Terminal hydroxyl group-containing cyclic olefin polymer, terminal aliphatic ring-containing cyclic olefin polymer, and polymer compound

Abstract

This terminal hydroxyl group-containing cyclic olefin polymer contains a cyclic olefin unit. The cyclic olefin unit contains an aliphatic carbon ring. The terminal hydroxyl group-containing cyclic olefin polymer contains a hydroxyl group at a terminal.

Description

Terminal hydroxyl group-containing cyclic olefin polymers, terminal aliphatic ring-containing cyclic olefin polymers, and polymer compounds

[0001] The present invention relates to terminal hydroxyl group-containing cyclic olefin polymers and methods for producing the same; terminal aliphatic ring-containing cyclic olefin polymers and methods for producing the same; polymer compounds produced from said terminal aliphatic ring-containing cyclic olefin polymers and methods for producing the same; and resin compositions using said polymer compounds and methods for producing the same, molded articles, films, polarizing plates, methods for producing stretched films, liquid crystal display devices, and organic electroluminescent display devices.

[0002] Conventionally, cyclic olefin polymers such as norbornene polymers have been used as film materials. These films can be used in conjunction with various components. For example, polarizing films have been manufactured by laminating cyclic olefin polymer films with polarizers. On the other hand, the technology described in Patent Document 1 is publicly known.

[0003] International Publication No. 2021 / 125222

[0004] Conventional films using cyclic olefin polymers tended to delaminate easily when bonded to any material. Specifically, they were prone to delamination, a phenomenon where the film would peel off from the material due to damage to the area near the surface. From the standpoint of improving reliability, it is desirable that films using cyclic olefin polymers do not easily delaminate when bonded to any material, and specifically, that they have high peel strength. The term "peel strength" refers to the amount of force required to peel the film.

[0005] The present invention was conceived in view of the above-mentioned problems, and aims to provide: a terminal hydroxyl group-containing cyclic olefin polymer and a method for producing the same that can produce a film material with high peel strength; a terminal aliphatic ring-containing cyclic olefin polymer and a method for producing the same that can produce a film material with high peel strength; a polymer compound and a method for producing the same that can produce a film material with high peel strength; a resin composition and the resin composition that can produce a film with high peel strength; a molded article, a film, a polarizing plate, a liquid crystal display device, and an organic electroluminescent display device containing the resin composition; and a method for producing a stretched film using the resin composition.

[0006] The inventors diligently studied to solve the aforementioned problems. As a result, they discovered that a film with high peel strength can be realized by using a novel polymer compound synthesized using a specific cyclic olefin polymer containing hydroxyl groups at its ends, and thus completed the present invention. That is, the present invention includes the following.

[0007] <1> A terminal hydroxyl group-containing cyclic olefin polymer containing a cyclic olefin unit, wherein the cyclic olefin unit contains an aliphatic carbon ring, and the terminal hydroxyl group-containing cyclic olefin polymer contains a hydroxyl group at its end. <2> The terminal hydroxyl group-containing cyclic olefin polymer according to claim 1, wherein the cyclic olefin unit includes a structure formed by ring-opening polymerization and hydrogenation of a cyclic olefin compound, and the hydrogenation rate of the cyclic olefin unit is 50% or more. <3> The terminal hydroxyl group-containing cyclic olefin polymer according to <1> or <2>, wherein the terminal hydroxyl group-containing cyclic olefin polymer contains a hydroxyl group at both ends. <4> A method for producing a terminal hydroxyl group-containing cyclic olefin polymer according to any one of <1> to <3>, comprising the step of polymerizing a cyclic olefin compound and an olefin compound containing a hydroxyl group. <5> A terminal aliphatic ring-containing cyclic olefin polymer containing a cyclic olefin unit, wherein the cyclic olefin unit contains an aliphatic carbon ring, and the terminal aliphatic ring-containing cyclic olefin polymer contains an unsaturated cyclic aliphatic hydrocarbon group at its end. <6> The terminal aliphatic ring-containing cyclic olefin polymer according to <5>, wherein the cyclic olefin unit includes a structure formed by ring-opening polymerization and hydrogenation of a cyclic olefin compound, and the hydrogenation rate of the cyclic olefin unit is 50% or more. <7> The terminal aliphatic ring-containing cyclic olefin polymer according to <5> or <6>, wherein the terminal aliphatic ring-containing cyclic olefin polymer contains unsaturated cyclic aliphatic hydrocarbon groups at both ends. A method for producing a terminal aliphatic ring-containing cyclic olefin polymer according to any one of items <5> to <7>, comprising reacting a terminal hydroxyl group-containing cyclic olefin polymer according to any one of items <1> to <3> with a cyclic olefin compound containing an unsaturated cyclic aliphatic hydrocarbon group and a carboxyl group, or a cyclic olefin compound containing an unsaturated cyclic aliphatic hydrocarbon group and an alkyl halogenate.<9> A polymer compound which is a polymer of a terminal aliphatic ring-containing cyclic olefin polymer described in any one of <5> to <7>. <10> A method for producing the polymer compound described in <9>, comprising the step of polymerizing a terminal aliphatic ring-containing cyclic olefin polymer described in any one of <5> to <7>. <11> A resin composition comprising the polymer compound described in <9> and a cyclic olefin polymer. <12> A method for producing the resin composition described in <11>, comprising the step of polymerizing a cyclic olefin compound in the presence of the polymer compound described in <9>. <13> A method for producing the resin composition described in <11>, comprising the step of mixing the polymer compound described in <9> and a cyclic olefin polymer. <14> A molded article comprising the resin composition described in <11>. <15> A film comprising the resin composition described in <11>. <16> A polarizing plate comprising the film described in <15> and a polarizer. <17> A method for manufacturing a stretched film, comprising the steps of: forming a pre-stretched film with the resin composition described in <11>; and stretching the pre-stretched film. <18> The method for manufacturing a stretched film according to <17>, wherein the step of forming the pre-stretched film comprises forming a long pre-stretched film, and the step of stretching the pre-stretched film comprises stretching the pre-stretched film in an oblique direction. <19> The method for manufacturing a stretched film according to <17> or <18>, wherein the step of stretching the pre-stretched film comprises stretching the pre-stretched film in one or two stretching directions. <20> The method for manufacturing a stretched film according to any one of <17> to <19>, wherein the step of stretching the pre-stretched film comprises stretching the pre-stretched film at a surface stretching ratio of 1.1 times or more. <21> A liquid crystal display device comprising the film described in <15>. <22> An organic electroluminescent display device comprising the film described in <15>.

[0008] The present invention provides a terminal hydroxyl group-containing cyclic olefin polymer capable of producing a film material with high peel strength and a method for producing the same; a terminal aliphatic ring-containing cyclic olefin polymer capable of producing a film material with high peel strength and a method for producing the same; a polymer compound capable of producing a film material with high peel strength and a method for producing the same; a resin composition capable of producing a film with high peel strength and the resin composition; a molded article, a film, a polarizing plate, a liquid crystal display device, and an organic electroluminescent display device containing the resin composition; and a method for producing a stretched film using the resin composition.

[0009] Figure 1 is a schematic perspective view showing the ring-shaped structure of a polymer compound (C) according to one example. Figure 2 is a schematic perspective view showing the ring-shaped structure of a polymer compound (C) according to another example.

[0010] The present invention will be described in detail below with reference to embodiments and examples. However, the present invention is not limited to the embodiments and examples shown below, and may be implemented with modifications as appropriate without departing from the scope of the claims and their equivalents.

[0011] In the following explanation, unless otherwise specified, the term "organic EL display device" refers to "organic electroluminescent display device." Similarly, unless otherwise specified, the term "organic EL element" refers to "organic electroluminescent element."

[0012] In the following explanation, unless otherwise specified, the notation "AA to BB" in the description of a numerical range means "AA or greater and BB or less." Here, "AA" and "BB" represent numerical values, and AA < BB. Furthermore, if multiple upper and lower limits or both are listed in the description of a numerical range, unless otherwise specified, you may arbitrarily combine a number selected from the group of numbers listed as the lower limit and a number selected from the group of numbers listed as the upper limit. In addition, you may use the numbers described in the examples as either the lower limit or both of the upper limits of the numerical range.

[0013] <Terminal Hydroxyl Group-Containing Cyclic Olefin Polymer (A)> (Overview of Terminal Hydroxyl Group-Containing Cyclic Olefin Polymer (A)) The terminal hydroxyl group-containing cyclic olefin polymer (A) according to one embodiment of the present invention contains cyclic olefin units containing aliphatic carbon rings and has hydroxyl groups at its ends. Using this terminal hydroxyl group-containing cyclic olefin polymer (A), a polymer compound (C) can be produced via the terminal aliphatic ring-containing cyclic olefin polymer (B) described later, and a resin composition (D) containing the polymer compound (C) can be produced. Since the resin composition (D) has high mechanical strength, it can be used as a material for films with high peel strength.

[0014] (Cyclic olefin units containing aliphatic carbon rings) The cyclic olefin units contained in the terminal hydroxyl group-containing cyclic olefin polymer (A) represent structural units derived from cyclic olefin compounds as monomers. The term "cyclic olefin unit" includes structural units having a structure formed by polymerizing cyclic olefin compounds, and structural units having a structure formed by hydrogenating said structural units.

[0015] As described above, cyclic olefin units contain aliphatic carbon rings. Examples of aliphatic carbon rings include saturated aliphatic carbon rings (cycloalkane rings) and unsaturated aliphatic carbon rings (cycloalkene rings, cycloalkyne rings, etc.). Among these, cycloalkane rings and cycloalkene rings are preferred from the viewpoint of mechanical strength and heat resistance, and cycloalkane rings are even more preferred.

[0016] The range of the number of carbon atoms constituting an aliphatic carbocyclic ring is preferably 4 or more, more preferably 5 or more, preferably 30 or less, more preferably 20 or less, and particularly preferably 15 or less per aliphatic carbocyclic ring. When the number of carbon atoms constituting an aliphatic carbocyclic ring is within the above range, mechanical strength, heat resistance, and moldability are highly balanced.

[0017] As a cyclic olefin compound corresponding to a cyclic olefin unit containing an aliphatic carbocyclic ring, a cyclic olefin compound containing two or more rings is preferred, and among these, a cyclic olefin compound containing a norbornene ring is even more preferred. The term "norbornene ring" refers to the carbocyclic ring formed by the carbon atoms of bicyclo[2.2.1]hept-2-ene (i.e., norbornene). The number of rings in a cyclic olefin compound containing a norbornene ring is usually two or more, preferably two to five, and more preferably two to four. Furthermore, the cyclic olefin compound may also contain an aromatic ring in combination with the unsaturated aliphatic carbocyclic ring. In addition, the number of cycloolefin rings in one molecule of the cyclic olefin compound may be two or more, but one is preferred.

[0018] Examples of cyclic olefin compounds containing a norbornene ring include bicyclic cyclic olefin compounds such as bicyclo[2.2.1]hept-2-ene; and tricyclo[4.3.0.1 ２，５ ] Tricyclic olefin compounds such as deca-3,7-diene (i.e., dicyclopentadiene); tetracyclo[4.4.0.1 ２，５ 1. ７，１０ ]Two-ring cyclic olefin compounds such as dodeca-3-ene (i.e., tetracyclododecene); five-ring cyclic olefin compounds such as 4,4a,4b,5,8,8a,9,9a-octahydro-1,4:5,8-bismethano-1H-fluorene (i.e., tricyclopetadiene); 7,8-benzotricyclo[4.3.0.1 ２，５ Examples include cyclic olefin compounds containing aromatic rings such as deca-3-ene (common name: metanotetrahydrofluorene); and derivatives thereof. Examples of the derivatives include compounds in which substituents are bonded to the ring of the cyclic olefin compounds exemplified above.

[0019] Examples of substituents include linear saturated hydrocarbon groups and polar groups. The number of carbon atoms in the linear saturated hydrocarbon group is preferably 1 to 20, and more preferably 1 to 3. Examples of linear saturated hydrocarbon groups include alkyl groups such as methyl, ethyl, and butyl groups. Examples of polar groups include heteroatoms or groups of atoms having heteroatoms. Examples of heteroatoms include oxygen, nitrogen, sulfur, silicon, and halogen atoms. Specific examples of polar groups include carboxyl groups, carbonyloxycarbonyl groups, epoxy groups, hydroxyl groups, oxy groups, ester groups, silanol groups, silyl groups, amino groups, nitrile groups, and sulfonic acid groups. Multiple substituents may be bonded to the ring, either identical or in different phases. From the viewpoint of smoothly producing the polymer compound (C) containing the ring-shaped structure described later, linear saturated hydrocarbon groups are preferred as substituents.

[0020] The cyclic olefin unit containing an aliphatic carbon ring may be of one type or of two or more types. Therefore, the cyclic olefin compound corresponding to the cyclic olefin unit may be used alone or in combination of two or more types.

