WO2024127881A1 - Hydrure de polymère à cycle ouvert d'oléfine cyclique, composition de résine et film - Google Patents

Hydrure de polymère à cycle ouvert d'oléfine cyclique, composition de résine et film Download PDF

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WO2024127881A1
WO2024127881A1 PCT/JP2023/040822 JP2023040822W WO2024127881A1 WO 2024127881 A1 WO2024127881 A1 WO 2024127881A1 JP 2023040822 W JP2023040822 W JP 2023040822W WO 2024127881 A1 WO2024127881 A1 WO 2024127881A1
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ring
cyclic olefin
opening polymer
olefin ring
mass
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Japanese (ja)
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聖 山田
克久 吉村
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日本ゼオン株式会社
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    • 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
    • C08G61/02—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes
    • C08G61/04—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms
    • C08G61/06—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds
    • C08G61/08—Macromolecular compounds containing only carbon atoms in the main chain of the macromolecule, e.g. polyxylylenes only aliphatic carbon atoms prepared by ring-opening of carbocyclic compounds of carbocyclic compounds containing one or more carbon-to-carbon double bonds in the ring
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
    • C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
    • C08J5/18—Manufacture of films or sheets

Definitions

  • the present invention relates to a hydrogenated cyclic olefin ring-opening polymer, and a resin composition and a film that contain the hydrogenated cyclic olefin ring-opening polymer.
  • Hydrogenated ring-opening polymers of cyclic olefins have excellent optical properties such as transparency, heat resistance, and low birefringence, as well as moldability and chemical resistance, and are therefore attracting attention as molding materials that can be used in a variety of applications, including optical applications.
  • various proposals have been made to improve the physical properties of hydrogenated ring-opening polymers of cyclic olefins.
  • Patent Document 1 discloses that in a hydrogenated cyclic olefin ring-opening polymer consisting of repeating units derived from tetracyclododecene and repeating units derived from other norbornene-based monomers, the heat yellowing resistance, dimensional stability at high temperatures, and moldability of the hydrogenated cyclic olefin ring-opening polymer can be improved by controlling the respective content ratios of the repeating units derived from tetracyclododecene and the repeating units derived from other norbornene-based monomers, the racemodiat ratio of the repeating units derived from tetracyclododecene, and the weight average molecular weight.
  • Patent Document 2 also discloses that in a tetracyclododecene-containing ring-opening polymer hydrogenation product, which is a cyclic olefin ring-opening polymer hydrogenation product containing a repeating unit (A) derived from tetracyclododecene and a repeating unit (B) derived from methanotetrahydrofluorene, the content ratio of repeating unit (A) and repeating unit (B) and the ratio of racemo dyads and meso dyads in repeating unit (A) are controlled to improve the solubility, fluidity, transparency, low birefringence, and the like of the tetracyclododecene-containing ring-opening polymer hydrogenation product.
  • a tetracyclododecene-containing ring-opening polymer hydrogenation product which is a cyclic olefin ring-opening polymer hydrogenation product
  • hydrogenated cyclic olefin ring-opening polymer having excellent surface hardness as an optical material used in molding an optical film used as a surface member in display devices such as liquid crystal displays, organic EL displays, and ⁇ LED displays.
  • hydrogenated cyclic olefin ring-opening polymers used as materials for films such as optical films are also required to be free from breakage or cracks when formed into a film and wound into a roll (i.e., to have excellent film-forming properties).
  • the hydrogenated cyclic olefin ring-opening polymers of the above-mentioned prior art did not necessarily have sufficient surface hardness and film-forming properties.
  • the present invention aims to provide a hydrogenated cyclic olefin ring-opening polymer that has excellent surface hardness and film-forming properties, as well as a resin composition and a film that contain the hydrogenated cyclic olefin ring-opening polymer.
  • the present inventors have conducted extensive research with the aim of solving the above problems.
  • the inventors have discovered that a hydrogenated cyclic olefin ring-opening polymer containing two or more types of structural units derived from polycyclic norbornene monomers having a polycyclic structure with four or more rings, and structural units derived from polycyclic norbornene monomers having a polycyclic structure with two or three rings, each in a specified ratio, and having a weight-average molecular weight within a specified range, has excellent surface hardness and film-forming properties, and have completed the present invention.
  • an object of the present invention is to advantageously solve the above-mentioned problems, and the present invention provides: [1] a hydrogenated cyclic olefin ring-opening polymer comprising two or more types of structural units (A) derived from a polycyclic norbornene monomer having a polycyclic structure of four or more rings, and a structural unit (B) derived from a polycyclic norbornene monomer having a polycyclic structure of two or three rings, wherein, when the content of all repeating units contained in the hydrogenated cyclic olefin ring-opening polymer is taken as 100 mass%, the content of the structural unit (A) is 80 mass% or more and the content of the structural unit (B) is 5 mass% or more and 20 mass% or less, and the weight average molecular weight is 27,000 or more and 50,000 or less.
  • a hydrogenated cyclic olefin ring-opening polymer containing two or more types of structural units (A) derived from a polycyclic norbornene monomer having a polycyclic structure with four or more rings, and a structural unit (B) derived from a polycyclic norbornene monomer having a polycyclic structure with two or three rings, by controlling the contents of the structural units (A) and (B) within the above-mentioned specified ranges, respectively, and controlling the weight average molecular weight of the hydrogenated cyclic olefin ring-opening polymer within the above-mentioned specified ranges, it is possible to obtain a hydrogenated cyclic olefin ring-opening polymer having excellent surface hardness and film formability.
