition containing norbornene has an excellent balance of properties such as heat resistance, transparency, light resistance, low water absorbency, water vapor barrier property, chemical resistance, solvent resistance, dielectric properties, low birefringence, rigidity, and laser resistance, and is therefore used in a wide range of fields, such as optical materials, medical equipment, electrical insulating materials, and equipment for processing electronic components.
  • studies have been conducted to further improve the performance of resin compositions containing hydrogenated norbornene ring-opening polymers.
  • the present inventors conducted extensive research with the aim of solving the above problems. They discovered that by using a resin composition containing a crystalline hydrogenated norbornene ring-opening polymer having specified properties and an amorphous cyclic olefin polymer in a specified ratio, it is possible to form a molded article with excellent solvent resistance and heat sealability, and thus completed the present invention.
  • the object of this invention is to advantageously solve the above problems, and the present invention provides the following resin compositions [1] to [6], the following molded article [7], and the following method for producing the resin composition [8].
  • a resin composition comprising a crystalline hydrogenated norbornene ring-opening polymer and an amorphous cyclic olefin polymer, wherein the hydrogenated norbornene ring-opening polymer is a hydrogenated ring-opening polymer containing a structural unit derived from norbornene, and the norbornene-derived structural unit contains a compound represented by the following formula (I): and the mass ratio of the hydrogenated norbornene ring-opening polymer to the cyclic olefin polymer (hydrogenated norbornene ring-opening polymer/cyclic olefin polymer) is 75/25 or more and 95/5 or less.
  • the "proportion of meso dyads" of the cis structural unit (I) can be obtained as the proportion of the signal intensity of meso dyads to the total signal intensity of meso dyads and racemo dyads observed in 13C -NMR measurement. More specifically, the "proportion of meso dyads" of the "structural unit having a cis-1,3-cyclopentane structure represented by formula (I)" can be determined using the method described in the Examples of this specification.
  • the hydrogenated norbornene ring-opening polymer further has the following formula (II):
  • the ratio of the trans structural unit (II) to the total of the cis structural unit (I) and the structural unit having a trans-1,3-cyclopentane structure represented by the above formula (II) hereinafter, sometimes referred to as the "trans structural unit (II)"
  • this ratio may be referred to as the "isomerization rate"
  • the heat sealability of the molded article can be further improved.
  • the ratio of the trans structural unit (II) to the total of the cis structural unit (I) and the trans structural unit (II) can be determined by 13C -NMR measurement. More specifically, the isomerization ratio can be determined by the method described in the Examples of this specification.
  • the weight average molecular weight of the hydrogenated norbornene ring-opening polymer is 60,000 or more and 200,000 or less.
  • the weight-average molecular weight of the hydrogenated norbornene ring-opening polymer is within the above-mentioned range, the heat-sealability of the molded article can be further improved, and an excessive increase in the viscosity of the resin composition can be suppressed, thereby ensuring sufficient processability of the resin composition.
  • the "weight average molecular weight” is a value measured by gel permeation chromatography (GPC), and specifically, it can be measured using the method described in the examples of this specification.
  • the molded article obtained by molding the above-mentioned resin composition has excellent solvent resistance and heat sealability.
  • [8] A method for producing the resin composition according to any one of [1] to [6] above, comprising a step of kneading the hydrogenated norbornene ring-opening polymer and the cyclic olefin polymer to obtain the resin composition.
  • a resin composition capable of forming a molded article having excellent solvent resistance and heat sealability, and a method for producing the same. Furthermore, according to the present invention, a molded article having excellent solvent resistance and heat sealability can be provided.
  • the resin composition of the present invention can be used in various fields as a resin material for constituting various molded articles (particularly films, sheets, and bioreactor bags).
  • the resin composition of the present invention can be produced using the method for producing a resin composition of the present invention.
  • the molded article of the present invention can be obtained by molding the resin composition of the present invention.
  • the resin composition of the present invention contains a hydrogenated norbornene ring-opening polymer and a cyclic olefin polymer, and may optionally further contain components (other components) other than the hydrogenated norbornene ring-opening polymer and the cyclic olefin polymer.