[0021] The content range of cyclic olefin units containing aliphatic carbon rings in the terminal hydroxyl group-containing cyclic olefin polymer (A) is preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, and even more preferably 20% by weight or more, based on 100% by weight of the terminal hydroxyl group-containing cyclic olefin polymer (A). In particular, from the viewpoint of producing materials for optical films where high transparency is required, the content of cyclic olefin units containing aliphatic carbon rings is preferably 55% by weight or more, more preferably 70% by weight or more, and even more preferably 90% by weight or more. The upper limit is usually less than 100% by weight, and may be 99.9% by weight or less or 99.5% by weight or less.

[0022] When a cyclic olefin compound is polymerized to form a cyclic olefin unit, the cyclic olefin unit may contain a non-aromatic carbon-carbon unsaturated bond. For example, a cyclic olefin unit obtained by ring-opening polymerization of a cyclic olefin compound may contain a non-aromatic carbon-carbon unsaturated bond. As described above, since the cyclic olefin unit may include a structure formed by polymerizing and hydrogenating the cyclic olefin compound, the unsaturated bond contained in the cyclic olefin unit may be hydrogenated and become a single bond.

[0023] The degree of hydrogenation can be expressed as a hydrogenation rate. This hydrogenation rate represents the ratio of the number of single bonds resulting from hydrogenation to 100% of the number of non-aromatic carbon-carbon unsaturated bonds contained in the cyclic olefin units formed by polymerizing cyclic olefin compounds. The hydrogenation rate range of the cyclic olefin units in the terminal hydroxyl group-containing cyclic olefin polymer (A) is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, even more preferably 80% or more, and particularly preferably 90% or more, and may be 100%.

[0024] The hydrogenation rate of the polymer is orthodichlorobenzene-d ４ Using as a solvent, at 145°C, １ It can be measured by H-NMR.

[0025] (Arbitrary structural units) The terminal hydroxyl group-containing cyclic olefin polymer (A) may further contain arbitrary structural units in combination with the aliphatic carbocyclic cyclic olefin unit. Examples of arbitrary structural units include cyclic olefin units that do not contain aliphatic carbocyclics. Examples of cyclic olefin compounds corresponding to cyclic olefin units that do not contain aliphatic carbocyclics include monocyclic cyclic olefin compounds such as cyclopropene, cyclobutene, cyclopentene, methylcyclopentene, cyclohexene, methylcyclohexene, cycloheptene, cyclooctene, cyclohexadiene, methylcyclohexadiene, cyclooctadiene, and methylcyclooctadiene; and derivatives thereof. Examples of derivatives of monocyclic cyclic olefin compounds include compounds in which substituents are bonded to the ring of the cyclic olefin compound. The substituents may be the same as those that can be bonded to the ring of a cyclic olefin compound containing a norbornene ring. There may be one or more arbitrary structural units.

[0026] (Terminal Hydroxyl Groups) A terminal hydroxyl group-containing cyclic olefin polymer (A) contains hydroxyl groups at the ends of its polymer chains. A terminal hydroxyl group-containing cyclic olefin polymer (A) contains hydroxyl groups at one or more ends, preferably at multiple ends. Typically, a terminal hydroxyl group-containing cyclic olefin polymer (A) has a main chain containing cyclic olefin units including the aliphatic carbon rings described above, and contains hydroxyl groups at the ends of the main chain. In this case, the terminal hydroxyl group-containing cyclic olefin polymer (A) may contain hydroxyl groups at only one end of its main chain, or it may contain hydroxyl groups at both ends of its main chain. Among these, it is preferable that the terminal hydroxyl group-containing cyclic olefin polymer (A) contains hydroxyl groups at both ends.

[0027] The terminally hydroxyl-containing cyclic olefin polymer (A) may be used in the form of a composition containing polymers with different numbers of hydroxyl groups. Examples of such compositions include a single-terminally hydroxyl-containing cyclic olefin polymer containing a hydroxyl group at only one end, and a double-terminally hydroxyl-containing cyclic olefin polymer containing hydroxyl groups at both ends. When used in the form of such a composition, it is preferable that the proportion of the double-terminally hydroxyl-containing cyclic olefin polymer is large. In one example, the proportion of the double-terminally hydroxyl-containing cyclic olefin polymer is preferably 20% by weight or more, more preferably 40% by weight or more, even more preferably 60% by weight or more, and particularly preferably 80% by weight or more, relative to 100% by weight of the total amount of the terminally hydroxyl-containing cyclic olefin polymer (A) (usually the sum of the single-terminally hydroxyl-containing cyclic olefin polymer and the double-terminally hydroxyl-containing cyclic olefin polymer). The upper limit is usually 100% by weight or less. In particular, it is preferable that the terminally hydroxyl-containing cyclic olefin polymer (A) is entirely a double-terminally hydroxyl-containing cyclic olefin polymer containing hydroxyl groups at both ends.

[0028] The ratio of the cyclic olefin polymer containing hydroxyl groups at both ends to the total amount of the cyclic olefin polymer (A) (100% by weight) is: １ The molecular weight can be measured from the results of 1H-NMR and the weight-average molecular weight Mw. The weight-average molecular weight Mw can be measured using gel permeation chromatography (GPC). The specific measurement method may be the one described in the examples below.

[0029] Also, among the terminals of the polymer chains of the terminal hydroxyl group-containing cyclic olefin polymer (A), it is preferable that the proportion of the terminals containing hydroxyl groups is large. In one example, with respect to 100% of the number of terminals of the polymer chains possessed by the total amount of the terminal hydroxyl group-containing cyclic olefin polymer (A) (usually the total amount of the mono-terminal hydroxyl group-containing cyclic olefin polymer and the both-terminal hydroxyl group-containing cyclic olefin polymer), the range of the proportion of the number of terminals containing hydroxyl groups is preferably 50% or more, more preferably 60% or more, still more preferably 70% or more, and particularly preferably 80% or more. In the following description, the proportion of the number of terminals containing hydroxyl groups to 100% of the number of terminals of the polymer chains possessed by the total amount of the terminal hydroxyl group-containing cyclic olefin polymer (A) may be referred to as the "introduction rate of terminal hydroxyl groups". The upper limit of the introduction rate of terminal hydroxyl groups is usually 100% or less. Among them, it is preferable that the terminal hydroxyl group-containing cyclic olefin polymer (A) contains hydroxyl groups at all of its terminals.

[0030] The introduction rate of the terminal hydroxyl groups of the terminal hydroxyl group-containing cyclic olefin polymer (A) １ can be measured from the measurement results of 1H-NMR and the number average molecular weight Mn. The number average molecular weight Mn can be measured using gel permeation chromatography (GPC). A specific measurement method may adopt the method described in the examples described later.

[0031] In a preferred embodiment, the terminal hydroxyl group-containing cyclic olefin polymer (A) has a hydroxyalkyl group or a hydroxyalkylidene group at its terminal. In this case, the hydroxyl groups contained in those hydroxyalkyl groups or hydroxyalkylidene groups correspond to the hydroxyl groups at the terminals of the polymer chains of the terminal hydroxyl group-containing cyclic olefin polymer (A). The terminal hydroxyl group-containing cyclic olefin polymer (A) in such an embodiment can be produced, for example, by a production method including the polymerization of a cyclic olefin compound and an olefin compound containing a hydroxyl group, as described in the production method described later.

[0032] (Weight-average molecular weight) The weight-average molecular weight Mw of the terminal hydroxyl group-containing cyclic olefin polymer (A) preferably ranges from 5,000 or more, more preferably 10,000 or more, particularly preferably 15,000 or more, and preferably 100,000 or less, more preferably 80,000 or less, particularly preferably 50,000 or less. The weight-average molecular weight Mw can be measured using gel permeation chromatography (GPC). Examples of the solvent used in GPC include cyclohexane, toluene, and tetrahydrofuran. When GPC is used, the weight-average molecular weight is measured as the relative molecular weight in terms of polystyrene or polyisoprene. A specific measurement method may adopt the method described in the examples below.

[0033] (Glass transition temperature) The glass transition temperature Tg of the terminal hydroxyl group-containing cyclic olefin polymer (A) preferably ranges from -20°C or higher, more preferably -10°C or higher, particularly preferably -5°C or higher, and preferably 250°C or lower, more preferably 200°C or lower, particularly preferably 180°C or lower. The glass transition temperature Tg can be measured using a differential scanning calorimeter under the condition of a heating rate of 10°C / min based on JIS K 6911.

[0034] (Method for producing terminal hydroxyl group-containing cyclic olefin polymer (A)) Terminal hydroxyl group-containing cyclic olefin polymer (A) can be produced, for example, by a production method that includes the step of polymerizing the above-mentioned cyclic olefin compound and an olefin compound containing a hydroxyl group. In such polymerization, ring-opening metathesis polymerization of the cyclic olefin compound proceeds to form a polymer chain containing cyclic olefin units, and an olefin compound containing a hydroxyl group can react at the end of the chain to introduce a hydroxyl group. In addition, since the cyclic olefin units that are usually formed contain a non-aromatic carbon-carbon unsaturated bond, it is preferable that the method for producing terminal hydroxyl group-containing cyclic olefin polymer (A) includes a step of converting the unsaturated bond into a single bond by hydrogenation. To give a specific example, as shown in formula (A1) below, when norbornene as a cyclic olefin compound and 2-butene-1,4-diol as an olefin compound containing a hydroxyl group are polymerized, terminal hydroxyl group-containing cyclic olefin polymer (A) shown in formula (a1) can be produced. Subsequently, it is preferable to hydrogenate the non-aromatic carbon-carbon unsaturated bonds contained in the cyclic olefin unit to convert them into single bonds as shown in formula (a2). In formulas (a1) and (a2), n represents the number of repetitions. Furthermore, while cis-trans isomers may exist for the terminal hydroxyl group-containing cyclic olefin polymer (A) shown in formula (a1), formula (a1) does not distinguish between the cis and trans isomers, but can encompass the cis, trans, and any combination thereof.

[0035]

[0036] As the cyclic olefin compound, it is preferable to use the ones described above as the cyclic olefin compound corresponding to the cyclic olefin unit containing an aliphatic carbocyclic ring. This cyclic olefin compound may be used alone or in combination of two or more. The charging ratio of the cyclic olefin compound is preferably set according to the content rate of the cyclic olefin unit containing an aliphatic carbocyclic ring in the terminal hydroxyl group-containing cyclic olefin polymer (A). In one example, the amount (charging ratio) of the cyclic olefin compound with respect to 100 mol% of the total monomers used in the synthesis of the terminal hydroxyl group-containing cyclic olefin polymer (A) is preferably 10 mol% or more, more preferably 30 mol% or more, still more preferably 50 mol% or more, still more preferably 70 mol% or more, particularly preferably 80 mol% or more. The upper limit can be, for example, 99 mol% or less, 95 mol% or less, 90 mol% or less, etc.

[0037] As the olefin compound containing a hydroxyl group, an olefin compound containing one or more hydroxyl groups in one molecule can be used. This olefin compound preferably contains two or more hydroxyl groups in one molecule. Examples of the preferable olefin compound include the compound represented by the following formula (A2).

[0038]

[0039] (In formula (A2), R ａ each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, preferably a hydrogen atom; m ａ１ and m ａ２ each independently represents an integer of 1 or more. m ａ１ and m ａ２ each independently represents preferably an integer of 1 to 20, more preferably an integer of 1 to 10, still more preferably an integer of 1 to 6, and 1 is particularly preferable.)

[0040] Examples of olefin compounds represented by formula (A2) include 2-butene-1,4-diol, 2-pentene-1,5-diol, 2-hexene-1,6-diol, and 3-hexene-1,6-diol. Olefin compounds containing hydroxyl groups may be used individually or in combination of two or more types.

[0041] The charging ratio of the olefin compound containing hydroxyl groups is preferably set according to the degree of hydroxyl group introduction in the terminal hydroxyl group-containing cyclic olefin polymer (A). In one example, the amount of the olefin compound containing hydroxyl groups (charging ratio) relative to 100 mol% of the total monomers used in the synthesis of the terminal hydroxyl group-containing cyclic olefin polymer (A) is preferably 1 mol% or more, more preferably 5 mol% or more, even more preferably 10 mol% or more, preferably 90 mol% or less, more preferably 80 mol% or less, and even more preferably 50 mol% or less.

[0042] As monomers used in the synthesis of the terminal hydroxyl group-containing cyclic olefin polymer (A), any monomer corresponding to any structural unit may be used in combination with the cyclic olefin compound and the olefin compound containing a hydroxyl group as described above. Therefore, the method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A) may include polymerizing a monomer mixture containing a cyclic olefin compound, an olefin compound containing a hydroxyl group, and any monomer as needed. Examples of arbitrary monomers include cyclic olefin compounds corresponding to the cyclic olefin unit that does not contain an aliphatic carbon ring as described above. Any monomer may be used alone or in combination of two or more types.