  • the weight average molecular weight of the hydrogenated cyclic olefin ring-opening polymer can be measured by the method described in the Examples, and the content ratio of the structural unit can be measured by a nuclear magnetic resonance (NMR) method such as 1 H-NMR or 13 C-NMR.
  • NMR nuclear magnetic resonance
  • the hydrogenated cyclic olefin ring-opening polymer of [1] above preferably contains a structural unit derived from tetracyclododecene and a structural unit derived from methanotetrahydrofluorene.
  • a structural unit derived from tetracyclododecene and a structural unit derived from methanotetrahydrofluorene the surface hardness and film-forming properties of the hydrogenated cyclic olefin ring-opening polymer can be further improved.
  • the hydrogenated cyclic olefin ring-opening polymer of the above [1] or [2] preferably contains a structural unit derived from dicyclopentadiene. In this way, by including a structural unit derived from dicyclopentadiene, the surface hardness of the hydrogenated cyclic olefin ring-opening polymer can be further increased.
  • the hydrogenated cyclic olefin ring-opening polymer according to any one of [1] to [3] above when formed into a film, has a scratch hardness of at least B as measured according to JIS K5600.
  • a hydrogenated cyclic olefin ring-opening polymer having a scratch hardness of at least B as measured according to JIS K5600 when formed into a film has excellent surface hardness.
  • the scratch hardness is measured by the pencil method, and can be measured by the method described in the examples.
  • the hydrogenated cyclic olefin ring-opening polymer according to any one of [1] to [4] above when molded into a film, has a yield point in a stress-strain curve in a tensile test carried out in accordance with JIS K 7127.
  • a hydrogenated cyclic olefin ring-opening polymer which has a yield point in a stress-strain curve in a predetermined tensile test when molded into a film has excellent film formability.
  • the tensile test and confirmation of the yield point in the stress-strain curve can be carried out by the method described in the Examples.
  • the present invention also aims to advantageously solve the above problems, and provides a resin composition [6] that contains any of the hydrogenated cyclic olefin ring-opening polymers [1] to [5] above.
  • a resin composition that contains any of the hydrogenated cyclic olefin ring-opening polymers described above it is possible to produce a film that has excellent surface hardness and is less susceptible to breakage or cracking when wound into a roll.
  • the present invention also aims to advantageously solve the above problems, and provides [7] a film formed from the resin composition of [6] above.
  • the film formed from the above-mentioned resin composition has excellent surface hardness and is less likely to break or crack when wound into a roll.
  • the present invention can provide a hydrogenated cyclic olefin ring-opening polymer having excellent surface hardness and film-forming properties, as well as a resin composition and a film that contain the hydrogenated cyclic olefin ring-opening polymer.
  • the hydrogenated cyclic olefin ring-opening polymer of the present invention has excellent surface hardness and film-forming properties, and therefore can be suitably used as a material for forming films such as optical films.
  • the resin composition of the present invention can be suitably used as a material for producing the film of the present invention, for example.
  • the film of the present invention can also be suitably used as an optical film for display devices.
  • the hydrogenated cyclic olefin ring-opening polymer can be obtained, for example, by ring-opening polymerization of a monomer composition containing a norbornene compound in the presence of a polymerization catalyst, and then hydrogenating the carbon-carbon unsaturated bonds present in the obtained cyclic olefin ring-opening polymer.
  • the hydrogenated cyclic olefin ring-opening polymer of the present invention contains two or more types of structural units (A) derived from a polycyclic norbornene monomer having a polycyclic structure with four or more rings, and the structural units (B) derived from a polycyclic norbornene monomer having a polycyclic structure with two or three rings, in proportions of 80 mass% or more and 5 mass% to 20 mass%, respectively, and optionally further contains other structural units.
  • the hydrogenated cyclic olefin ring-opening polymer of the present invention needs to have a weight average molecular weight of 27,000 or more and 50,000 or less. If the weight average molecular weight is 27,000 or more, film-forming properties can be ensured. On the other hand, if the weight average molecular weight is 50,000 or less, the solubility of the cyclic olefin ring-opening polymer or the hydrogenated cyclic olefin ring-opening polymer in a solvent can be suppressed from deteriorating in the ring-opening polymerization step or the hydrogenation step, so that productivity can be ensured and surface hardness can be ensured.
  • the weight average molecular weight of the hydrogenated cyclic olefin ring-opening polymer is preferably 30,000 or more, more preferably 33,000 or more, and more preferably 45,000 or less, and more preferably 42,000 or less.
  • the weight average molecular weight of the hydrogenated cyclic olefin ring-opening polymer can be adjusted, for example, by changing the type and/or the amount of a molecular weight regulator (chain transfer agent) used in preparing the cyclic olefin ring-opening polymer as a precursor of the hydrogenated cyclic olefin ring-opening polymer.
  • the polycyclic norbornene monomer having a polycyclic structure with four or more rings which can form the structural unit (A) (hereinafter, also simply referred to as "structural unit (A)") derived from a polycyclic norbornene monomer having a polycyclic structure with four or more rings, include compounds having one or more norbornene rings and two or more ring structures (excluding norbornene rings) in the molecule.
  • the ring structure and the norbornene ring may exist separately as a single ring, or may form a condensed ring.
  • the hydrogenated cyclic olefin ring-opening polymer it is preferable that at least one ring structure and the norbornene ring form a condensed ring, and it is more preferable that all ring structures and the norbornene rings form a condensed ring.