  • the resin composition of the present invention is characterized in that the hydrogenated norbornene ring-opening polymer is crystalline, the cyclic olefin polymer is amorphous, the mass ratio of the hydrogenated norbornene ring-opening polymer to the cyclic olefin polymer is 75/25 or more and 95/5 or less, and the proportion of meso-dyads in the hydrogenated norbornene ring-opening polymer is less than 30%.
  • the norbornene-based hydrogenated ring-opening polymer is a hydrogenated ring-opening polymer containing structural units derived from norbornene.
  • the norbornene-based hydrogenated ring-opening polymer must be crystalline.
  • the norbornene-based structural units include at least cis structural units (I) represented by the following formula (I), which are obtained by hydrogenating norbornene units, and optionally trans structural units (II) represented by the following formula (II).
  • the hydrogenated norbornene ring-opening polymer contains at least a structural unit derived from norbornene, and may optionally contain a structural unit derived from a monomer other than norbornene (another monomer).
  • the hydrogenated norbornene ring-opening polymer preferably contains norbornene-derived structural units in an amount of 90% by mass or more, more preferably 93% by mass or more, even more preferably 96% by mass or more, and particularly preferably 99% by mass or more, of which total structural units are 100% by mass.
  • the proportion of norbornene-derived structural units in the total structural units of the hydrogenated norbornene ring-opening polymer is 90% by mass or more, heat resistance can be improved.
  • the proportion of norbornene-derived structural units in the total structural units of the hydrogenated norbornene ring-opening polymer is preferably 90% by mass or more.
  • the upper limit of the proportion of norbornene-derived structural units in all structural units of the hydrogenated norbornene ring-opening polymer is not particularly limited, and can be 100% by mass or less.
  • the other monomers that can be used to prepare the hydrogenated norbornene ring-opening polymers are not particularly limited as long as they are capable of ring-opening copolymerization with norbornene.
  • Examples of the other monomers include monomers other than norbornene that have a norbornene skeleton (hereinafter referred to as "norbornene monomers").
  • the other monomers may be used alone or in combination of two or more.
  • norbornene-based monomers include norbornene-based monomers that do not have a ring fused with a norbornene ring (non-fused ring norbornene-based monomers), and norbornene-based monomers that have a ring fused with a norbornene ring (fused ring norbornene-based monomers).
  • non-condensed ring-forming norbornene monomers examples include norbornenes having an alkyl group such as 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, 5-decylnorbornene, 5-cyclohexylnorbornene, and 5-cyclopentylnorbornene; norbornenes having an alkenyl group such as 5-ethylidenenorbornene, 5-vinylnorbornene, 5-propenylnorbornene, 5-cyclohexenylnorbornene, and 5-cyclopentenylnorbornene; norbornenes having an aromatic ring such as 5-phenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, and 5-ethoxycarbonylnorbornene
  • norbornene having a polar group containing an oxygen atom such as norbornene, 5-methyl-5-methoxycarbonylnorbornene, 5-methyl-5-ethoxycarbonylnorbornene, norbornenyl-2-methylpropionate, norbornenyl-2-methyloctanate, 5-hydroxymethylnorbornene, 5,6-di(hydroxymethyl)norbornene, 5,5-di(hydroxymethyl)norbornene, 5-hydroxyisopropylnorbornene, 5,6-dicarboxynorbornene, and 5-methoxycarbonyl-6-carboxynorbornene; and norbornenes having a polar group containing a nitrogen atom, such as 5-cyanonorbornene. These may be used alone or in combination of two or more.
  • fused ring-forming norbornene monomer examples include monomers represented by the following formulae (III) and (IV).
  • R1 and R2 each independently represent a hydrogen atom, a halogen atom, a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent, or a substituent containing a silicon atom, an oxygen atom, or a nitrogen atom (excluding those which fall under the category of hydrocarbon groups having 1 to 20 carbon atoms which may have a substituent), and may be bonded to each other to form a ring.
  • R3 is a divalent hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
  • Examples of the monomer represented by formula (IV) above include tetracyclododecenes where m is 1 and hexacycloheptadecenes where m is 2.