[0043] From the viewpoint of smoothly carrying out ring-opening metathesis polymerization of cyclic olefin compounds, the polymerization is preferably carried out in the presence of a ring-opening polymerization catalyst. Preferred ring-opening polymerization catalysts include transition metal complexes; complexes of long-period Group 6 metals such as molybdenum and tungsten, and complexes of long-period Group 8 metals such as ruthenium and osmium; and carbene complexes of tungsten or ruthenium are particularly preferred. Specific examples of tungsten catalysts include tungsten hexachloride and tungsten oxytetrachloride. Furthermore, specific examples of ruthenium catalysts include bis(tricyclohexylphosphine)benzylideneruthenium dichloride, bis(triphenylphosphine)-3,3-diphenylpropenylideneruthenium dichloride, bis(tricyclohexylphosphine)t-butylvinylideneruthenium dichloride, dichloro-(3-phenyl-1H-indene-1-ylidene)bis(tricyclohexylphosphine)ruthenium, bis(1,3-diisopropylimidazoline-2-ylidene)benzylideneruthenium dichloride, and bis(1,3-dicyclohexyl Examples include midazoline-2-ylidene)benzylidene ruthenium dichloride, (1,3-dimethylimidazoline-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichloride, (1,3-dimethylimidazolidin-2-ylidene)(tricyclohexylphosphine)benzylidene ruthenium dichloride, bis(tricyclohexylphosphine)ethoxymethylidene ruthenium dichloride, and (1,3-dimethylimidazolidin-2-ylidene)(tricyclohexylphosphine)ethoxymethylidene ruthenium dichloride. Furthermore, if necessary, co-catalysts such as organolithium compounds, organomagnesium compounds, organozinc compounds, organoaluminum compounds, and organotin compounds may be used. The ring-opening polymerization catalyst may be used alone or in combination of two or more types.

[0044] The range of the amount of ring-opening polymerization catalyst used is preferably 1 / 2,000,000 moles or more, more preferably 1 / 1,500,000 moles or more, even more preferably 1 / 1,000,000 moles or more, preferably 1 / 500 moles or less, more preferably 1 / 700 moles or less, and even more preferably 1 / 1,000 moles or less, per mole of monomer.

[0045] Polymerization reactions may be carried out in solvent-free conditions or in a solvent. When polymerization is carried out in a solvent, it is preferable to use a solvent that is inert in the polymerization reaction and can dissolve the monomer and polymerization catalyst. Preferred solvents include hydrocarbon solvents, ether solvents, and halogen solvents. Examples of hydrocarbon solvents include aromatic hydrocarbon solvents such as benzene, toluene, xylene, and ethylbenzene; aliphatic hydrocarbon solvents such as hexane, n-heptane, and n-octane; and alicyclic hydrocarbon solvents such as cyclohexane, cyclopentane, and methylcyclohexane. Examples of ether solvents include 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, and 1,3-dioxolane. Examples of halogen solvents include haloalkane solvents such as dichloromethane and chloroform; and aromatic halogen solvents such as chlorobenzene and dichlorobenzene. One type of solvent may be used alone, or two or more types may be used in combination.

[0046] The polymerization reaction temperature can be set within a range in which the polymerization reaction can proceed. In one example, the polymerization reaction temperature range is preferably -100°C or higher, more preferably -50°C or higher, even more preferably 0°C or higher, particularly preferably 15°C or higher, and also preferably less than 120°C, more preferably less than 100°C, even more preferably less than 90°C, and particularly preferably less than 80°C.

[0047] The polymerization reaction time can be set within a range that yields the desired terminal hydroxyl group-containing cyclic olefin polymer (A). In one example, the polymerization reaction time is preferably 1 minute or more, more preferably 10 minutes or more, preferably 72 hours or less, and more preferably 20 hours or less.

[0048] The terminal hydroxyl group-containing cyclic olefin polymer (A) obtained by the polymerization described above may contain non-aromatic carbon-carbon unsaturated bonds. It is preferable to convert such unsaturated bonds into single bonds by hydrogenation. Therefore, the method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A) preferably includes a step of hydrogenating the obtained terminal hydroxyl group-containing cyclic olefin polymer (A) after the polymerization step described above. In such hydrogenation, hydrogen gas is usually reacted with the terminal hydroxyl group-containing cyclic olefin polymer (A) to convert the non-aromatic carbon-carbon unsaturated bonds into single bonds.

[0049] Hydrogenation is usually carried out using a hydrogenation catalyst. A wide range of catalysts used in the hydrogenation of olefin compounds can be used as hydrogenation catalysts. Homogeneous or heterogeneous catalysts may be used. Examples of homogeneous catalysts include Ziegler catalysts consisting of combinations of transition metal compounds and alkali metal compounds, such as cobalt acetate and triethylaluminum, nickel acetylacetonate and triisobutylaluminum, titanocene dichloride and n-butyllithium, zirconocene dichloride and sec-butyllithium, and tetrabutoxytitanate and dimethylmagnesium; dichlorotris(t Examples of noble metal complex catalysts include rhodium (riphenylphosphine), bis(tricyclohexylphosphine)benzyridine ruthenium (IV) dichloride, chlorohydride carbonyltris(triphenylphosphine)ruthenium, and catalysts described in Japanese Patent Publication No. 7-2929, Japanese Patent Publication No. 7-149823, Japanese Patent Publication No. 11-209460, Japanese Patent Publication No. 11-158256, Japanese Patent Publication No. 11-193323, or Japanese Patent Publication No. 11-209460. Heterogeneous catalysts include, for example, catalysts in which metals such as nickel, palladium, platinum, rhodium, and ruthenium are supported on carriers such as carbon, silica, diatomaceous earth, alumina, and titanium oxide. Specific examples of such heterogeneous catalysts include nickel / silica, nickel / diatomaceous earth, nickel / alumina, palladium / carbon, palladium / silica, palladium / diatomaceous earth, and palladium / alumina. Hydrogenation catalysts may be used individually or in combination of two or more types.

[0050] The hydrogenation reaction is preferably carried out in a solvent. Examples of solvents for the hydrogenation reaction include aromatic hydrocarbon solvents, aliphatic hydrocarbon solvents, alicyclic hydrocarbon solvents, ether solvents, and aromatic ether solvents. The same solvent used in the polymerization reaction described above may also be used as the solvent for the hydrogenation reaction. Therefore, the hydrogenation reaction may be carried out without changing the solvent after the polymerization reaction. One type of solvent may be used alone, or two or more types may be used in combination.

[0051] The hydrogenation reaction temperature can be selected depending on the type of hydrogenation catalyst. In one example, the range of the hydrogenation reaction temperature is preferably -20°C or higher, more preferably -10°C or higher, even more preferably 0°C or higher, and also preferably 250°C or lower, more preferably 220°C or lower, and even more preferably 200°C or lower.

[0052] The hydrogen gas pressure range in the hydrogenation reaction is preferably 0.01 MPa or higher, more preferably 0.05 MPa or higher, from the viewpoint of accelerating the rate of the hydrogenation reaction. The upper limit is preferably 10 MPa or lower, more preferably 8 MPa or lower, from the viewpoint of eliminating the need for a high-pressure reactor and enabling inexpensive manufacturing.

[0053] The hydrogenation reaction time can be set within a range that yields the desired hydrogenation rate. In one example, the hydrogenation reaction time is preferably 0.1 hours or more, and preferably 50 hours or less.

[0054] The method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A) may include any additional steps in combination with the polymerization and hydrogenation steps described above. For example, the method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A) may include a step of removing the used catalyst after obtaining the terminal hydroxyl group-containing cyclic olefin polymer (A). Examples of methods for removing the catalyst include centrifugation and filtration. At this time, catalyst removal may be accelerated by mixing in a catalyst deactivator such as water and alcohol, or by mixing in an adsorbent such as activated clay, alumina, and diatomaceous earth.

[0055] Furthermore, the method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A) may include a step of removing the solvent. When the terminal hydroxyl group-containing cyclic olefin polymer (A) is used in the production of the terminal aliphatic ring-containing cyclic olefin polymer (B) described later, from the viewpoint of simplifying handling, the terminal hydroxyl group-containing cyclic olefin polymer (A) may be used in the polymer solution without removing the solvent.

[0056] <Terminal Aliphatic Ring-Containing Cyclic Olefin Polymer (B)> (Overview of Terminal Aliphatic Ring-Containing Cyclic Olefin Polymer (B)) The terminal aliphatic ring-containing cyclic olefin polymer (B) according to one embodiment of the present invention contains cyclic olefin units containing aliphatic carbon rings and has an unsaturated cyclic aliphatic hydrocarbon group at its end. A polymer compound (C) can be produced from this terminal aliphatic ring-containing cyclic olefin polymer (B), and a resin composition (D) containing the polymer compound (C) can be produced. Since the resin composition (D) has high mechanical strength, it can be used as a material for films with high peel strength.

[0057] (Cyclic olefin units containing aliphatic carbon rings) The cyclic olefin units contained in terminal aliphatic ring-containing cyclic olefin polymer (B) are the same as the cyclic olefin units contained in terminal hydroxyl group-containing cyclic olefin polymer (A). Therefore, the cyclic olefin units containing aliphatic carbon rings contained in terminal aliphatic ring-containing cyclic olefin polymer (B) are the same as the cyclic olefin units containing aliphatic carbon rings contained in terminal hydroxyl group-containing cyclic olefin polymer (A).

[0058] Therefore, with respect to the terminal aliphatic ring-containing cyclic olefin polymer (B), the matters relating to the cyclic olefin unit containing an aliphatic carbon ring are the same as those relating to the terminal hydroxyl group-containing cyclic olefin polymer (A). The matters relating to the aforementioned aliphatic carbon ring-containing cyclic olefin unit include, for example, the range of the aliphatic carbon ring contained in the cyclic olefin unit, the range of the cyclic olefin compound corresponding to the aliphatic carbon ring-containing cyclic olefin unit, and the fact that the cyclic olefin unit may include a structure formed by polymerizing and hydrogenating a cyclic olefin compound, and therefore the unsaturated bonds contained in the cyclic olefin unit may be hydrogenated to become single bonds.

[0059] Furthermore, the range of the content of cyclic olefin units containing aliphatic carbon rings in the terminal aliphatic ring-containing cyclic olefin polymer (B) may be the same as the range of the content of cyclic olefin units containing aliphatic carbon rings in the terminal hydroxyl group-containing cyclic olefin polymer (A). Therefore, preferably, the range of the content of cyclic olefin units containing aliphatic carbon rings in the terminal aliphatic ring-containing cyclic olefin polymer (B) per 100% by weight of the terminal aliphatic ring-containing cyclic olefin polymer (B) is the same as the range of the content of cyclic olefin units containing aliphatic carbon rings in the terminal hydroxyl group-containing cyclic olefin polymer (A) per 100% by weight of the terminal hydroxyl group-containing cyclic olefin polymer (A).

[0060] Furthermore, the range of hydrogenation rates of cyclic olefin units in terminal aliphatic ring-containing cyclic olefin polymer (B) may be the same as the range of hydrogenation rates of cyclic olefin units in terminal hydroxyl group-containing cyclic olefin polymer (A).

[0061] (Arbitrary structural units) The terminal aliphatic ring-containing cyclic olefin polymer (B) may contain any additional structural units in combination with the aliphatic carbon ring-containing cyclic olefin unit. Examples of arbitrary structural units contained in the terminal aliphatic ring-containing cyclic olefin polymer (B) are the same as those contained in the terminal hydroxyl group-containing cyclic olefin polymer (A).

[0062] (Terminal unsaturated cyclic aliphatic hydrocarbon group) A terminal aliphatic ring-containing cyclic olefin polymer (B) contains an unsaturated cyclic aliphatic hydrocarbon group at the end of the polymer chain of the terminal aliphatic ring-containing cyclic olefin polymer (B). A terminal aliphatic ring-containing cyclic olefin polymer (B) contains an unsaturated cyclic aliphatic hydrocarbon group at one or more ends, preferably at multiple ends. Typically, a terminal aliphatic ring-containing cyclic olefin polymer (B) has a main chain containing a cyclic olefin unit including the aliphatic carbon ring described above, and contains an unsaturated cyclic aliphatic hydrocarbon group at the end of the main chain. In this case, the terminal aliphatic ring-containing cyclic olefin polymer (B) may contain an unsaturated cyclic aliphatic hydrocarbon group at only one end of its main chain, or it may contain an unsaturated cyclic aliphatic hydrocarbon group at both ends of its main chain. In particular, it is preferable that the terminal aliphatic ring-containing cyclic olefin polymer (B) contains an unsaturated cyclic aliphatic hydrocarbon group at both ends.

[0063] An unsaturated cyclic aliphatic hydrocarbon group represents a group obtained by removing one hydrogen atom from an unsaturated cyclic aliphatic hydrocarbon. Furthermore, an unsaturated cyclic aliphatic hydrocarbon represents a hydrocarbon containing an unsaturated aliphatic carbon ring. The number of unsaturated bonds contained in one unsaturated aliphatic carbon ring is 1 or 2 or more, preferably 1. Also, the number of carbon rings contained in an unsaturated cyclic aliphatic hydrocarbon group may be 1 or 2 or more.