  • the ring structure and/or norbornene ring may have one or more substituents.
  • the substituents are not particularly limited, and include halogen atoms such as chlorine, fluorine, and bromine; chain alkyl groups such as methyl, ethyl, and butyl; cyclic alkyl groups such as cyclopentane and cyclohexane; aryl groups such as phenyl and tolyl; alkenyl groups such as vinyl and propenyl; alkoxy groups such as methoxy and ethoxy; hydroxyalkyl groups such as hydroxymethyl; alkoxycarbonyl groups such as methoxycarbonyl; alkylpropionate groups such as methylpropionate; amine groups; imide groups; cyano groups; carboxyl groups; silyl groups; hydroxyl groups; and cyclic anhydride groups such as dicarboxylic anhydride.
  • halogen atoms such as chlorine, fluorine, and bromine
  • chain alkyl groups such as methyl, ethyl, and butyl
  • the ring structure is not particularly limited, and examples thereof include an aliphatic ring and an aromatic ring.
  • the ring structure may be a monocyclic structure or a polycyclic structure formed by condensing at least one ring selected from the group consisting of an aliphatic ring and an aromatic ring.
  • the aliphatic ring is not particularly limited, and examples thereof include an aliphatic hydrocarbon ring and an aliphatic heterocycle.
  • the aliphatic hydrocarbon ring include cycloalkyl rings such as a cyclopentane ring and a cyclohexane ring; cycloalkenyl rings such as a cyclopentene ring and a cyclohexene ring; and saturated bridged hydrocarbon rings such as a bicycloheptane ring (norbornane ring) and a bicyclooctane ring.
  • the aliphatic heterocycle examples include nitrogen-containing heterocycles such as a piperidine ring, a piperazine ring, and a hexamethyleneimine ring.
  • the above-mentioned aliphatic ring is preferably an aliphatic hydrocarbon ring.
  • Aromatic rings include, but are not limited to, aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring; and aromatic heterocycles such as a thiophene ring, a pyrrole ring, and a pyridine ring.
  • aromatic hydrocarbon rings such as a benzene ring, a naphthalene ring, and an anthracene ring
  • aromatic heterocycles such as a thiophene ring, a pyrrole ring, and a pyridine ring.
  • the aromatic ring is an aromatic hydrocarbon ring.
  • tetracyclododecene tetracyclo[4.4.0.1 2,5 .1 7,10 ]-dodec-3-ene
  • tetracyclododecenes having an alkyl group such as 8-methyltetracyclododecene, 8-ethyltetracyclododecene, 8-cyclohexyltetracyclododecene, and 8-cyclopentyltetracyclododecene
  • tetracyclododecenes having a double bond outside the ring such as 8-methylidenetetracyclododecene, 8-ethylidenetetracyclododecene, 8-vinyltetracyclododecene
  • the polycyclic norbornene monomer having a polycyclic structure with four or more rings as described above must be used in two or more types.
  • the hydrogenated cyclic olefin ring-opening polymer must contain two or more types of structural unit (A).
  • A structural unit
  • the surface hardness and film-formability of the hydrogenated cyclic olefin ring-opening polymer can be ensured.
  • the combination of two or more types of polycyclic norbornene monomers having a polycyclic structure of four or more rings preferably includes tetracyclo[ 4.4.0.12,5.17,10 ]-dodec-3-ene ( tetracyclododecene ) and 1,4-methano-1,4,4a,9a-tetrahydrofluorene (methanotetrahydrofluorene), and the polycyclic norbornene monomer having a polycyclic structure of four or more rings is more preferably a combination of tetracyclododecene and methanotetrahydrofluorene. That is, the hydrogenated cyclic olefin ring-opening polymer preferably includes a structural unit derived from tetracyclododecene and a structural unit derived from meth
  • the mass ratio of structural units derived from tetracyclododecene to structural units derived from methanotetrahydrofluorene in the hydrogenated cyclic olefin ring-opening polymer is preferably 40/60 or more and 80/20 or less.
  • the content of structural units derived from tetracyclododecene is preferably 50 mass% or more, more preferably 55 mass% or more, and even more preferably 60 mass% or more.
  • the content of structural units derived from methanotetrahydrofluorene is preferably 10 mass% or more, more preferably 15 mass% or more, and even more preferably 20 mass% or more.
  • the proportion of structural units (A) in all structural units (100% by mass) contained in the hydrogenated cyclic olefin ring-opening polymer must be 80% by mass or more (the total proportion of two or more types of structural units (A)). If the proportion of structural units (A) is less than 80% by mass, the surface hardness cannot be ensured. From the viewpoint of obtaining a hydrogenated cyclic olefin ring-opening polymer having even greater surface hardness, it is preferable that the proportion of structural units (A) is 85% by mass or more.
  • the polycyclic norbornene monomer having a two- or three-ring polycyclic structure which can form the structural unit (B) (hereinafter also simply referred to as "structural unit (B)") derived from a polycyclic norbornene monomer having a two- or three-ring polycyclic structure, include a compound having only one norbornene ring as a ring structure in the molecule (a polycyclic norbornene monomer having a two-ring polycyclic structure) and a compound having one norbornene ring and one monocyclic structure in the molecule (a polycyclic norbornene monomer having a three-ring polycyclic structure). From the viewpoint of further increasing the surface hardness of the hydrogenated cyclic olefin ring-opening polymer, it is preferable to use a polycyclic norbornene monomer having
  • the compound having only one norbornene ring as a ring structure in the molecule is not particularly limited as long as it has one norbornene ring and no ring structure other than the norbornene ring, and examples thereof include compounds having one norbornene ring which may have one or more substituents in the molecule.