  • the norbornene-based ring-opening polymer hydrogenation product must have a meso-dyad ratio of the cis structural unit (I) contained in the norbornene-derived structural unit of less than 30%. If the meso-dyad ratio of the cis structural unit (I) is 30% or more, the stereoregularity of the molecular chain portion formed by the cis structural unit (I) in the norbornene-based ring-opening polymer hydrogenation product is reduced (i.e., the molecular chain portion formed by the cis structural unit (I) has an atactic structure).
  • the meso-dyad ratio of the cis structural unit (I) is 30% or more, the heat-sealing property of the resin composition is reduced.
  • the meso-dyad ratio of the cis structural unit (I) is less than 30% (i.e., the molecular chain portion formed by the cis structural unit (I) has a syndiotactic structure), the resin composition can have excellent heat-sealing property.
  • the proportion of trans structural units (II) in the total of cis structural units (I) and trans structural units (II) is preferably 0.5% or more, more preferably 2% or more, even more preferably more than 5%, and is preferably 30% or less, more preferably 25% or less, even more preferably 23% or less, and particularly preferably 20% or less.
  • the heat-sealability of the resin composition can be further improved.
  • the isomerization rate of the hydrogenated norbornene ring-opening polymer can be adjusted by changing the method for producing the hydrogenated norbornene ring-opening polymer, for example, by changing the type and/or amount of the hydrogenation catalyst used when subjecting the precursor norbornene ring-opening polymer to a hydrogenation reaction.
  • the weight-average molecular weight of the norbornene ring-opening polymer hydrogenated product is preferably 60,000 or more, more preferably 65,000 or more, and even more preferably 70,000 or more, and is preferably 200,000 or less, more preferably 150,000 or less, still more preferably 90,000 or less, and particularly preferably 80,000 or less. If the weight-average molecular weight of the norbornene ring-opening polymer hydrogenated product is 60,000 or more, the heat-sealability of the resin composition can be further improved.
  • the weight-average molecular weight of the norbornene ring-opening polymer hydrogenated product is 200,000 or less, the viscosity of the resin composition can be prevented from excessively increasing, and the processability of the resin composition can be sufficiently ensured.
  • the weight-average molecular weight of the hydrogenated norbornene ring-opening polymer can be adjusted by changing the method for producing the hydrogenated norbornene ring-opening polymer, for example, by changing the type and/or amount of a ring-opening polymerization catalyst, a molecular weight modifier, etc., used when preparing the norbornene ring-opening polymer, which is a precursor of the hydrogenated norbornene ring-opening polymer.
  • the hydrogenated norbornene ring-opening polymer must be crystalline, i.e., when the hydrogenated norbornene ring-opening polymer is subjected to differential scanning calorimetry (DSC), the melting point must be observable by optimizing the measurement conditions.
  • the melting point of the hydrogenated norbornene ring-opening polymer is preferably 110° C. or higher, more preferably 120° C. or higher, and even more preferably 130° C. or higher, and is preferably 150° C. or lower, and more preferably 140° C. or lower. If the melting point of the hydrogenated norbornene ring-opening polymer is 110° C.
  • the heat resistance of the hydrogenated norbornene ring-opening polymer can be sufficiently ensured.
  • the melting point of the hydrogenated norbornene ring-opening polymer is 150° C. or lower, the heat sealability of the molded article can be further improved.
  • the melting point of the hydrogenated norbornene ring-opening polymer can be adjusted by changing the method for producing the hydrogenated norbornene ring-opening polymer, for example, by changing the type and/or amount of a monomer having a norbornene skeleton other than norbornene when preparing the norbornene ring-opening polymer, which is a precursor of the hydrogenated norbornene ring-opening polymer.
  • the hydrogenation rate of the hydrogenated norbornene ring-opening polymer (the proportion of hydrogenated carbon-carbon double bonds in the precursor norbornene ring-opening polymer) is usually 90% or more, preferably 95% or more, and more preferably 99% or more.
  • the hydrogenation rate of the hydrogenated norbornene ring-opening polymer can be determined by 1 H-NMR measurement.
  • the hydrogenation rate of the hydrogenated norbornene ring-opening polymer can be adjusted, for example, by changing the conditions of the hydrogenation reaction.