[0064] The unsaturated cyclic aliphatic hydrocarbon group is preferably an aliphatic hydrocarbon group that does not contain an aromatic ring, and more preferably a cycloalkenyl group which may have an alkyl group. A cycloalkenyl group represents a group obtained by removing one hydrogen atom from a cycloalkene. The number of carbon rings contained in such a cycloalkenyl group may be one or two or more. Among cycloalkenyl groups, a cycloalkenyl group containing a norbornene ring is preferred. Examples of preferred cycloalkenyl groups include norbornenyl (a group obtained by removing one hydrogen atom from norbornene), dicyclopentadienyl (a group obtained by removing one hydrogen atom from dicyclopentadiene), tetracyclododecenyl (a group obtained by removing one hydrogen atom from tetracyclododecene), and groups in which an alkyl group is bonded to the ring of these groups. The number of carbon atoms in the alkyl group is preferably 1 to 20, more preferably 1 to 3. Examples of alkyl groups include methyl, ethyl, and butyl groups.

[0065] The terminal aliphatic ring-containing cyclic olefin polymer (B) may be used in the form of a composition containing polymers with different numbers of unsaturated cyclic aliphatic hydrocarbon groups. Examples of such compositions include a single-terminal aliphatic ring-containing cyclic olefin polymer containing an unsaturated cyclic aliphatic hydrocarbon group at only one end, and a double-terminal aliphatic ring-containing cyclic olefin polymer containing unsaturated cyclic aliphatic hydrocarbon groups at both ends. When used in the form of such a composition, it is preferable that the proportion of the double-terminal aliphatic ring-containing cyclic olefin polymer is large. In one example, the proportion of the double-terminal aliphatic ring-containing cyclic olefin polymer is preferably 20% by weight or more, more preferably 40% by weight or more, even more preferably 60% by weight or more, and particularly preferably 80% by weight or more, relative to 100% by weight of the total amount of the terminal aliphatic ring-containing cyclic olefin polymer (B) (usually the sum of the single-terminal aliphatic ring-containing cyclic olefin polymer and the double-terminal aliphatic ring-containing cyclic olefin polymer). The upper limit is usually 100% by weight or less. In particular, the terminal aliphatic ring-containing cyclic olefin polymer (B) is preferably a biterminal aliphatic ring-containing cyclic olefin polymer in which all of the polymers contain unsaturated cyclic aliphatic hydrocarbon groups at both ends.

[0066] The ratio of the cyclic olefin polymer containing both terminal aliphatic rings to the total amount of the cyclic olefin polymer containing terminal aliphatic rings (B) is: １ It can be measured from the 1H-NMR measurement results and the weight-average molecular weight Mw.

[0067] Furthermore, it is preferable that the proportion of terminals containing unsaturated cyclic aliphatic hydrocarbon groups among the terminal aliphatic ring-containing cyclic olefin polymer (B) is high. In one example, the proportion of terminals containing unsaturated cyclic aliphatic hydrocarbon groups relative to 100% of the total number of terminals in the polymer chain of the terminal aliphatic ring-containing cyclic olefin polymer (B) (usually the sum of a single-terminal aliphatic ring-containing cyclic olefin polymer and a double-terminal aliphatic ring-containing cyclic olefin polymer) is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, and particularly preferably 80% or more. In the following description, the proportion of terminals containing unsaturated cyclic aliphatic hydrocarbon groups relative to 100% of the total number of terminals in the polymer chain of the terminal aliphatic ring-containing cyclic olefin polymer (B) may be referred to as the "introduction rate of terminal unsaturated cyclic aliphatic hydrocarbon groups." The upper limit of the introduction rate of terminal unsaturated cyclic aliphatic hydrocarbon groups is usually 100% or less. In particular, the terminal aliphatic ring-containing cyclic olefin polymer (B) is preferably one in which all of its terminals contain unsaturated cyclic aliphatic hydrocarbon groups.

[0068] The introduction rate of terminally unsaturated cyclic aliphatic hydrocarbon groups in terminally aliphatic ring-containing cyclic olefin polymer (B) is: １ It can be measured from the H-NMR measurement results and the number-average molecular weight Mn.

[0069] In a preferred embodiment, the terminal aliphatic ring-containing cyclic olefin polymer (B) has an unsaturated cyclic aliphatic hydrocarbon oxy group or an unsaturated cyclic aliphatic hydrocarbon carbonyloxy group at its terminal. "Unsaturated cyclic aliphatic hydrocarbon oxy group" refers to a group in which an unsaturated cyclic aliphatic hydrocarbon group is bonded to an oxy group (-O-). "Unsaturated cyclic aliphatic hydrocarbon carbonyloxy group" refers to a group in which an unsaturated cyclic aliphatic hydrocarbon group is bonded to the carbonyl group (-C(=O)-) of a carbonyloxy group (-O-C(=O)-). In this case, the unsaturated cyclic aliphatic hydrocarbon group contained in the unsaturated cyclic aliphatic hydrocarbon oxy group or the unsaturated cyclic aliphatic hydrocarbon carbonyloxy group corresponds to the terminal unsaturated cyclic aliphatic hydrocarbon group at the end of the polymer chain of the terminal aliphatic ring-containing cyclic olefin polymer (B). Such a terminal aliphatic ring-containing cyclic olefin polymer (B) can be produced, for example, by a production method that includes reacting a terminal hydroxyl group-containing cyclic olefin polymer (A) with a cyclic olefin compound containing an unsaturated cyclic aliphatic hydrocarbon group and a carboxyl group, or a cyclic olefin compound containing an unsaturated cyclic aliphatic hydrocarbon group and an alkyl halogenate, as described in the production method described later.

[0070] (Weight-average molecular weight) The weight-average molecular weight Mw range of the terminal aliphatic ring-containing cyclic olefin polymer (B) may be the same as the weight-average molecular weight Mw range of the terminal hydroxyl group-containing cyclic olefin polymer (A). The weight-average molecular weight Mw of the terminal aliphatic ring-containing cyclic olefin polymer (B) can be measured by the same method as the weight-average molecular weight Mw of the terminal hydroxyl group-containing cyclic olefin polymer (A). The specific measurement method may be the method described in the examples below.

[0071] (Glass transition temperature) The glass transition temperature Tg range of the terminal aliphatic ring-containing cyclic olefin polymer (B) is preferably -20°C or higher, more preferably -10°C or higher, particularly preferably -5°C or higher, preferably 250°C or lower, more preferably 200°C or lower, and particularly preferably 180°C or lower.

[0072] (Method for producing terminal aliphatic ring-containing cyclic olefin polymer (B)) Terminal aliphatic ring-containing cyclic olefin polymer (B) can be produced, for example, by a production method that includes reacting terminal hydroxyl group-containing cyclic olefin polymer (A) with a "cyclic olefin compound containing an unsaturated cyclic aliphatic hydrocarbon group and a carboxyl group" or a "cyclic olefin compound containing an unsaturated cyclic aliphatic hydrocarbon group and an alkyl halogenate". The "cyclic olefin compound containing an unsaturated cyclic aliphatic hydrocarbon group and a carboxyl group" may hereafter be referred to as a "carboxycyclic olefin compound". Also, the "cyclic olefin compound containing an unsaturated cyclic aliphatic hydrocarbon group and an alkyl halogenate" may hereafter be referred to as an "alkyl halogenated cyclic olefin compound".

[0073] In a method of reacting a terminally hydroxyl-containing cyclic olefin polymer (A) with a carboxycyclic olefin compound, the terminal hydroxyl groups of the terminally hydroxyl-containing cyclic olefin polymer (A) and the carboxyl groups of the carboxycyclic olefin compound undergo a dehydration condensation reaction to obtain a terminally aliphatic ring-containing cyclic olefin polymer (B). In this reaction, a terminally aliphatic ring-containing cyclic olefin polymer (B) having an unsaturated cyclic aliphatic hydrocarbon group introduced at the terminal via an ester bond can usually be obtained. For example, as shown in formula (B1) below, when a terminally hydroxyl-containing cyclic olefin polymer (A) shown in formula (a2) is reacted with 5-norbornenecarboxylic acid as a carboxycyclic olefin compound, a terminally aliphatic ring-containing cyclic olefin polymer (B) shown in formula (b1) can be produced. In formula (b1), n ​​represents the number of repeats.

[0074]

[0075] As the carboxycyclic olefin compound, a compound containing an unsaturated cyclic aliphatic hydrocarbon group and a carboxyl group is used. Preferably, the carboxycyclic olefin compound is one in which one hydrogen atom of the unsaturated cyclic aliphatic hydrocarbon is substituted with a carboxyl group or a carboxyalkyl group, and more preferably, one hydrogen atom of the unsaturated cyclic aliphatic hydrocarbon is substituted with a carboxyl group. Examples of carboxycyclic olefin compounds include norbornenecarboxylic acid and 3-cyclopentenecarboxylic acid. The carboxycyclic olefin compound may be used alone or in combination of two or more types.

[0076] In the reaction between a terminal hydroxyl group-containing cyclic olefin polymer (A) and a carboxycyclic olefin compound, the amount of the carboxycyclic olefin compound is preferably set within a range that yields the desired terminal aliphatic ring-containing cyclic olefin polymer (B). In one example, the range of the amount of the carboxycyclic olefin compound is preferably 0.5 moles or more, more preferably 1.0 mole or more, preferably 2.0 moles or less, and more preferably 1.5 moles or less, per mole of hydroxyl groups in the terminal hydroxyl group-containing cyclic olefin polymer (A).

[0077] In the reaction between a terminal hydroxyl group-containing cyclic olefin polymer (A) and a carboxycyclic olefin compound, catalysts such as acid catalysts and base catalysts may be used, and condensing agents may also be used. Examples of acid catalysts include inorganic acids such as hydrochloric acid and sulfuric acid, and sulfonic acids such as methanesulfonic acid and p-toluenesulfonic acid, with sulfonic acids being preferred. One type of catalyst may be used alone, or two or more types may be used in combination. The amount of catalyst is preferably set within a range that yields the desired terminal aliphatic ring-containing cyclic olefin polymer (B). In one example, the amount of catalyst is preferably 0.01 moles or more, more preferably 0.05 moles or more, preferably 1.5 moles or less, and more preferably 1.0 mole or less, per mole of hydroxyl groups in the terminal hydroxyl group-containing cyclic olefin polymer (A). Examples of condensing agents include dicyclohexylcarbodiimide, diisopropylcarbodiimide, 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide, 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride, and bis(2,6-diisopropylphenyl)carbodiimide. One type of condensing agent may be used alone, or two or more types may be used in combination. The amount of condensing agent is preferably set within a range that yields the desired terminal aliphatic ring-containing cyclic olefin polymer (B). In one example, the amount of condensing agent is preferably 0.01 moles or more, more preferably 0.05 moles or more, preferably 1.5 moles or less, and more preferably 1.0 mole or less, per mole of hydroxyl groups in the terminal hydroxyl group-containing cyclic olefin polymer (A). Furthermore, an activator such as 4-(dimethylamino)pyridine may be present in the reaction system during the reaction. In addition, the reaction may be carried out while the water generated by condensation is removed from the system by azeotropic dehydration.

[0078] The reaction between the terminal hydroxyl group-containing cyclic olefin polymer (A) and the carboxycyclic olefin compound may be carried out in solvent-free or solvent-based conditions. When polymerization is carried out in a solvent, it is preferable to use a solvent that is inert in the reaction and capable of dissolving both the terminal hydroxyl group-containing cyclic olefin polymer (A) and the carboxycyclic olefin compound. Preferred solvents include, for example, chlorinated solvents such as chloroform, methylene chloride, and dichloromethane; amide solvents such as N-methylpyrrolidone, N,N-dimethylformamide, N,N-dimethylacetamide, and hexamethyltriphosphate; ether solvents such as 1,4-dioxane, cyclopentyl methyl ether, tetrahydrofuran, tetrahydropyran, and 1,3-dioxolane; sulfur-containing solvents such as dimethyl sulfoxide and sulfolane; aromatic hydrocarbon solvents such as benzene, toluene, and xylene; aliphatic hydrocarbon solvents such as n-pentane, n-hexane, and n-octane; and alicyclic hydrocarbon solvents such as cyclopentane and cyclohexane. One type of solvent may be used alone, or two or more types may be used in combination.

[0079] The reaction temperature for the reaction between the terminal hydroxyl group-containing cyclic olefin polymer (A) and the carboxycyclic olefin compound can be set within a range that allows the condensation reaction to proceed. In one example, the reaction temperature range is preferably 0°C or higher, more preferably 15°C or higher, and also preferably less than 100°C, more preferably less than 80°C, and even more preferably less than 60°C.

[0080] The reaction time for the reaction between the terminal hydroxyl group-containing cyclic olefin polymer (A) and the carboxycyclic olefin compound can be set within a range that yields the terminal aliphatic ring-containing cyclic olefin polymer (B). In one example, the reaction time range is preferably 1 hour or more, more preferably 10 hours or more, preferably 120 hours or less, and more preferably 96 hours or less.

[0081] Furthermore, in a method of reacting a terminal hydroxyl group-containing cyclic olefin polymer (A) with an alkyl halide cyclic olefin compound, the terminal hydroxyl group of the terminal hydroxyl group-containing cyclic olefin polymer (A) is reacted with the alkyl halide of the alkyl halide cyclic olefin compound to obtain a terminal aliphatic ring-containing cyclic olefin polymer (B). In this reaction, an ether bond is usually formed by the Williamson method, and a terminal aliphatic ring-containing cyclic olefin polymer (B) having an unsaturated cyclic aliphatic hydrocarbon group introduced at the end can be obtained via this ether bond. Specifically, as shown in formula (B2) below, when the terminal hydroxyl group-containing cyclic olefin polymer (A) shown in formula (a2) is reacted with 5-chloromethylnorbornene as an alkyl halide cyclic olefin compound, a terminal aliphatic ring-containing cyclic olefin polymer (B) shown in formula (b2) can be produced. In formula (b2), n represents the number of repetitions.