  • the substituent is not particularly limited as long as it does not have a ring structure, and examples of the substituent include halogen atoms such as chlorine, fluorine, bromine, etc.; chain alkyl groups such as methyl group, ethyl group, butyl group, etc.; chain alkenyl groups such as vinyl group, propenyl group, etc.; chain alkoxy groups such as methoxy group, ethoxy group, etc.; chain hydroxyalkyl groups such as hydroxymethyl group, etc.; chain alkoxycarbonyl groups such as methoxycarbonyl group, etc.; alkyl propionate groups such as methyl propionate, etc.; amine groups; amide groups; imide groups; cyano groups; carboxyl groups; silyl groups; hydroxyl groups; and the like.
  • halogen atoms such as chlorine, fluorine, bromine, etc.
  • chain alkyl groups such as methyl group, ethyl group, butyl group, etc.
  • polycyclic norbornene monomers having a two-ring polycyclic structure include bicyclo[2.2.1]hept-2-ene (common name: norbornene); norbornenes having a chain alkyl group such as 5-methylnorbornene, 5-ethylnorbornene, 5-butylnorbornene, 5-hexylnorbornene, and 5-decylnorbornene; norbornenes having a chain alkenyl group such as 5-ethylidenenorbornene, 5-vinylnorbornene, and 5-propenylnorbornene; 5-methoxycarbonylnorbornene, 5-ethoxycarbonylnorbornene, 5- Examples of such norbornenes include norbornenes having a polar group containing an oxygen atom, such as methyl-5-methoxycarbonylnorbornene, 5-methyl-5-e
  • Compound having one norbornene ring and one monocyclic structure in the molecule include compounds having one monocyclic structure which may have one or more substituents and one norbornene ring which may have one or more substituents in the molecule.
  • the substituent is not particularly limited as long as it does not have a cyclic structure, and includes the substituents explained in the above section "Compounds having only one norbornene ring as a cyclic structure in the molecule".
  • the monocyclic structure and the norbornene ring may exist separately as monocyclic rings, or may form a condensed ring.
  • the monocyclic structure and the norbornene ring form a condensed ring.
  • the monocyclic structure is not particularly limited, and may be an aliphatic monocyclic ring or an aromatic monocyclic ring.
  • the aliphatic monocyclic ring may be a saturated or unsaturated aliphatic hydrocarbon ring such as a cycloalkyl ring or a cycloalkenyl ring; or a nitrogen-containing aliphatic heterocyclic ring such as a piperidine ring, a piperazine ring, or a hexamethyleneimine ring.
  • an aliphatic hydrocarbon ring is preferred.
  • Examples of the cycloalkyl ring include a cyclopentane ring, a cyclohexane ring, etc.
  • Examples of the cycloalkene ring include a cyclopentene ring, a cyclohexene ring, etc.
  • Examples of the aromatic monocycle include aromatic hydrocarbon rings such as a benzene ring, and aromatic heterocycles such as a thiophene ring, a pyrrole ring, and a pyridine ring. Among these, aromatic hydrocarbon rings are preferred from the viewpoint of increasing the surface hardness and film-forming properties of the hydrogenated cyclic olefin ring-opening polymer.
  • polycyclic norbornene monomers having a three-ring polycyclic structure include dicyclopentadienes such as dicyclopentadiene, tricyclo[4.3.0.1 2,5 ]dec-3-ene, and tricyclo[4.4.1 2,5 .0]unda-3-ene; norbornenes having one cyclic alkyl group such as 5-cyclohexylnorbornene and 5-cyclopentylnorbornene; norbornenes having one cyclic alkenyl group such as 5-cyclohexenylnorbornene and 5-cyclopentenylnorbornene; phenylnorbornenes having one phenyl group such as 5-phenyl-2-norbornene; and 5-methyl-5-phenyl-bicyclo[2.2.1]hepta-3-ene.
  • dicyclopentadienes such as dicyclopentadiene, tricyclo[4.3.0.1 2,5 ]dec-3-ene, and tricyclo[4.4.1 2,5
  • dicyclopentadiene is preferably used from the viewpoint of further increasing the surface hardness of the hydrogenated cyclic olefin ring-opening polymer. That is, the hydrogenated cyclic olefin ring-opening polymer preferably contains a structural unit derived from dicyclopentadiene.
  • the proportion of structural unit (B) in all structural units (100% by mass) contained in the hydrogenated cyclic olefin ring-opening polymer must be 5% by mass or more and 20% by mass or less. If the proportion of structural unit (B) is 5% by mass or more, film formability can be ensured. If the proportion of structural unit (B) is 20% by mass or less, surface hardness can be ensured. From the viewpoint of obtaining a hydrogenated cyclic olefin ring-opening polymer having even greater surface hardness and film formability, the proportion of structural unit (B) is preferably 10% by mass or more and more preferably 15% by mass or less.
  • the other structural units that may be optionally contained in the hydrogenated cyclic olefin ring-opening polymer are not particularly limited as long as they are other than the above-mentioned structural unit (A) and structural unit (B), and examples thereof include structural units derived from non-norbornene compounds.