  • the hydrogenated norbornene ring-opening polymer can be prepared by ring-opening polymerizing a monomer composition containing norbornene and subjecting the resulting norbornene ring-opening polymer to a hydrogenation reaction. After the hydrogenation reaction, post-treatment may be carried out as necessary.
  • the ring-opening polymerization of the monomer composition containing norbornene can be carried out using a ring-opening polymerization catalyst.
  • a polymerization aid such as a molecular weight modifier may be added to the polymerization system.
  • the ring-opening polymerization may be carried out in the absence of a solvent or in the presence of a solvent.
  • the ring-opening polymerization catalyst is not particularly limited as long as it is capable of ring-opening polymerization of a monomer composition containing norbornene and can produce a norbornene-based ring-opening polymer that can be used as a precursor to a hydrogenated norbornene-based ring-opening polymer having predetermined properties.
  • a ring-opening polymerization catalyst that can impart stereoregularity to the norbornene-based ring-opening polymer is preferred as the ring-opening polymerization catalyst used to prepare the norbornene-based ring-opening polymer.
  • Transition metals of Group 6 of the periodic table contained in the complex catalyst include chromium, tungsten, and molybdenum, with tungsten and molybdenum being preferred.
  • complex catalysts containing transition metals of Group 6 of the periodic table include tungsten(ethylimide)(tetrachloride)(diethyl ether), tungsten(ethylimide)(t-butoxide)(trichloride), tungsten(ethylimide)[di(t-butoxide)](dichloride), tungsten(ethylimide)[tri(t-butoxide)](chloride), tungsten(ethylimide)[tetra(t-butoxide)], tungsten(ethylimide)(phenoxide)(tetrachloride)(diethyl ether), tungsten(n-butylimide)(tetrachloride)(tetrahydrofuran), tungsten(n-hexylimide)(tetrachloride)(diethyl ether), tungsten(n-hexylimide)(tetrachloride)(diethyl ether),
  • Examples include tungsten(i-propylimide)(tetrachloride)(diethyl ether), tungsten(cyclohexylimide)(tetrachloride)(diethyl ether), tungsten(adamantylimide)(tetrachloride)(diethyl ether), tungsten(benzylimide)(tetrachloride)(diethyl ether), tungsten(phenylimide)(tetrachloride)(diethyl ether), tungsten(phenylimide)(tetrachloride)(tetrahydrofuran), tungsten(2,6-dimethylphenylimide)(tetrachloride)(diethyl ether), and tungsten[2,6-di(i-propyl)(phenylimide)](tetrachloride)(diethyl ether).
  • complex catalysts containing transition metals from Group 6 of the periodic table include bis ⁇ 3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy ⁇ oxymolybdenum(VI), bis ⁇ 3,3',5,5'-tetramethyl-2,2'-biphenoxy ⁇ oxymolybdenum(VI), and ⁇ 3,3'-di(t-butyl)-5,5',6,6'-tetramethyl-2,2'-biphenoxy ⁇ oxymolybdenum(VI).
  • a complex catalyst containing a transition metal of Group 6 of the periodic table is a complex catalyst represented by the following formula (V):
  • the complex catalyst containing a transition metal from Group 6 of the periodic table may be used alone or in combination of two or more.
  • Tungsten phenylimide
  • tetrachloride tetrahydrofuran
  • the ring-opening polymerization catalyst it is preferable to use the above-mentioned complex catalyst containing a transition metal of Group 6 of the periodic table in combination with a co-catalyst other than the complex catalyst in order to enhance catalytic activity.
  • organolithium compound examples include n-butyllithium, methyllithium, phenyllithium, neopentyllithium, and neophyllithium.
  • organic magnesium compound examples include butylethyl magnesium, butyloctyl magnesium, dihexyl magnesium, ethyl magnesium chloride, n-butyl magnesium chloride, allyl magnesium bromide, neopentyl magnesium chloride, and neophyl magnesium chloride.
  • the organic zinc compounds include dimethyl zinc, diethyl zinc, and diphenyl zinc.
  • the hydrogenation catalyst may be used alone or in combination of two or more.
  • a supported heterogeneous catalyst is preferred as the hydrogenation catalyst, since the hydrogenation catalyst can be easily removed by filtering the reaction solution after the hydrogenation reaction.