[0082]

[0083] As the alkyl halogenated cyclic olefin compound, a compound containing an unsaturated cyclic aliphatic hydrocarbon group and an alkyl halogenated group is used. Preferably, this alkyl halogenated cyclic olefin compound is a compound in which one hydrogen atom of the unsaturated cyclic aliphatic hydrocarbon is substituted with an alkyl halogenated group. The number of carbon atoms in the alkyl halogenated group is preferably 1 to 20, more preferably 1 to 10, and even more preferably 1 to 6. Examples of alkyl halogenated cyclic olefin compounds include 5-chloromethylnorbornene, 5-bromomethylnorbornene, and 5-iodomethylnorbornene. The alkyl halogenated cyclic olefin compound may be used alone or in combination of two or more types.

[0084] In the reaction between a terminal hydroxyl group-containing cyclic olefin polymer (A) and an alkyl halide cyclic olefin compound, the amount of the alkyl halide cyclic olefin compound is preferably set within a range that yields the desired terminal aliphatic ring-containing cyclic olefin polymer (B). In one example, the range of the amount of the alkyl halide cyclic olefin compound is preferably 0.5 moles or more, more preferably 1.0 mole or more, preferably 2.0 moles or less, and more preferably 1.5 moles or less, per mole of hydroxyl groups in the terminal hydroxyl group-containing cyclic olefin polymer (A).

[0085] The reaction between a terminal hydroxyl group-containing cyclic olefin polymer (A) and an alkyl halide cyclic olefin compound is usually carried out in the presence of a base. Examples of bases include sodium carbonate, potassium carbonate, cesium carbonate, sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium hydride, potassium hydride, metallic sodium, and metallic potassium. One type of base may be used alone, or two or more types may be used in combination. The amount of base is preferably set within a range in which the desired terminal aliphatic ring-containing cyclic olefin polymer (B) can be obtained. In one example, the amount of base is preferably 1.6 moles or more, more preferably 2 moles or more, preferably 20 moles or less, and more preferably 10 moles or less, per mole of hydroxyl groups in the terminal hydroxyl group-containing cyclic olefin polymer (A). Furthermore, a catalyst that can be used in the Williamson process may be present in the reaction system during the reaction.

[0086] The reaction between the terminal hydroxyl group-containing cyclic olefin polymer (A) and the alkyl halide cyclic olefin compound may be carried out in solvent-free or solvent-based conditions. When polymerization is carried out in a solvent, it is preferable to use a solvent that is inert in the reaction and capable of dissolving both the terminal hydroxyl group-containing cyclic olefin polymer (A) and the alkyl halide cyclic olefin compound. Preferred solvents include, for example, the same solvent used in the reaction between the terminal hydroxyl group-containing cyclic olefin polymer (A) and the carboxycyclic olefin compound. The solvent may be used alone or in combination of two or more types.

[0087] The reaction temperature for the reaction between the terminal hydroxyl group-containing cyclic olefin polymer (A) and the alkyl halogenated cyclic olefin compound can be set within a range in which the reaction can proceed. In one example, the reaction temperature range is preferably 0°C or higher, more preferably 15°C or higher, preferably less than 100°C, more preferably less than 80°C, and even more preferably less than 60°C.

[0088] The reaction time for the reaction between the terminal hydroxyl group-containing cyclic olefin polymer (A) and the alkyl halogenated cyclic olefin compound can be set within a range that yields the terminal aliphatic ring-containing cyclic olefin polymer (B). In one example, the reaction time range is preferably 1 hour or more, more preferably 10 hours or more, preferably 120 hours or less, and more preferably 96 hours or less.

[0089] The method for producing the terminal aliphatic ring-containing cyclic olefin polymer (B) may include any additional steps in addition to the reaction steps described above. For example, the method for producing the terminal aliphatic ring-containing cyclic olefin polymer (B) may include steps to remove the used catalyst and / or solvent after obtaining the terminal aliphatic ring-containing cyclic olefin polymer (B). These optional steps can be carried out in the same manner as the steps in the method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A).

[0090] <Polymer Compound (C)> The polymer compound (C) according to one embodiment of the present invention is a polymer of the terminal aliphatic ring-containing cyclic olefin polymer (B) described above. This polymer compound (C) can be combined with the cyclic olefin polymer (E) to produce a resin composition (D). Since the resin composition (D) has high mechanical strength, it can be used as a material for films with high peel strength.

[0091] In the polymerization reaction of the terminal aliphatic ring-containing cyclic olefin polymer (B), the terminal unsaturated cyclic aliphatic hydrocarbon groups of the terminal aliphatic ring-containing cyclic olefin polymer (B) can undergo ring-opening polymerization. Therefore, the polymer compound (C) may have a structure formed by the polymerization of the terminal unsaturated cyclic aliphatic hydrocarbon groups of the terminal aliphatic ring-containing cyclic olefin polymer (B).

[0092] (Explanation of the trunk-branch type) In the first example, the polymer compound (C) may have a tertiarily bulky structure having a trunk polymer formed by the polymerization of unsaturated cyclic aliphatic hydrocarbon groups and branch polymers extending from the trunk polymer. In such a structure, the branch polymer corresponds to the polymer chain of a terminal aliphatic ring-containing cyclic olefin polymer (B), and therefore contains cyclic olefin units containing aliphatic carbon rings. The polymer resin (C) having the structure according to the first example is usually obtained by the polymerization reaction of a terminal aliphatic ring-containing cyclic olefin polymer (B) having an unsaturated cyclic aliphatic hydrocarbon group at one end.

[0093] (Explanation of ring type) In the second example, the polymer compound (C) may include a ring-shaped structure formed by the polymerization of unsaturated cyclic aliphatic hydrocarbon groups contained within one molecule of the terminal aliphatic ring-containing cyclic olefin polymer (B). A polymer resin (C) having the structure according to the second example is usually obtained by a polymerization reaction of a terminal aliphatic ring-containing cyclic olefin polymer (B) containing multiple unsaturated cyclic aliphatic hydrocarbon groups at its ends.

[0094] For example, when polymerizing a terminal aliphatic ring-containing cyclic olefin polymer (B) containing unsaturated cyclic aliphatic hydrocarbon groups at both ends, as shown in formula (C1) below, a polymer compound (C) containing the ring-shaped structure shown in formula (c1) can be produced. In formula (c1), n ​​independently represents the number of repeats. The benzene ring at the left end of formula (c1) is a residue introduced into the polymer compound (C) from the polymerization catalyst, and usually varies depending on the type of catalyst used.

[0095]

[0096] Figures 1 and 2 are schematic perspective views showing the ring-shaped structure of a polymer compound (C) according to one example. In formula (c1) above, k represents the number of repeats and can correspond to the number of rings formed by the polymer chain of the terminal aliphatic ring-containing cyclic olefin polymer (B). For example, as shown in Figure 1, polymer compound (C) 10 formed when one molecule of the terminal aliphatic ring-containing cyclic olefin polymer (B) undergoes an intramolecular reaction has a single-ring structure having one ring 11. Another molecule of the terminal aliphatic ring-containing cyclic olefin polymer (B) can react with the active site of the single-ring structure thus formed (i.e., the part formed by the reaction of unsaturated cyclic aliphatic hydrocarbon groups). Therefore, another ring can be formed when an unsaturated cyclic aliphatic hydrocarbon group of another molecule of the terminal aliphatic ring-containing cyclic olefin polymer (B) reacts with the active site. As a result, as shown in Figure 2, a polymer compound (C) 20 with a multi-ring structure having multiple rings 21 to 23 overall is obtained.

[0097] Figure 2 shows an example with three rings, but the number of rings is not limited to three. The number of rings in a molecule of polymer compound (C) can usually be adjusted within the range of 1 to 20. Therefore, in formula (c1), k preferably represents an integer between 1 and 20. Furthermore, polymer compound (C) may be manufactured and used in the form of a composition containing molecules with different numbers of rings.

[0098] The polymer compound (C) may consist only of molecules having a stem polymer and branch polymer structure as described in the first example, or only of molecules having a ring-shaped structure as described in the second example, or may consist of a combination of both types of molecules.

[0099] (Hydrogenation Rate) The polymer compound (C) described above may contain non-aromatic carbon-carbon unsaturated bonds. For example, in a cyclic olefin polymer (B) containing terminal aliphatic rings, a non-aromatic carbon-carbon unsaturated bond may be formed at the active site by a ring-opening metathesis polymerization reaction of the unsaturated cyclic aliphatic hydrocarbon group at the terminal. In polymer compound (C), this non-aromatic carbon-carbon unsaturated bond may be hydrogenated to become a single bond. Therefore, polymer compound (C) may include such hydrogenated bonds.

[0100] The degree of hydrogenation can be expressed as a hydrogenation rate. This hydrogenation rate represents the ratio of the number of single bonds due to hydrogenation to 100% of the number of non-aromatic carbon-carbon unsaturated bonds contained in the repeating units formed by polymerizing the terminal aliphatic ring-containing cyclic olefin polymer (B). The hydrogenation rate of the polymer compound (C) is preferably 30% or more, more preferably 50% or more, even more preferably 70% or more, particularly preferably 80% or more, and may be 100%. This hydrogenation rate is orthodichlorobenzene-d ４ Using as a solvent, at 145°C, １ It can be measured by H-NMR.

[0101] (Weight-average molecular weight) The weight-average molecular weight Mw of polymer compound (C) is preferably 5,000 or more, more preferably 8,000 or more, particularly preferably 10,000 or more, preferably 200,000 or less, more preferably 180,000 or less, and particularly preferably 150,000 or less. The weight-average molecular weight Mw of polymer compound (C) can be measured by the same method as the weight-average molecular weight Mw of terminal hydroxyl group-containing cyclic olefin polymer (A). The specific measurement method may be the method described in the examples below.

[0102] (Glass transition temperature) The glass transition temperature Tg range of the polymer compound (C) is preferably -20°C or higher, more preferably -10°C or higher, particularly preferably -5°C or higher, preferably 250°C or lower, more preferably 200°C or lower, and particularly preferably 180°C or lower.

[0103] (Method for producing polymer compound (C)) Polymer compound (C) can be produced by a method that includes a step of polymerizing a terminal aliphatic ring-containing cyclic olefin polymer (B). In such polymerization, ring-opening metathesis polymerization of the terminal aliphatic ring-containing cyclic olefin polymer (B) proceeds to obtain polymer compound (C). In addition, since the obtained polymer compound (C) usually contains non-aromatic carbon-carbon unsaturated bonds, the method for producing polymer compound (C) may include a step of converting the unsaturated bonds into single bonds by hydrogenation.

[0104] From the viewpoint of smoothly carrying out the ring-opening metathesis polymerization of cyclic olefin compounds, it is preferable to carry out the polymerization in the presence of a ring-opening polymerization catalyst. Examples of preferred ring-opening polymerization catalysts include the same ones described in the method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A), with ruthenium catalysts being more preferred, and ruthenium carbene complex catalysts being even more preferred.

[0105] In particular, from the viewpoint of obtaining the polymer compound (C) having the ring-shaped structure described above, it is preferable to use a third-generation Grubbs catalyst. Examples of such third-generation Grubbs catalysts include those represented by the following formulas (g1) to (g3).

[0106]

[0107] The ring-opening polymerization catalyst may be used alone or in combination of two or more types.

[0108] The amount of ring-opening polymerization catalyst used is preferably 10 mol% or more, more preferably 25 mol% or more, preferably 50 mol% or less, and more preferably 30 mol% or less, based on 100 mol% of the terminal aliphatic ring-containing cyclic olefin polymer (B). Typically, the number of rings contained in the polymer compound (C) can be adjusted by adjusting the amount of such ring-opening polymerization catalyst.

[0109] The polymerization reaction may be carried out in a solvent-free environment or in a solvent. When polymerization is carried out in a solvent, it is preferable to use a solvent that is inert in the polymerization reaction and can dissolve the monomer and polymerization catalyst. Examples of solvents include the same solvents described in the method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A). One type of solvent may be used alone, or two or more types may be used in combination.

[0110] The polymerization reaction temperature can be set within a range in which the polymerization reaction can proceed. In one example, the polymerization reaction temperature range is preferably -100°C or higher, more preferably -50°C or higher, even more preferably 0°C or higher, particularly preferably 15°C or higher, and also preferably less than 120°C, more preferably less than 100°C, even more preferably less than 90°C, and particularly preferably less than 80°C.

[0111] The polymerization reaction time can be set within a range that yields the desired polymer compound (C). In one example, the polymerization reaction time is preferably 1 minute or more, more preferably 10 minutes or more, preferably 72 hours or less, and more preferably 20 hours or less.