  • Non-norbornene compounds that can form structural units derived from non-norbornene compounds are not particularly limited, and examples thereof include monocyclic cycloalkenes such as cyclobutene, cyclopentene, cyclohexene, cycloheptene, cyclooctene, 1,4-cyclooctadiene, and cyclodecene.
  • the above-mentioned non-norbornene compounds may be used alone or in combination of two or more.
  • the proportion of other structural units (total proportion of other structural units) among all structural units (100% by mass) contained in the hydrogenated cyclic olefin ring-opening polymer is usually 0% by mass or more and 15% by mass or less.
  • the cyclic olefin ring-opening polymer as a precursor of the hydrogenated cyclic olefin ring-opening polymer containing 80% by mass or more of the structural unit (A) and 5% by mass or more and 20% by mass or less of the structural unit (B) can be obtained by ring-opening polymerization of a monomer composition (mixture) containing the monomers described in the above section "Hydrogenated cyclic olefin ring-opening polymer".
  • the cyclic olefin ring-opening polymer can be prepared by ring-opening polymerization of the monomer composition using a known ring-opening polymerization method such as ring-opening polymerization using a metathesis polymerization catalyst.
  • a known ring-opening polymerization method such as ring-opening polymerization using a metathesis polymerization catalyst.
  • the metathesis polymerization catalyst is not particularly limited, and known catalysts can be used. Specifically, for example, a catalyst system consisting of a halide, nitrate, or acetylacetone compound of a metal selected from ruthenium, rhodium, palladium, osmium, iridium, platinum, etc., and a reducing agent; a catalyst system consisting of a halide or acetylacetone compound of a metal selected from titanium, vanadium, zirconium, tungsten, and molybdenum, and an organoaluminum compound as a promoter; or a known Schrock-type or Grubbs-type living ring-opening metathesis catalyst disclosed in JP-A-7-179575, J.
  • the above catalyst system can further contain a polar compound to enhance the polymerization activity and the selectivity of ring-opening polymerization.
  • polar compounds include molecular oxygen, alcohols, ethers, peroxides, carboxylic acids, acid anhydrides, acid chlorides, esters, ketones, nitrogen-containing compounds, sulfur-containing compounds, halogen-containing compounds, molecular iodine, and other Lewis acids.
  • the nitrogen-containing compounds are preferably aliphatic or aromatic tertiary amines, and specific examples include triethylamine, dimethylaniline, tri-n-butylamine, pyridine, and ⁇ -picoline. These polar compounds are used alone or in combination of two or more.
  • the amount of the polar compounds used is appropriately selected, but the ratio to the metal in the catalyst, i.e., the polar compound/metal ratio (molar ratio), is usually in the range of 1 to 100,000, and preferably 5 to 10,000.
  • the polymerization reaction may be carried out by bulk polymerization without using a solvent, or in a solvent such as an organic solvent.
  • a solvent such as an organic solvent.
  • the solvent includes aromatic hydrocarbons such as benzene, toluene, and xylene; aliphatic hydrocarbons such as n-pentane, hexane, and heptane; alicyclic hydrocarbons such as cyclohexane; halogenated hydrocarbons such as styrene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene, dichlorobenzene, and trichlorobenzene; and nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene, acetonitrile, and benzonitrile.
  • Polymerization conditions such as polymerization temperature, polymerization pressure, and polymerization time can be adjusted as appropriate.
  • the obtained cyclic olefin ring-opening polymer can be hydrogenated using hydrogen and a hydrogenation catalyst.
  • the cyclic olefin ring-opening polymer can be hydrogenated using any hydrogenation catalyst and hydrogenation conditions as long as the non-aromatic carbon-carbon unsaturated bonds, such as olefinic double bonds, present in the cyclic olefin ring-opening polymer can be hydrogenated.
  • the hydrogenation of the cyclic olefin ring-opening polymer is carried out so that the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bonds such as olefinic double bonds present in the cyclic olefin ring-opening polymer (the ratio of hydrogenated bonds to the non-aromatic carbon-carbon unsaturated bonds in the cyclic olefin ring-opening polymer) is usually 90% or more, preferably 95% or more, and more preferably 99% or more.
  • the carbon-carbon unsaturated bond of the aromatic ring may or may not be hydrogenated, as long as the effect of the present invention is not impaired.
  • the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bonds such as olefinic double bonds contained in the cyclic olefin ring-opening polymer is equal to or higher than the above lower limit, the hydrogenated cyclic olefin ring-opening polymer can be provided with good surface hardness and film-forming properties.
  • the hydrogenation rates of non-aromatic carbon-carbon unsaturated bonds and aromatic carbon-carbon unsaturated bonds can be measured by the method described in the Examples. Furthermore, the hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond and the aromatic carbon-carbon unsaturated bond can be adjusted, for example, by changing the type of hydrogenation catalyst and/or the hydrogenation reaction conditions.
  • hydrogenation catalysts examples include hydrogenation catalysts consisting of dicyclopentadienyl titanium halides, organic nickel carboxylates, organic cobalt carboxylates, etc., and organometallic compounds of Groups 1 to 3 of the periodic table; metal catalysts such as nickel, platinum, palladium, ruthenium, rhenium, and rhodium supported on carbon, silica, diatomaceous earth, etc., and metal catalysts such as cobalt, nickel, rhodium, and ruthenium complexes; and hydrogenation compounds such as lithium aluminum hydride and p-toluenesulfonyl hydrazide.
  • ruthenium compounds are preferred as hydrogenation catalysts, from the viewpoint of obtaining the target product in good yield without isomerization.