  • Specific preferred examples of supported heterogeneous catalysts include combinations of nickel/silica, nickel/diatomaceous earth, nickel/alumina, palladium/carbon, palladium/silica, palladium/diatomaceous earth, and palladium/alumina.
  • the conditions for the hydrogenation reaction are not particularly limited and can be appropriately set depending on the desired physical properties of the hydrogenated norbornene ring-opening polymer (for example, the hydrogenation rate and the isomerization rate).
  • post-treatment can be carried out as necessary to satisfactorily isolate the desired hydrogenated norbornene ring-opening polymer.
  • a heterogeneous catalyst when used, the hydrogenation reaction is filtered to remove the hydrogenation catalyst, followed by coagulation drying or direct drying using a thin-film dryer or the like.
  • a homogeneous catalyst when used as the hydrogenation catalyst, after the hydrogenation reaction, alcohol or water is added to deactivate the catalyst, making it insoluble in the solvent, and then filtering is carried out to remove the catalyst.
  • the hydrogenated norbornene ring-opening polymer can usually be obtained in the form of a powder or pellets.
  • the cyclic olefin polymer is not particularly limited as long as it is an amorphous polymer obtained by polymerizing a cyclic olefin.
  • cyclic olefin polymers include copolymers of cyclic olefins and linear olefins, ring-opening polymers of cyclic olefins, and hydrogenated ring-opening polymers of cyclic olefins.
  • the copolymer of a cyclic olefin and a chain olefin is usually a polymer obtained by addition copolymerization of a cyclic olefin and a chain olefin.
  • the hydrogenated product of the ring-opening polymer of a cyclic olefin is obtained by hydrogenating the above-mentioned ring-opening polymer of a cyclic olefin.
  • the method for hydrogenating the ring-opening polymer of a cyclic olefin is not particularly limited, and any known method can be used.
  • a method may be used in which a known hydrogenation catalyst containing a transition metal such as nickel or palladium is added to a solution of the ring-opening polymer of a cyclic olefin to hydrogenate the carbon-carbon double bonds in the ring-opening polymer.
  • the lower limit of the proportion of norbornene-derived structural units in all structural units of the cyclic olefin polymer is not particularly limited, and can be, for example, 0% by mass or more, 5% by mass or more, or 10% by mass or more.
  • the other components are not particularly limited, and examples thereof include polymers other than the above-mentioned hydrogenated norbornene ring-opening polymers and cyclic olefin polymers (such as thermoplastic elastomers), fillers, antioxidants such as tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl], release agents, flame retardants, antibacterial agents, wood flour, coupling agents, plasticizers, colorants, lubricants, silicone oil, foaming agents, surfactants, light stabilizers, dispersing aids, heat stabilizers, ultraviolet absorbers, antistatic agents, dispersants, chlorine scavengers, crystallization nucleating agents, antifogging agents, organic fillers, neutralizing agents, decomposing agents, metal deactivators, and antifouling agents.
  • One type of the other components may be used alone, or two or more types may be used in combination.
  • the mass ratio of norbornene-based ring-opening polymer hydrogenation to cyclic olefin-based polymer in the resin composition is preferably 75/25 or more, more preferably 80/20 or more, even more preferably 85/15 or more, and preferably 95/5 or less, more preferably 90/10 or less. If the norbornene-based ring-opening polymer hydrogenation/cyclic olefin-based polymer ratio is 75/25 or more, the solvent resistance of the molded article can be further improved.
  • the heat sealability of the molded article can be further improved and the haze value of the molded article can be reduced.
  • the method for producing a resin composition of the present invention includes at least a step (kneading step) of kneading a hydrogenated norbornene ring-opening polymer and a cyclic olefin polymer to obtain a resin composition.
  • the method for producing a resin composition of the present invention may further include a step (other step) other than the kneading step.
  • ⁇ Kneading process> the norbornene-based hydrogenated ring-opening polymer and the cyclic olefin polymer are kneaded to obtain a resin composition.
  • the norbornene-based hydrogenated ring-opening polymer and the cyclic olefin polymer are those described above in the "Resin composition” section.