[0112] The polymer compound (C) obtained by the polymerization described above may contain non-aromatic carbon-carbon unsaturated bonds. Such unsaturated bonds may be converted to single bonds by hydrogenation. Therefore, the method for producing polymer compound (C) may include a step of hydrogenating the obtained polymer compound (C) after the polymerization step described above. Such hydrogenation can be carried out, for example, by the same method as the hydrogenation described in the method for producing terminal hydroxyl group-containing cyclic olefin polymer (A).

[0113] The method for producing polymer compound (C) may include any additional steps in addition to the reaction steps described above. For example, the method for producing polymer compound (C) may include steps to remove the used catalyst and / or solvent after obtaining polymer compound (C). These optional steps can be carried out in the same manner as the steps in the method for producing terminal hydroxyl group-containing cyclic olefin polymer (A).

[0114] <Resin Composition (D)> A resin composition (D) according to one embodiment of the present invention comprises a polymer compound (C) and a cyclic olefin polymer (E). In this resin composition (D), the polymer compound (C) has a three-dimensionally bulky molecular structure. Therefore, when a film is formed using the resin composition (D) containing the polymer compound (C), the molecules of the polymer compound (C) can become highly entangled with the molecules of the cyclic olefin polymer (E). As a result of this entanglement, the resin composition (D) can have high toughness, and thus the fracture of the resin composition (D) is suppressed. Consequently, even when force is applied in the thickness direction, the film of the resin composition (D) is less prone to delamination, and thus can achieve high peel strength. This effect is in contrast to a film formed solely from the cyclic olefin polymer (E), which has less molecular entanglement and cannot withstand large forces in the thickness direction, making it prone to delamination.

[0115] (Polymer compound (C) in resin composition (D)) The polymer compound (C) contained in resin composition (D) may be one type or two or more types. For example, resin composition (D) may contain only polymer compounds (C) having a stem polymer and branch polymer structure, or only polymer compounds (C) having a ring-shaped structure, or a combination thereof. In particular, from the viewpoint of effectively suppressing delamination, it is preferable that resin composition (D) contains polymer compounds (C) having a ring-shaped structure. In this case, all of the polymer compounds (C) contained in resin composition (D) may be polymer compounds (C) having a ring-shaped structure.

[0116] When the resin composition (D) contains a polymer compound (C) having a ring-like structure, molecules of a cyclic olefin polymer (E) can be inserted so as to pass through the rings of the polymer compound (C). In this case, the molecules of the cyclic olefin polymer (E) can be linked together by the rings of the polymer compound (C), allowing the resin composition (D) to have particularly high mechanical strength. That is, not only is there simple molecular entanglement, but the rings of the polymer compound (C) strongly link the molecules of the cyclic olefin polymer (E), making the resin composition (D) less prone to fracture even when stress is applied. Therefore, a film of the resin composition (D) can particularly effectively suppress delamination and significantly increase peel strength.

[0117] When the resin composition (D) contains a polymer compound (C) having a ring-shaped structure, the range of the number of rings per molecule of the polymer compound (C) is preferably one or more, preferably 20 or less, more preferably 8 or less, and even more preferably 5 or less.

[0118] The amount of polymer compound (C) is preferably 1% by weight or more, more preferably 3% by weight or more, even more preferably 5% by weight or more, preferably 50% by weight or less, more preferably 40% by weight or less, and even more preferably 30% by weight or less, based on 100% by weight of the resin composition (D).

[0119] (Cyclic olefin polymer (E) in resin composition (D)) The cyclic olefin polymer (E) is a polymer that contains cyclic olefin units in its molecule. The cyclic olefin units contained in the cyclic olefin polymer (E) do not necessarily contain aliphatic carbon rings, but it is preferable that they do. Such aliphatic carbon rings may be the same as the aliphatic carbon rings of the terminal hydroxyl group-containing cyclic olefin polymer (A). Examples of cyclic olefin compounds corresponding to cyclic olefin units include the cyclic olefin compounds described in the section on terminal hydroxyl group-containing cyclic olefin polymer (A). The cyclic olefin polymer (E) may contain one type of cyclic olefin unit or two or more types. Therefore, the cyclic olefin compound corresponding to the cyclic olefin unit may be used alone or in combination of two or more types.

[0120] The content of cyclic olefin units is preferably 5% by weight or more, more preferably 10% by weight or more, even more preferably 15% by weight or more, and even more preferably 20% by weight or more, based on 100% by weight of the cyclic olefin polymer (E). In particular, from the viewpoint of producing materials for optical films where high transparency is required, the content of cyclic olefin units is preferably 55% by weight or more, more preferably 70% by weight or more, and even more preferably 90% by weight or more. The upper limit is usually 100% by weight or less.

[0121] When a cyclic olefin compound is polymerized to form a cyclic olefin unit, the cyclic olefin unit may contain a non-aromatic carbon-carbon unsaturated bond. In the cyclic olefin polymer (E), the cyclic olefin unit may be hydrogenated. Therefore, the unsaturated bond contained in the cyclic olefin unit may be hydrogenated to become a single bond. The hydrogenation rate of the non-aromatic carbon-carbon unsaturated bond in the cyclic olefin polymer (E) is preferably 50% or more, more preferably 60% or more, even more preferably 70% or more, even more preferably 80% or more, particularly preferably 90% or more, and may be 100%.

[0122] The cyclic olefin polymer (E) may contain any additional structural units in combination with the cyclic olefin units. Examples of such arbitrary structural units include those derived from α-olefins having 2 to 20 carbon atoms, such as ethylene, propylene, and 1-butene, and their derivatives. The cyclic olefin polymer (E) may contain one or more types of arbitrary structural units. Therefore, any monomer corresponding to the arbitrary structural unit may be used alone or in combination of two or more types.

[0123] Commercially available cyclic olefin polymers (E) may be used. Examples of commercially available cyclic olefin polymers (E) include "ZEONOR" and "ZEONEX" from Nippon Zeon Corporation; "ARTON" from JSR Corporation; and "APPEL" from Mitsui Chemicals, Inc.

[0124] The cyclic olefin polymer (E) may be used alone or in combination of two or more types.

[0125] The weight-average molecular weight Mw of the cyclic olefin polymer (E) is preferably 10,000 or more, more preferably 15,000 or more, particularly preferably 20,000 or more, preferably 100,000 or less, more preferably 80,000 or less, and particularly preferably 50,000 or less. When the weight-average molecular weight is within this range, the mechanical strength and moldability of the resin composition (D) are highly balanced.

[0126] The amount of cyclic olefin polymer (E) is preferably 1 part by weight or more, more preferably 5 parts by weight or more, even more preferably 10 parts by weight or more, preferably 300 parts by weight or less, more preferably 200 parts by weight or less, and even more preferably 100 parts by weight or less, per 100 parts by weight of polymer compound (C).

[0127] (Optional components in resin composition (D)) Resin composition (D) may further contain optional components in combination with the polymer compound (C) and the cyclic olefin polymer (E). Examples of optional components include any polymer other than the polymer compound (C) and the cyclic olefin polymer (E); colorants such as pigments and dyes; plasticizers; fluorescent whitening agents; dispersants; heat stabilizers; light stabilizers; ultraviolet absorbers; antistatic agents; antioxidants; fine particles; surfactants, etc. Optional components may be used individually or in combination of two or more types.

[0128] The resin composition (D) may contain a solvent. Generally, it is preferable that the amount of solvent in the resin composition (D) be small, and the resin composition (D) may not contain a solvent at all. The range of the amount of solvent contained in the resin composition (D) per 100% by weight of the resin composition (D) is preferably 10% by weight or less, more preferably 5% by weight or less, even more preferably 1% by weight or less, and may be 0% by weight.

[0129] (Weight-average molecular weight of resin composition (D)) The weight-average molecular weight Mw of resin composition (D) is preferably 15,000 or more, more preferably 20,000 or more, particularly preferably 25,000 or more, preferably 100,000 or less, more preferably 80,000 or less, and particularly preferably 50,000 or less. The weight-average molecular weight Mw of resin composition (D) usually represents the weight-average molecular weight of the total polymer contained in resin composition (D). The weight-average molecular weight Mw of resin composition (D) can be measured in the same way as the weight-average molecular weight Mw of the terminal hydroxyl group-containing cyclic olefin polymer (A). The specific measurement method may be the method described in the examples below.

[0130] (Glass transition temperature of resin composition (D)) The range of the glass transition temperature Tg of resin composition (D) is preferably 100°C or higher, more preferably 110°C or higher, even more preferably 120°C or higher, preferably 190°C or lower, more preferably 180°C or lower, and even more preferably 170°C or lower. The glass transition temperature of resin composition (D) can be measured using a differential scanning calorimetry analyzer (for example, "DSC6220SII" manufactured by Nanotechnology Inc.) under conditions of a heating rate of 10°C / min in accordance with JIS K 6911.

[0131] (Method for producing resin composition (D)) An example of a method for producing resin composition (D) is a method that includes the step of polymerizing a cyclic olefin compound in the presence of a polymer compound (C). Since a cyclic olefin polymer (E) is obtained by polymerizing a cyclic olefin compound, a resin composition (D) containing the polymer compound (C) and the cyclic olefin polymer (E) can be produced by performing the above polymerization in a system containing the polymer compound (C). In particular, when the polymer compound (C) has a ring-shaped structure, at least a portion of the cyclic olefin polymer (E) obtained by polymerization can be smoothly inserted so as to pass through the ring of the polymer compound (C). Therefore, since the resin composition (D) can have particularly high mechanical strength, it can be expected that a film with particularly high peel strength can be obtained.

[0132] The cyclic olefin polymer (E) can be produced by a manufacturing method that includes a step of polymerizing the cyclic olefin compound described above. In this polymerization, ring-opening metathesis polymerization is usually performed. Since the formed cyclic olefin unit may contain non-aromatic carbon-carbon unsaturated bonds, the method for producing the resin composition (D) may include a step of converting the unsaturated bonds into single bonds by hydrogenation.

[0133] As the cyclic olefin compound, the above-mentioned compounds can be used as cyclic olefin compounds corresponding to the cyclic olefin units of the cyclic olefin polymer (E). In particular, it is preferable to use the above-mentioned compounds as cyclic olefin compounds corresponding to cyclic olefin units containing aliphatic carbon rings. This cyclic olefin compound may be used alone or in combination of two or more types. The charging ratio of the cyclic olefin compound is preferably set according to the content of cyclic olefin units in the cyclic olefin polymer (E). In one example, the amount of the cyclic olefin compound (charging ratio) relative to 100 mol% of the total monomers used in the synthesis of the cyclic olefin polymer (E) is preferably 10 mol% or more, more preferably 30 mol% or more, even more preferably 50 mol% or more, even more preferably 70 mol% or more, and particularly preferably 80 mol% or more. The upper limit may be, for example, 100 mol% or less, 99 mol% or less, 95 mol% or less, 90 mol% or less, etc.

[0134] As monomers used in the synthesis of the cyclic olefin polymer (E), any monomer corresponding to any structural unit may be used in combination with the cyclic olefin compound described above. Therefore, the method for producing the resin composition (D) may include polymerizing a monomer mixture containing a cyclic olefin compound and, if necessary, any monomer. Examples of the arbitrary monomers include α-olefins and their derivatives. Any monomer may be used individually or in combination of two or more types.

[0135] From the viewpoint of smoothly carrying out the ring-opening metathesis polymerization of cyclic olefin compounds, it is preferable to carry out the polymerization in the presence of a ring-opening polymerization catalyst. Examples of ring-opening polymerization catalysts include those mentioned above. One type of ring-opening polymerization catalyst may be used alone, or two or more types may be used in combination.

[0136] The range of the amount of ring-opening polymerization catalyst used is preferably 1 / 2,000,000 moles or more, more preferably 1 / 1,500,000 moles or more, even more preferably 1 / 1,000,000 moles or more, preferably 1 / 500 moles or less, more preferably 1 / 700 moles or less, and even more preferably 1 / 1,000 moles or less, per mole of monomer.

[0137] The polymerization reaction may be carried out in a solvent-free environment or in a solvent. Examples of solvents include those described in the method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A). One type of solvent may be used alone, or two or more types may be used in combination.

[0138] The polymerization reaction temperature can be set within a range that allows the polymerization reaction to proceed. The polymerization reaction time can also be set within a range that yields the desired cyclic olefin polymer (E). In one example, the range of polymerization reaction temperature and time for the polymerization of the cyclic olefin polymer (E) may be the same as the range of polymerization reaction temperature and time for the polymerization of the terminal hydroxyl group-containing cyclic olefin polymer (A).

[0139] The cyclic olefin polymer (E) obtained by the polymerization described above may contain non-aromatic carbon-carbon unsaturated bonds. Such unsaturated bonds may be converted to single bonds by hydrogenation. Therefore, the method for producing the resin composition (D) may include a step of hydrogenating the obtained cyclic olefin polymer (E) after the polymerization described above. Such hydrogenation can be carried out, for example, by the same method as the hydrogenation described in the method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A).