  • ruthenium compounds include RuHCl(CO)(PPh 3 ) 3 and RuHCl. (CO)[P(p-Me-Ph) 3 ] 3 , RuHCl(CO)( PCy3 ) 2 , RuHCl(CO)[P(n-Bu) 3 ] 3 , RuHCl(CO)[P(i-Pr) 3 ] 2 , RuH2 (CO)( PPh3 ) 3 , RuH2 (CO)[P(p-Me-Ph) 3 ] 3 , RuH2 (CO)( PCy3 ) 3 , RuH2 (CO)[P(n-Bu) 3 ] 3 , RuH( OCOCH3 )(CO)( PPh3 ) 2 , RuH(OCOPh)(CO)( PPh3 ) 2 , RuH(OCOPh- CH3 ) )(CO)( PPh3 ) 2 , RuH(OCOPh- OCH3 )(CO)
  • the hydrogenation reaction of the cyclic olefin ring-opening polymer can usually be carried out in an inert organic solvent.
  • inert organic solvents include aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as pentane and hexane; alicyclic hydrocarbon solvents such as cyclohexane and decahydronaphthalene; and ether solvents such as tetrahydrofuran and ethylene glycol dimethyl ether.
  • the reaction temperature when hydrogen is added to a system in which a cyclic olefin ring-opening polymer and a hydrogenation catalyst are present to hydrogenate the cyclic olefin ring-opening polymer varies depending on the hydrogenation catalyst used, but is usually ⁇ 20° C. to 250° C., preferably ⁇ 10° C. to 220° C., and more preferably 0° C. to 200° C. If the reaction temperature is too low, the hydrogenation rate may become too slow, and if the reaction temperature is too high, side reactions may occur.
  • the hydrogen pressure is usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, and more preferably 0.1 to 10 MPa.
  • the reaction time varies depending on the reaction scale, but is usually 0.1 to 10 hours.
  • the resulting hydrogenated cyclic olefin ring-opening polymer can be recovered in a conventional manner.
  • catalyst residues can be removed by filtration or other methods.
  • the hydrogenated cyclic olefin ring-opening polymer obtained by hydrogenating a cyclic olefin ring-opening polymer usually has two or more types of structural units (A) derived from a polycyclic norbornene monomer having a polycyclic structure with four or more rings, and a structural unit (B) derived from a polycyclic norbornene monomer having a polycyclic structure with two or three rings, and optionally further has other structural units.
  • the structural unit (A) derived from a polycyclic norbornene monomer having a polycyclic structure of 4 or more rings in the hydrogenated cyclic olefin ring-opening polymer includes a structural unit obtained when a polycyclic norbornene monomer having a polycyclic structure of 4 or more rings is ring-opened and a structural unit obtained by hydrogenating the structural unit.
  • the structural unit (B) derived from a polycyclic norbornene monomer having a polycyclic structure of 2 or 3 rings in the hydrogenated cyclic olefin ring-opening polymer includes a structural unit obtained when a polycyclic norbornene monomer having a polycyclic structure of 2 or 3 rings is ring-opened and a structural unit obtained by hydrogenating the structural unit.
  • the "structural unit obtained upon ring-opening polymerization of a polycyclic norbornene monomer having a polycyclic structure with four or more rings” and the "structural unit obtained upon ring-opening polymerization of a polycyclic norbornene monomer having a polycyclic structure with two or three rings" in the hydrogenated cyclic olefin ring-opening polymer are unhydrogenated structural units (repeating units) that were not hydrogenated during the hydrogenation of the cyclic olefin ring-opening polymer.
  • the hydrogenated cyclic olefin ring-opening polymer preferably has the following properties:
  • the hydrogenated cyclic olefin ring-opening polymer When molded into a film, the hydrogenated cyclic olefin ring-opening polymer preferably has a scratch hardness of B or more, more preferably HB or more, measured according to JIS K5600.
  • a hydrogenated cyclic olefin ring-opening polymer having a scratch hardness of B or more has excellent surface hardness
  • a hydrogenated cyclic olefin ring-opening polymer having a scratch hardness of HB or more has even more excellent surface hardness.
  • the resin composition of the present invention contains the above-mentioned hydrogenated cyclic olefin ring-opening polymer of the present invention, and optionally further contains polymer materials other than the hydrogenated cyclic olefin ring-opening polymer of the present invention and/or various additives.
  • the polymeric materials and additives that may be contained in the resin composition are not particularly limited, and examples thereof include the polymeric materials and additives described in JP-A-10-139865.
  • the resin composition contains an antioxidant such as a phenol-based antioxidant, a phosphorus-based antioxidant, or a sulfur-based antioxidant.
  • an antioxidant such as a phenol-based antioxidant, a phosphorus-based antioxidant, or a sulfur-based antioxidant.
  • the polymeric material and the additives can be mixed with the hydrogenated cyclic olefin ring-opening polymer by any method without any particular limitation as long as they can be sufficiently dispersed in the hydrogenated cyclic olefin ring-opening polymer.
  • the polymeric material and the additives may be added at any stage during the preparation of the hydrogenated cyclic olefin ring-opening polymer, may be kneaded with the hydrogenated cyclic olefin ring-opening polymer by using a kneader, or may be mixed with the hydrogenated cyclic olefin ring-opening polymer in a molding device.
  • the blending amounts of the polymer material and the additives are not particularly limited as long as the effects of the present invention are not impaired, and can be, for example, 0.01 parts by mass or more and 2.0 parts by mass or less per 100 parts by mass of the hydrogenated cyclic olefin ring-opening polymer.