  • other components described above in the "Resin composition” section can also be added to the norbornene-based hydrogenated ring-opening polymer and the cyclic olefin polymer.
  • a melt kneader such as a single-screw extruder, twin-screw extruder, Banbury mixer, kneader, or feeder ruder can be used.
  • the kneading temperature is preferably in the range of 200 to 400°C, and more preferably in the range of 240 to 300°C.
  • the components may be added all at once and kneaded, or may be added in several portions and kneaded at the same time.
  • Processes include, for example, a process of preparing a hydrogenated norbornene ring-opening polymer prior to the kneading process (preparation process), and a process of extruding the resin composition obtained in the kneading process to form pellets (extrusion process).
  • the method for preparing the hydrogenated norbornene ring-opening polymer in the preparation step can be the method described above in the "Resin Composition" section.
  • the molded article of the present invention is formed using the resin composition of the present invention described above. Since the molded article of the present invention is formed by molding the resin composition of the present invention, it has excellent solvent resistance and heat sealability.
  • the method for producing the molded article is not particularly limited.
  • the resin composition can be molded into a molded article using, for example, known molding methods such as injection molding, compression molding, extrusion molding, blow molding, inflation molding, calendar molding, and solution casting.
  • the shape of the molded article can be selected appropriately depending on the application.
  • Optical materials such as optical disks, optical lenses, prisms, light diffusion plates, optical cards, optical fibers, optical mirrors, liquid crystal display element substrates, light guide plates, polarizing films, and retardation films;
  • Containers for liquid, powder, or solid medicines liquid medicine containers for injection, ampoules, vials, prefilled syringes, bioreactor bags, infusion bags, inner layers, middle layers, outer layers of multilayer films, sealant films, sealed medicine bags, press-through packages, solid medicine containers, eye drop containers, etc.), sampling containers (blood test sampling test tubes, medicine container caps, blood collection tubes, specimen containers, etc.), medical instruments (syringes, etc.), sterilized containers for medical instruments (for scalpels, forceps, gauze, contact lenses, etc.), laboratory and analytical instruments (beakers, petri dishes, flasks, test tubes, centrifuge tubes, etc.), medical optical components (plastic lenses for medical testing, etc.
  • the thickness of the film or sheet used as the molded article of the present invention is not particularly limited, but is typically 1 ⁇ m to 20 mm, preferably 5 ⁇ m to 5 mm, and more preferably 10 ⁇ m to 2 mm.
  • the film and sheet as the molded article of the present invention may be a laminate having a layer containing the resin composition of the present invention and a layer containing a known polymer that is generally used in the fields of home appliances, food, medicine, etc.
  • the number of layers to be laminated is usually 2 or 3, but a laminate of more layers can be used.
  • the order of arrangement of layers according to the polymer species in a multilayer structure of 3 or more layers can be determined depending on the purpose and application.
  • ⁇ Copolymerization Composition Ratio of Norbornene Ring-Opening Polymer> Based on 1 H-NMR measurement, the ratio of the number of hydrogen atoms derived from norbornene units to the number of hydrogen atoms derived from other monomer units was determined, and the copolymerization composition ratio of the norbornene ring-opening polymer was calculated based on this ratio.
  • the norbornene ring-opening polymer for measurement was collected by pouring a large amount of acetone into a polymerization reaction solution containing the norbornene ring-opening polymer, filtering the resulting aggregate, washing the filtered product with methanol, and drying it under reduced pressure at 40°C for 24 hours.
  • Example 6 Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 4, except that the amount of hydrogenated norbornene ring-opening polymer B used was changed from 95 parts to 85 parts and the amount of cyclic olefin polymer Y used was changed from 5 parts to 15 parts during the preparation of the resin compositions. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 7 Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 4, except that the amount of hydrogenated norbornene ring-opening polymer B used was changed from 95 parts to 75 parts and the amount of cyclic olefin polymer Y used was changed from 5 parts to 25 parts during the preparation of the resin compositions. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 1.
  • Example 8 A molded article was produced in the same manner as in Example 1, except that the resin composition prepared as follows was used, and evaluation was carried out in the same manner as in Example 1. The results are shown in Table 1.