[0140] Another example of a method for producing the resin composition (D) is a method that includes a step of mixing a polymer compound (C) and a cyclic olefin polymer (E). By mixing a pre-prepared polymer compound (C) and a pre-prepared cyclic olefin polymer (E), a resin composition (D) containing the polymer compound (C) and the cyclic olefin polymer (E) can be produced. If the polymer compound (C) has a ring-shaped structure, even by this method, at least a portion of the cyclic olefin polymer (E) can be inserted through the ring of the polymer compound (C), so a resin composition (D) with high mechanical strength can be produced, and thus a film with high peel strength can be obtained.

[0141] There are no particular restrictions on the mixing method. For example, the polymer compound (C) and the cyclic olefin polymer (E) may be mixed together with a solvent capable of dissolving the polymer compound (C) and the cyclic olefin polymer (E). The amount of solvent is preferably 100 to 10,000 parts by weight per 100 parts by weight of the total of the polymer compound (C) and the cyclic olefin polymer (E).

[0142] Alternatively, the polymer compound (C) and the cyclic olefin polymer (E) may be mixed by a melt-kneading method. In the melt-kneading method, the polymer compound (C) and the cyclic olefin polymer (E) are heated to a melt state and then kneaded. The kneading temperature can be set within a range in which the polymer compound (C) and the cyclic olefin polymer (E) are in a melt state, for example, in the range of "Tg + 10°C" to "Tg + 200°C". Here, "Tg" represents the glass transition temperature of the resin composition (D).

[0143] The method for producing the resin composition (D) may further include any optional steps. For example, after obtaining the resin composition (D), the method for producing the resin composition (D) may include steps to remove the used catalyst and / or solvent. These optional steps can be carried out in the same manner as the steps in the method for producing the terminal hydroxyl group-containing cyclic olefin polymer (A). The method for producing the resin composition (D) may also include a step of mixing any components. The components may be mixed all at once or sequentially. Furthermore, from the viewpoint of improving the handling of the resin composition (D), the method for producing the resin composition (D) may include a step of pelletizing the obtained resin composition (D).

[0144] <Molded Article> The resin composition (D) can be used as a material for a molded article. Such a molded article may contain the resin composition (D) or contain only the resin composition (D). There are no restrictions on the shape of such a molded article; for example, it may be in the form of a film, syringe, bag, cup, tube, etc. Such a molded article can be manufactured by a manufacturing method that includes molding the resin composition (D). Examples of molding methods include extrusion molding.

[0145] <Film> From the viewpoint of effectively utilizing the effects of the present invention, it is preferable to use the resin composition (D) as a material for a film. Such a film may contain the resin composition (D), or it may contain only the resin composition (D). By containing the resin composition (D), this film can achieve high peel strength.

[0146] The peel strength of a film can be expressed as the magnitude of the force required to peel the film, which has been bonded to an adherend, from that adherend. For example, a high peel strength can be achieved when a 90-degree peel test is performed to measure the peel strength using the method described in (6. Method for Measuring the Peel Strength of a Stretched Film) in the examples described later. In one example, the peel strength of the film in the 90-degree peel test described later may be 0.5 N or higher.

[0147] The film thickness can be set according to the intended use of the film. For example, the film thickness range is preferably 1 μm or more, more preferably 5 μm or more, even more preferably 10 μm or more, preferably 500 μm or less, more preferably 200 μm or less, and even more preferably 100 μm or less.

[0148] The film may be in sheet form or in elongated form. Unless otherwise specified, an elongated film is a film that is usually five times or more in length than its width, preferably ten times or more in length, and specifically a film that is long enough to be wound into a roll for storage or transport. The upper limit of the length of an elongated film may be, for example, 100,000 times or less its width.

[0149] The film may be subjected to a stretching treatment. Hereinafter, a film that has undergone such a stretching treatment may be referred to as a "stretched film." Also, for the sake of distinction, a film before stretching treatment may be referred to as a "pre-stretched film." Stretching treatment can adjust the physical properties of the film and bring out optical properties such as birefringence. Furthermore, conventional stretched films formed from cyclic olefin polymers tended to be particularly susceptible to delamination after stretching. From the viewpoint of utilizing the advantage of the present invention, which is that such delamination can be effectively suppressed, it is preferable to apply the resin composition (D) to the material of the stretched film.

[0150] A stretched film can be produced, for example, by a manufacturing method that includes the steps of forming a pre-stretched film with a resin composition (D) and stretching the pre-stretched film.

[0151] Methods for forming the film before stretching include, for example, casting, extrusion, and inflation molding. Among these, the melt extrusion method, which does not use solvents, is preferable from the viewpoint of the working environment and manufacturing efficiency, as it can efficiently reduce the amount of volatile components.

[0152] In the melt extrusion method, for example, a molten resin composition (D) is extruded from a die in the form of a film, and the film-like resin composition (D) is cooled to form a pre-stretched film. The melting temperature of the extruded resin composition (D) can be set to obtain the desired stretched film. In one example, the melting temperature range of the extruded resin composition (D) is preferably Tg + 50°C or higher, preferably Tg + 80°C or higher, more preferably Tg + 100°C or higher, preferably Tg + 180°C or lower, and more preferably Tg + 170°C or lower. Here, "Tg" represents the glass transition temperature of the resin composition (D).

[0153] The film-like resin composition (D) extruded from the die may be received by a cooling roll and cooled by the cooling roll. If necessary, part or all of the film-like resin composition (D) may be brought into contact with the cooling roll by an appropriate method such as an air knife method, a vacuum box method, or an electrostatic contact method. The number of cooling rolls is not particularly limited and may be, for example, two or more. Examples of arrangement methods for the cooling rolls include a straight type, a Z type, an L type, etc.

[0154] The step of forming the pre-stretched film preferably includes forming a long pre-stretched film. According to the melt extrusion method described above, a long pre-stretched film can be formed. By using a long pre-stretched film, a long stretched film can be manufactured continuously, thus enabling the efficient production of stretched films.

[0155] After the pre-stretched film is formed, the pre-stretched film is stretched to obtain a stretched film. There are no restrictions on the direction of this stretching; for example, it can be in the longitudinal direction, the width direction, or an oblique direction. Here, the oblique direction refers to a direction perpendicular to the thickness direction, and neither parallel nor perpendicular to the width direction. Therefore, in one example, the step of stretching the pre-stretched film may include stretching the pre-stretched film in an oblique direction.

[0156] The stretching direction may be one direction or two or more directions. Therefore, in one example, the step of stretching the pre-stretched film may include stretching the pre-stretched film in one or two stretching directions.

[0157] Examples of stretching methods include uniaxial stretching methods such as stretching the film in the longitudinal direction (longitudinal uniaxial stretching method) and stretching the film in the width direction (horizontal uniaxial stretching method); biaxial stretching methods such as simultaneous biaxial stretching, in which the film is stretched in the longitudinal direction and simultaneously in the width direction; sequential biaxial stretching, in which the film is stretched in one direction (longitudinal or width direction) and then in the other direction; and diagonal stretching methods.

[0158] The stretching temperature of the film before stretching can be set to obtain the desired stretched film. In one example, the stretching temperature range is preferably "Tg + 5°C" or higher, more preferably "Tg + 10°C" or higher, preferably "Tg + 100°C" or lower, and more preferably "Tg + 90°C" or lower. Here, "Tg" represents the glass transition temperature of the resin composition (D).

[0159] The surface stretching ratio of the pre-stretched film can be set to obtain the desired stretched film. In one example, the range of the surface stretching ratio is preferably 1.1 times or more, more preferably 1.2 times or more, even more preferably 1.3 times or more, preferably 7.0 times or less, more preferably 6.0 times or less, and even more preferably 5.0 times or less. When the step of stretching the pre-stretched film includes stretching the pre-stretched film at a surface stretching ratio within the above range, the changes in physical properties or optical properties due to the stretching process can be greatly increased, making it possible to smoothly obtain a stretched film having the desired physical properties or optical properties.

[0160] The method for manufacturing a stretched film may include any additional steps in addition to the steps described above. For example, the method for manufacturing a stretched film may include a step of winding the manufactured long stretched film into a roll. Furthermore, the method for manufacturing a stretched film may include a step of cutting the long stretched film into a desired shape.

[0161] <Polarizing Plate> A film containing the resin composition (D) can be applied to a polarizing plate. Such a polarizing plate comprises the above-described film and a polarizer. In a polarizing plate, the film containing the resin composition (D) can function as, for example, a protective film, a phase difference film, etc. Preferably, this polarizing plate can function as a linear polarizing plate, a circular polarizing plate, or an elliptical polarizing plate.

[0162] Typically, linear polarizers are used as polarizers. Examples of such linear polarizers include films obtained by adsorbing iodine or a dichroic dye onto a polyvinyl alcohol film and then uniaxially stretching it in a boric acid bath; and films obtained by adsorbing iodine or a dichroic dye onto a polyvinyl alcohol film, stretching it, and further modifying some of the polyvinyl alcohol units in the molecular chain into polyvinylene units. Other examples of polarizers include grid polarizers and multilayer polarizers, which have the function of separating polarized light into reflected light and transmitted light. Of these, polarizers containing polyvinyl alcohol are preferred.

[0163] When natural light is incident on a polarizer, only one type of polarization is transmitted. The degree of polarization of this polarizer is not particularly limited, but is preferably 98% or higher, more preferably 99% or higher. The thickness of the polarizer is preferably 5 μm to 80 μm.

[0164] A polarizing plate may include any additional layers besides the polarizer and film. Examples of such additional layers include an adhesive layer for bonding the polarizer and the film together, and a polarizer protective film layer for protecting the polarizer.

[0165] The aforementioned polarizing plate can be manufactured, for example, by a manufacturing method that includes laminating a film containing a resin composition (D) with a polarizer. An adhesive may be used for lamination, if necessary.

[0166] <Liquid Crystal Display Device> The film containing the resin composition (D) can be applied to a liquid crystal display device. Therefore, a liquid crystal display device equipped with the film can be obtained using the film containing the resin composition (D). In the liquid crystal display device, the film may function as a protective film, a viewing angle compensation film, or a phase difference film.

[0167] A liquid crystal display device typically comprises a liquid crystal cell and a polarizing plate. In this case, the polarizing plate may be made of the aforementioned film containing a resin composition (D), thereby obtaining a liquid crystal display device equipped with the film.

[0168] Liquid crystal cells can be of any mode, such as in-plane switching (IPS) mode, vertical alignment (VA) mode, multi-domain vertical alignment (MVA) mode, continuous spinwheel alignment (CPA) mode, hybrid alignment nematic (HAN) mode, twisted nematic (TN) mode, super-twisted nematic (STN) mode, and optically compensated bend (OCB) mode.

[0169] <Organic EL Display Device> The film containing the resin composition (D) can be applied to an organic EL display device. Therefore, an organic EL display device equipped with the film can be obtained using the film containing the resin composition (D). In the organic EL display device, the film may function as a protective film or a phase difference film.

[0170] Organic EL display devices typically include organic EL elements. Furthermore, to suppress the reflection of ambient light from the organic EL elements, organic EL display devices may include a circular polarizer as a reflection-suppressing film. In this case, an organic EL display device may be obtained by providing the circular polarizer with the aforementioned film containing a resin composition (D).

[0171] Organic EL devices typically comprise a transparent electrode layer, an emissive layer, and an electrode layer in that order, and the emissive layer can emit light when a voltage is applied from the transparent electrode layer and the electrode layer. Examples of materials that constitute the organic emissive layer include poly(p-phenylenevinylene), polyfluorene, and polyvinylcarbazole materials. The emissive layer may also have a laminate of multiple layers with different emission colors, or a mixed layer in which a layer of one dye is doped with a different dye. Furthermore, organic EL devices may include functional layers such as a hole injection layer, a hole transport layer, an electron injection layer, an electron transport layer, an equipotential surface forming layer, and a charge generation layer.

[0172] The present invention will be specifically described below with reference to examples. However, the present invention is not limited to the examples shown below, and can be modified and implemented as appropriate without departing from the scope of the claims and their equivalents. In the following description, "%" and "parts" representing quantities are based on weight unless otherwise specified. Furthermore, the operations described below were carried out under normal temperature and pressure (23°C, 1 atm) conditions in the atmosphere unless otherwise specified.

[0173] <Evaluation Method> (1. Method for measuring the weight-average molecular weight of the total polymer in the terminal hydroxyl group-containing cyclic olefin polymer (A-1), polymer compound (C-1), and resin composition (D-1)) The weight-average molecular weight of the total polymer in the terminal hydroxyl group-containing cyclic olefin polymer (A-1), polymer compound (C-1), and resin composition (D-1) was determined as polystyrene-equivalent molecular weight by gel permeation chromatography. In addition, for the terminal hydroxyl group-containing cyclic olefin polymer (A-1), the number-average molecular weight in polystyrene equivalent was also measured by the same gel permeation chromatography. Specifically, the measurements were performed under the following conditions: Measuring instrument: High-performance liquid chromatograph (manufactured by Tosoh Corporation, product name "HLC-8220") Column: Two columns of Tosoh Corporation product name "GMH-HR-H" connected in series. Detector: Differential refractometer (Tosoh Corporation, product name "RI-8220") Eluent: Tetrahydrofuran column Temperature: 40°C

[0174] (2. Method for measuring the weight-average molecular weight Mw of the terminal hydroxyl group-containing cyclic olefin polymer (A-2) and the total polymer in the resin composition (D-2)) The weight-average molecular weight Mw of the terminal hydroxyl group-containing cyclic olefin polymer (A-2) as a hydrogenated polymer and the total polymer in the resin composition (D-2) was determined as the molecular weight equivalent to standard polyisoprene by gel permeation chromatography (GPC) using cyclohexane as the eluent. Standard polyisoprene manufactured by Tosoh Corporation (Mw = 602, 1390, 3920, 8050, 13800, 22700, 58800, 71300, 109000, 280000) was used as the standard polyisoprene. The measurements were performed using three Tosoh Corporation columns (TSKgel G5000HXL, TSKgel G4000HXL, and TSKgel G2000HXL) connected in series, under the conditions of a flow rate of 1.0 mL / min, a sample injection volume of 100 μL, and a column temperature of 40°C.