  • the film of the present invention is produced by molding the above-mentioned resin composition of the present invention into a film shape. Since the film of the present invention contains the above-mentioned hydrogenated cyclic olefin ring-opening polymer of the present invention, the film of the present invention has excellent surface hardness and is suppressed from breaking or cracking when wound into a roll.
  • the film of the present invention is not particularly limited, but is preferably an optical film. This is because the film of the present invention has excellent surface hardness and can be suitably used as a surface member in display devices such as liquid crystal displays, organic EL displays, and ⁇ LED displays.
  • the molding method is not particularly limited as long as it can mold the resin composition into a film, and for example, molding methods such as extrusion molding, cast molding, blow molding, inflation molding, etc. Among them, the extrusion method is preferred, and the melt extrusion method is more preferred.
  • the film of the present invention can be obtained, for example, by heating and melting pellets of the resin composition, melt-extruding the resulting molten resin to obtain a film, and then winding up the film in a roll.
  • the film of the present invention may have a multi-layer structure in which any intermediate layer is sandwiched between a plurality of films of the present invention.
  • the film of the present invention thus obtained preferably has the following properties:
  • the film of the present invention preferably has a scratch hardness of B or more, more preferably HB or more, on at least one side, as measured according to JIS K5600. If the scratch hardness is B or more, the surface hardness is excellent, and if it is HB or more, the surface hardness is even more excellent.
  • the film of the present invention preferably has a scratch hardness of B or more, more preferably HB or more, on both sides.
  • the film of the present invention preferably has a yield point in a stress-strain curve of a tensile test carried out based on JIS K 7127.
  • a film having a yield point in the stress-strain curve of the tensile test is prevented from breaking or cracking when wound into a roll.
  • the film of the present invention preferably has a thickness of 20 ⁇ m or more. If the thickness is equal to or more than the above lower limit, the occurrence of breakage or cracks during winding into a roll is further suppressed.
  • the film of the present invention may have a hard coat on the surface.
  • the film of the present invention has excellent surface hardness, and the strength after the hard coat is provided can be further improved.
  • the hard coat may be provided on only one side of the film, or on both sides.
  • Weight Average Molecular Weight of Hydrogenated Cyclic Olefin Ring-Opening Polymer The weight average molecular weight (Mw) of the hydrogenated cyclic olefin ring-opening polymer was measured by gel permeation chromatography (GPC) using cyclohexane as an eluent, and calculated as a value equivalent to standard polyisoprene.
  • GPC gel permeation chromatography
  • the measurement was performed using three columns (TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL, manufactured by Tosoh Corporation) connected in series, under conditions of a flow rate of 1.0 mL/min, a sample injection amount of 100 ⁇ L, and a column temperature of 40°C.
  • TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL manufactured by Tosoh Corporation
  • the hydrogenation rate of non-aromatic carbon-carbon unsaturated bonds was measured by 1 H-NMR.
  • Example 1 Into a polymerization reactor whose inside had been dried and substituted with nitrogen, tetracyclo[4.4.0.1 2,5 . 2.0 parts (1% relative to the total amount of monomers used in polymerization) of a monomer mixture consisting of 55% by mass of 1,4-methano-1,4,4a,9a-tetrahydrofluorene (hereinafter sometimes abbreviated as "TCD”) and 30% by mass of 1,4-methano-1,4,4a,9a-tetrahydrofluorene (hereinafter sometimes abbreviated as "MTF") as well as 15% by mass of dicyclopentadiene (hereinafter sometimes abbreviated as "DCPD”) as a polycyclic norbornene monomer having a polycyclic structure of two or three rings, 583 parts of dehydrated cyclohexane, 0.87 parts of 1-hexene as a molecular weight regulator (chain transfer agent), 1.10 parts of an n-hexane solution of dieth
  • the mixture was filtered at a pressure of 0.25 MPa using a pressure filter (manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.; Funda Filter) with diatomaceous earth (Radiolite (registered trademark) #500) as a filter bed to obtain a colorless and transparent solution containing a hydrogenated cyclic olefin ring-opening polymer.
  • a pressure filter manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.; Funda Filter
  • diatomaceous earth Radiolite (registered trademark) #500
  • the solid content contained in the solution was extruded in a molten state into strands from a die directly connected to the concentrating machine, and after cooling with water, cut using a pelletizer (manufactured by Nagata Seisakusho; "OSP-2"). In this way, pellets of a resin composition containing a hydrogenated cyclic olefin ring-opening polymer were obtained.
  • the hydrogenation rate of the carbon-carbon double bonds (non-aromatic carbon-carbon unsaturated bonds) present in the hydrogenated cyclic olefin ring-opening polymer was 99% or more.
  • the pellets were charged into a film extruder (Optical Control Systems, Measuring Extruder Type Me-20/2800 V3) and melt extruded at a resin temperature of 280° C. and a screw rotation speed of 50 rpm to obtain a film having a thickness of 30 ⁇ m and a width of 120 mm.
  • Various evaluations were then carried out, and the results are shown in Table 1.
  • Example 2 Various operations and evaluations were carried out in the same manner as in Example 1, except that a monomer mixture consisting of 60 mass % TCD, 30 mass % MTF, and 10 mass % norbornene (hereinafter sometimes abbreviated as "NB") as a polycyclic norbornene monomer having a two- or three-ring polycyclic structure was used, and the amount of 1-hexene as a molecular weight regulator was changed to 1.05 parts. The results are shown in Table 1.