  • ⁇ Preparation of Resin Composition> [Preparation of hydrogenated norbornene ring-opening polymer C] A norbornene-based ring-opening polymer hydride (norbornene-based ring-opening polymer hydride C) was prepared and pelletized in the same manner as in Example 1, except that 99 parts of norbornene and 1 part of dicyclopentadiene were used instead of 100 parts of norbornene, and the amount of the diatomaceous earth-supported nickel catalyst used was changed from 3 parts to 5 parts.
  • norbornene-based ring-opening polymer hydride C was crystalline according to the definition of the present invention.
  • [Mixing and Extrusion] 90 parts of pellets of the hydrogenated norbornene ring-opening polymer C obtained as described above and 10 parts of cyclic olefin polymer Y were mixed, and the mixture was kneaded and extruded in the same manner as in Example 1 to obtain a pelletized resin composition.
  • Example 9 Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 2, except that the amount of norbornene ring-opening polymer hydride B used was changed from 95 parts to 90 parts, and 10 parts of ring-opening polymer hydride Z obtained in Production Example 3 were used instead of 5 parts of ring-opening polymer hydride X as the cyclic olefin polymer. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 2.
  • Example 1 A resin composition and a molded article were prepared or produced in the same manner as in Example 1, except that cyclic olefin polymer X was not used when preparing the resin composition. Evaluations were then carried out in the same manner as in Example 1. The results are shown in Table 2.
  • Comparative Example 2 Resin compositions and molded articles were prepared or fabricated in the same manner as in Example 1, except that the amount of hydrogenated norbornene ring-opening polymer A used was changed from 95 parts to 97 parts and the amount of cyclic olefin polymer X used was changed from 5 parts to 3 parts during the preparation of the resin compositions. Evaluations were then performed in the same manner as in Example 1. The results are shown in Table 2.
  • Example 4 A resin composition and a molded article were prepared or produced in the same manner as in Example 2, except that cyclic olefin polymer X was not used when preparing the resin composition. Evaluations were then carried out in the same manner as in Example 1. The results are shown in Table 2.
  • Example 5 A resin composition and a molded article were prepared or produced in the same manner as in Example 8, except that cyclic olefin polymer Y was not used when preparing the resin composition. Evaluations were then carried out in the same manner as in Example 1. The results are shown in Table 2.
  • the polymerization reaction solution obtained above was transferred to a pressure-resistant hydrogenation reactor, and 0.5 parts of a diatomaceous earth-supported nickel catalyst (manufactured by JGC Chemical Industries, Ltd.; "T8400RL", nickel loading 58 wt%, manufactured by Süd-Chemie Catalysts) was added thereto, and the reaction was carried out for 6 hours at 160 ° C. and a hydrogen pressure of 4.5 MPa.
  • This solution was filtered through a filter equipped with a stainless steel wire mesh using 1 part of separately added diatomaceous earth as a filter aid, and the catalyst was removed.
  • the resulting reaction solution was dried for 48 hours in a vacuum dryer set at 0.13 ⁇ 10 3 Pa or less and 100 ° C.
  • norbornene-based ring-opening polymer hydrogenated product D was crystalline according to the definition in the present invention.
  • an antioxidant tetrakis[methylene-3-(3',5'-di-tert-butyl-4'-hydroxyphenyl)propionate]methane, Irganox 1010, manufactured by BASF
  • TEM-35B twin-screw kneader
  • Hydrogenated products A to D respectively represent “Hydrogenated products A to D of norbornene-based ring-opening polymers”
  • Polymers X to Z respectively represent “cyclic olefin polymers X to Z”
  • NB represents a structural unit derived from norbornene
  • DCPD refers to a structural unit derived from dicyclopentadiene
  • TCD represents a structural unit derived from tetracyclododecene
  • Mw indicates the weight average molecular weight
  • Tg refers to the glass transition temperature.
  • Tables 1 and 2 show that in Examples 1 to 9, which used resin compositions in which the mass ratio of the hydrogenated norbornene ring-opening polymer to the cyclic olefin polymer was within a predetermined range and the proportion of meso-dyads in the cis structural unit (I) was less than a predetermined value, molded articles with excellent solvent resistance and heat sealability were produced.
  • Comparative Example 6 which uses a resin composition in which the proportion of meso-dyads in the cis structural unit (I) is equal to or greater than a predetermined value, it can be seen that both the solvent resistance and heat sealability of the molded body are reduced compared to Examples 1 to 9.
  • a resin composition capable of forming a molded article having excellent solvent resistance and heat sealability, and a method for producing the same. Furthermore, according to the present invention, a molded article having excellent solvent resistance and heat sealability can be provided.

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  • Chemical & Material Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Medicinal Chemistry (AREA)
  • Polymers & Plastics (AREA)
  • Organic Chemistry (AREA)
  • Polyoxymethylene Polymers And Polymers With Carbon-To-Carbon Bonds (AREA)

Abstract

Le but de la présente invention est de fournir une composition de résine qui permet de former un corps moulé présentant une excellente résistance aux solvants et une excellente thermoscellabilité. La présente invention concerne une composition de résine contenant un hydrure de polymère à cycle ouvert à base de norbornène cristallin et un polymère à base d'oléfine cyclique amorphe, l'hydrure de polymère à cycle ouvert à base de norbornène étant un hydrure de polymère à cycle ouvert contenant un motif structural dérivé de norbornène ; le rapport méso-dyade d'un motif structural cis, qui est représenté par la formule (I), contenu dans le motif structural dérivé du norbornène est inférieur à 30 % ; et le rapport en masse de l'hydrure de polymère à cycle ouvert à base de norbornène sur le polymère à base d'oléfine cyclique est 75/25 à 95/5.
PCT/JP2025/007557 2024-03-27 2025-03-03 Composition de résine, son procédé de production, et corps moulé Pending WO2025204544A1 (fr)

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Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007016102A (ja) * 2005-07-06 2007-01-25 Nippon Zeon Co Ltd 環状オレフィン系重合体組成物および成形材料
WO2009001724A1 (fr) * 2007-06-22 2008-12-31 Zeon Corporation Composition de résine et film l'utilisant
WO2009066511A1 (fr) * 2007-11-21 2009-05-28 Zeon Corporation Composition de polymère et son utilisation
JP2011006498A (ja) * 2009-06-23 2011-01-13 Nippon Zeon Co Ltd 樹脂組成物およびフィルム
JP2011111573A (ja) * 2009-11-30 2011-06-09 Nippon Zeon Co Ltd 非晶質環状オレフィン重合体及び結晶性ノルボルネン系重合体からなる樹脂組成物。
JP2018507949A (ja) * 2015-03-09 2018-03-22 日本ゼオン株式会社 シンジオタクチック−ノルボルネン系開環重合体水素化物
WO2020195801A1 (fr) * 2019-03-27 2020-10-01 日本ゼオン株式会社 Hydrure de polymère à ouverture de cycle, composition de résine et article moulé
WO2022209818A1 (fr) * 2021-04-01 2022-10-06 日本ゼオン株式会社 Film optique et son procédé de fabrication

Patent Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2007016102A (ja) * 2005-07-06 2007-01-25 Nippon Zeon Co Ltd 環状オレフィン系重合体組成物および成形材料
WO2009001724A1 (fr) * 2007-06-22 2008-12-31 Zeon Corporation Composition de résine et film l'utilisant
WO2009066511A1 (fr) * 2007-11-21 2009-05-28 Zeon Corporation Composition de polymère et son utilisation
JP2011006498A (ja) * 2009-06-23 2011-01-13 Nippon Zeon Co Ltd 樹脂組成物およびフィルム
JP2011111573A (ja) * 2009-11-30 2011-06-09 Nippon Zeon Co Ltd 非晶質環状オレフィン重合体及び結晶性ノルボルネン系重合体からなる樹脂組成物。
JP2018507949A (ja) * 2015-03-09 2018-03-22 日本ゼオン株式会社 シンジオタクチック−ノルボルネン系開環重合体水素化物
WO2020195801A1 (fr) * 2019-03-27 2020-10-01 日本ゼオン株式会社 Hydrure de polymère à ouverture de cycle, composition de résine et article moulé
WO2022209818A1 (fr) * 2021-04-01 2022-10-06 日本ゼオン株式会社 Film optique et son procédé de fabrication

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