  • Example 3 Various operations and evaluations were carried out in the same manner as in Example 1, except that a monomer mixture consisting of 75 mass % of TCD, 20 mass % of MTF, and 5 mass % of NB was used. The results are shown in Table 1.
  • Example 4 Various operations and evaluations were carried out in the same manner as in Example 1, except that a monomer mixture consisting of 50 mass % TCD, 40 mass % MTF, and 10 mass % DCPD was used, and the amount of 1-hexene as a molecular weight regulator was changed to 0.67 parts. The results are shown in Table 1.
  • Example 1 Various operations and evaluations were carried out in the same manner as in Example 1, except that a monomer mixture consisting of 80 mass % TCD, 10 mass % MTF, and 10 mass % DCPD was used and the amount of 1-hexene as a molecular weight regulator was changed to 1.35 parts. The results are shown in Table 1.
  • Example 2 Various operations and evaluations were carried out in the same manner as in Example 1, except that a monomer mixture consisting of 75 mass % TCD and 25 mass % MTF was used and the amount of 1-hexene as a molecular weight regulator was changed to 1.05 parts. The results are shown in Table 1.
  • Example 3 Various operations and evaluations were carried out in the same manner as in Example 1, except that a monomer mixture consisting of 40 mass% TCD, 20 mass% MTF, and 40 mass% DCPD was used and the amount of 1-hexene as a molecular weight regulator was changed to 0.56 parts. The results are shown in Table 1.
  • Example 4 Various operations and evaluations were carried out in the same manner as in Example 1, except that a monomer mixture consisting of 75 mass % of TCD, 15 mass % of NB, and 10 mass % of DCPD was used. The results are shown in Table 1.
  • TCD stands for tetracyclododecene
  • MTF methanotetrahydrofluorene
  • NB stands for norbornene
  • DCPD dicyclopentadiene.
  • the hydrogenated cyclic olefin ring-opening polymers of Examples 1 to 4 which contain two or more types of structural units (A) derived from a polycyclic norbornene monomer having a polycyclic structure with four or more rings and a structural unit (B) derived from a polycyclic norbornene monomer having a polycyclic structure with two or three rings, have excellent surface hardness and film-forming properties, and the content of the structural units (A) is 80% by mass or more, the content of the structural units (B) is 5% by mass or more and 20% by mass or less, and the weight average molecular weight is 27,000 to 50,000.
  • the present invention can provide a hydrogenated cyclic olefin ring-opening polymer having excellent surface hardness and film-forming properties, as well as a resin composition and a film that contain the hydrogenated cyclic olefin ring-opening polymer.

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Abstract

L'objet de la présente invention est de fournir un hydrure de polymère à cycle ouvert d'oléfine cyclique qui présente une excellente dureté de surface et d'excellentes propriétés filmogènes. Un hydrure de polymère à cycle ouvert d'oléfine cyclique selon la présente invention contient au moins deux types de motifs structuraux (A) qui sont chacun dérivés d'un monomère norbornène polycyclique ayant une structure cyclique tétracyclique ou supérieure, et un motif structural (B) qui est dérivé d'un monomère norbornène polycyclique ayant une structure bicyclique ou tricyclique, et cet hydrure de polymère à cycle ouvert d'oléfine cyclique est caractérisé en ce que : si le rapport de teneur de tous les motifs répétitifs contenus dans cet hydrure de polymère à cycle ouvert d'oléfine cyclique est défini comme étant de 100 % en masse, le rapport de teneur des motifs structuraux (A) est supérieur ou égal à 80 % en masse et le rapport de teneur du motif structural (B) est de 5 % en masse à 20 % en masse (inclus) ; et la masse moléculaire moyenne en poids est de 27 000 à 50 000 (inclus).
PCT/JP2023/040822 2022-12-13 2023-11-13 Hydrure de polymère à cycle ouvert d'oléfine cyclique, composition de résine et film WO2024127881A1 (fr)

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Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008013604A (ja) * 2006-07-03 2008-01-24 Nippon Zeon Co Ltd テトラシクロドデセン含有開環重合体水素化物、光学樹脂材料および光学成形体
WO2014103788A1 (fr) * 2012-12-25 2014-07-03 日本ゼオン株式会社 Polymère optique et élément optique obtenu par formage de celui-ci
JP2014148634A (ja) * 2013-02-04 2014-08-21 Nippon Zeon Co Ltd ノルボルネン系開環重合体水素化物
WO2016052302A1 (fr) * 2014-09-29 2016-04-07 日本ゼオン株式会社 Hydrure de polymère à cycle ouvert d'oléfine cyclique, corps moulé en résine, et élément optique

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2008013604A (ja) * 2006-07-03 2008-01-24 Nippon Zeon Co Ltd テトラシクロドデセン含有開環重合体水素化物、光学樹脂材料および光学成形体
WO2014103788A1 (fr) * 2012-12-25 2014-07-03 日本ゼオン株式会社 Polymère optique et élément optique obtenu par formage de celui-ci
JP2014148634A (ja) * 2013-02-04 2014-08-21 Nippon Zeon Co Ltd ノルボルネン系開環重合体水素化物
WO2016052302A1 (fr) * 2014-09-29 2016-04-07 日本ゼオン株式会社 Hydrure de polymère à cycle ouvert d'oléfine cyclique, corps moulé en résine, et élément optique

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