[0175] (3. Method for measuring the hydrogenation rate of polymers) The hydrogenation rate of polymers is measured by orthodichlorobenzene-d ４ Using as a solvent, at 145°C, １ Measured by 1H-NMR.

[0176] (4. Method for measuring the rate of introduction of terminal hydroxyl groups) For terminal hydroxyl group-containing cyclic olefin polymer (A-1), １ ¹H-NMR spectroscopy was used to measure the ratio of the peak integral value derived from active hydrogen in the terminal hydroxyl groups to the peak integral value derived from hydrogen in the cyclic olefin units. Based on the measured ratio of peak integral values ​​and the number-average molecular weight (Mn) measurement results by GPC described above, the introduction rate of terminal hydroxyl groups in the terminal hydroxyl group-containing cyclic olefin polymer (A-1) was calculated. The introduction rate of terminal hydroxyl groups was defined as the ratio of the number of terminal hydroxyl groups to the number of terminals in the polymer chain of the terminal hydroxyl group-containing cyclic olefin polymer (A-1). That is, a terminal hydroxyl group content of 100% indicates that two terminal hydroxyl groups are introduced per polymer chain.

[0177] (5. Method for measuring the glass transition temperature Tg) The glass transition temperature (Tg) was measured using a differential scanning calorimetry analyzer (DSC6220SII, manufactured by Nanotechnology Inc.) in accordance with JIS K 6911, under conditions of a heating rate of 10°C / min.

[0178] (6. Method for Measuring the Peel Strength of Stretched Films) An unstretched film made of a resin containing norbornene polymer (Zeonor Film, manufactured by Zeon Corporation, 100 μm thick, glass transition temperature of the resin 160°C, no stretching treatment applied) was prepared as the adherend. One side of the stretched film, which was to be measured, and one side of the unstretched film were subjected to corona treatment. Adhesive (UV adhesive CRB series, manufactured by Toyo Chem Co., Ltd.) was applied to both the corona-treated side of the stretched film and the corona-treated side of the unstretched film. The sides with the adhesive applied were bonded together. Then, the adhesive was cured by irradiating it with ultraviolet light using an electrodeless UV irradiation device (Heraeus Corporation). For the ultraviolet irradiation, a D bulb was used as the lamp, and the peak illuminance was 100 mW / cm². ２ , cumulative light intensity 3000 mJ / cm ２ The experiment was conducted under the following conditions. This resulted in obtaining a sample film having a layer structure of "unstretched film / adhesive layer / stretched film".

[0179] A 90-degree peel test was performed on the obtained sample film using the following procedure. The sample film was cut into 15 mm wide strips to obtain film pieces. The stretched film side of these film pieces was attached to the surface of a glass slide using an adhesive. Double-sided adhesive tape (Nitto Denko Corporation, part number "CS9621") was used as the adhesive. An unstretched film contained in the film piece was clamped to the tip of a high-performance digital force gauge (IMADA Corporation, "ZP-5N"), and the unstretched film was pulled at a speed of 300 mm / min in the direction normal to the surface of the glass slide. The amount of pulling force required to peel the unstretched film from the stretched film was measured as the peel strength. The determined peel strength was evaluated according to the following criteria: Good: The peel strength was 0.5 N or more, or the unstretched film broke before peeling. Poor: The peel strength was less than 0.5 N.

[0180] <Example 1> (1-1. Production of terminal hydroxyl group-containing cyclic olefin polymer) Under a nitrogen atmosphere, 100 parts norbornene, 141 parts cyclohexane, 144 parts tetrahydrofuran, and 77.7 parts cis-2-butene-1,4-diol were added to a glass container with a stirring bar. Then, while vigorously stirring, 7.3 parts of a 1.06 wt% ring-opening polymerization catalyst / toluene solution were added. Dichloro(3-phenyl-1H-inden-1-ylidene)bis(triphenylphosphine)ruthenium(II), "Grubbs Catalyst® M101" manufactured by Merck, was used as the ring-opening polymerization catalyst. Subsequently, the polymer solution was obtained by stirring at room temperature for 3 hours.

[0181] The polymer solution in the glass reaction vessel was poured into a large excess of isopropanol. The precipitated polymer was then collected and washed with isopropanol. The polymer was then vacuum-dried at 40°C for 3 days to obtain 50 parts of terminally hydroxyl-containing cyclic olefin polymer (A-1). The weight-average molecular weight of the obtained terminally hydroxyl-containing cyclic olefin polymer (A-1) was 1.0 × 10⁻⁶. ４ The glass transition temperature Tg was 27.5°C.

[0182] Terminal hydroxyl group-containing cyclic olefin polymer (A-1) １ ¹H-NMR was measured, and the following results were obtained. From these results, it was confirmed that the terminal hydroxyl group-containing cyclic olefin polymer (A-1) has the structure represented by formula (a1). １ H-NMR (400MHz, CDCl ３ ): δ (ppm) 5.99 (m), 5.82-5.75 (m), 5.39-5.30 (m), 5.24-5.16 (m), 4.30-4.20 (m), 2.52-2.35 (m), 1.96-1.65 (m), 1.44-1.28 (m)

[0183] (1-2. Hydrogenation of Terminal Hydroxyl Group-Containing Cyclic Olefin Polymer) 100 parts (30 parts polymer) of a solution of the terminal hydroxyl group-containing cyclic olefin polymer (A-1) produced in step (1-1) above were mixed with 200 parts of cyclohexane and 0.05 parts of chlorohydridecarbonyltris(triphenylphosphine)ruthenium. A hydrogenation reaction was carried out at a hydrogen pressure of 6 MPa and 180°C for 6 hours. This hydrogenation reaction yielded a reaction solution containing the terminal hydroxyl group-containing cyclic olefin polymer (A-2) as a hydrogenated product of the terminal hydroxyl group-containing cyclic olefin polymer (A-1).

[0184] The resulting reaction solution was poured into a large amount of isopropanol to precipitate the terminal hydroxyl group-containing cyclic olefin polymer (A-2). After filtering off the precipitated terminal hydroxyl group-containing cyclic olefin polymer (A-2), it was dried in a vacuum dryer (200°C, 1 Torr) for 6 hours to obtain terminal hydroxyl group-containing cyclic olefin polymer (A-2). The weight-average molecular weight of terminal hydroxyl group-containing cyclic olefin polymer (A-2) was 1.9 × 10⁻⁶. ４ The glass transition temperature Tg was -2°C, and the hydrogenation rate was 100%.

[0185] (1-3. Production of cyclic olefin polymer containing terminal aliphatic rings) Under a nitrogen atmosphere, 30 parts of the cyclic olefin polymer containing terminal hydroxyl groups (A-2) obtained in step (1-2) above, 0.044 parts of exo-norbornenecarboxylic acid, 0.058 parts of dimethylaminopyridine, 0.091 parts of 1-[3-(dimethylamino)propyl]-3-ethylcarbodiimide hydrochloride, and 10.6 parts of dichloromethane were added to a glass container with a stirring bar and stirred at room temperature for 3 days. The solution in the glass reaction vessel was poured into a large excess of hexane. Then, a large excess of methanol was added and the precipitated polymer was recovered. After washing the recovered polymer with methanol, 15 parts of cyclic olefin polymer containing terminal aliphatic rings (B-1) were obtained by vacuum drying at 40°C for 3 days. The weight-average molecular weight of cyclic olefin polymer containing terminal aliphatic rings (B-1) is 1.9 × 10⁻⁶. ４ The glass transition temperature Tg was -2°C.

[0186] (1-4. Production of Polymer Compounds) Under a nitrogen atmosphere, 1 part of the terminal aliphatic ring-containing cyclic olefin polymer (B-1) obtained in step (1-3) above, 0.0686 parts of the third-generation Grubbs catalyst represented by formula (g1) above, and 1543 parts of dichloromethane were added to a glass container with a stirring bar, and the mixture was stirred at room temperature for 2 hours. An excess amount of ethyl vinyl ether was added to the solution in the glass reaction vessel to inactivate the catalyst. The solvent was then concentrated and the polymer precipitated. The precipitated polymer was dissolved in n-hexane, washed five times with methanol, and then purified by size exclusion chromatography (preparative SEC) to obtain 0.8 parts of polymer compound (C-1). The weight-average molecular weight of polymer compound (C-1) was 1.6 × 10⁻⁶. ４ The glass transition temperature Tg was 0°C.

[0187] (1-5. Synthesis of Cyclic Olefin Polymers) In a glass reaction vessel with the interior purged with nitrogen, 450 g of dehydrated cyclohexane, 0.7 mol% of 1-hexene, 0.15 mol% of diisopropyl ether, and 0.44 mol% of triisobutylaluminum were placed at room temperature and mixed. Then, while maintaining the temperature at 55°C, 8.04 mol% (10 wt%) of methanolotetrahydrofluorene (MTF), 36.56 mol% (40 wt%) of tetracyclododecene (TCD), 55.40 mol% (50 wt%) of dicyclopentadiene (DCPD), 0.09 mol% (10 wt%) of the polymer compound (C-1) obtained in step (1-4) above, and 0.02 mol% of tungsten hexachloride (0.65 wt% toluene solution) were added in parallel and continuously over 2 hours to carry out polymerization. Next, 0.2 mol% isopropyl alcohol was added to the polymerization solution to inactivate the polymerization catalyst and stop the polymerization reaction. Here, the amount of each component expressed in "mol%" represents the sum of MTF, TCD, and DCPD, which is 100 mol%.

[0188] As a result of the polymerization described above, a cyclic olefin polymer (E-1) was synthesized, and a resin composition (D-1) containing the polymer compound (C-1) and the cyclic olefin polymer (E-1) was obtained. The weight-average molecular weight Mw of the total polymer (i.e., the polymer compound (C-1) and the cyclic olefin polymer (E-1)) in the resin composition (D-1) is 2.3 × 10⁻⁶.４ Furthermore, for the cyclic olefin polymer (E-1), the conversion rate of monomers (MTF, TCD, and DCPD) to polymer was 100%. The conversion rate of monomers to polymer was measured by detecting the monomer (MTF, TCD, and DCPD) peaks using gas chromatography.

[0189] (1-6. Hydrogenation of Cyclic Olefin Polymer) To 183 g of a solution of resin composition (D-1) containing the polymer compound (C-1) and cyclic olefin polymer (E-1) obtained in step (1-5) above, 67 g of cyclohexane was added, and 1.8% by weight of diatomaceous earth-supported nickel catalyst (JGC Chemical Co., Ltd. "T8400RL", nickel support rate 57%) was added as a hydrogenation catalyst. The mixture was pressurized to 4.5 MPa with hydrogen and heated to 190°C while stirring, and the hydrogenation reaction was carried out for 8 hours. This hydrogenation reaction yielded a reaction solution containing the polymer compound (C-1) and cyclic olefin polymer (E-2). The cyclic olefin polymer (E-2) corresponds to the hydride of the cyclic olefin polymer (E-1).

[0190] The reaction solution was subjected to pressure filtration at 0.25 MPa using Radiolite #500 as a filter bed (using a "Fundaback filter" manufactured by Ishikawajima-Harima Heavy Industries Co., Ltd.) to remove the hydrogenation catalyst and obtain a colorless, transparent solution. Next, the obtained solution was poured into a large amount of isopropanol to precipitate the polymer compound (C-1) and the cyclic olefin polymer (E-2). After filtering off the precipitated polymer compound (C-1) and cyclic olefin polymer (E-2), they were dried in a vacuum dryer (200°C, 1 Torr) for 6 hours to obtain a resin composition (D-2) containing the polymer compound (C-1) and the cyclic olefin polymer (E-2).

[0191] The weight-average molecular weight of the total polymer (i.e., polymer compound (C-1) and cyclic olefin polymer (E-2)) in the resin composition (D-2) is 3.6 × 10⁻¹⁴. ４The glass transition temperature Tg was 115.0°C. In the state where it was not mixed with the polymer compound (C-1), the glass transition temperature of the cyclic olefin polymer (E-2) was 127.5°C. Furthermore, the hydrogenation rate of the cyclic olefin polymer (E-2) in the resin composition (D-2) was 99.7%.

[0192] (1-7. Production of pre-stretched film) The resin composition (D-2) obtained in step (1-6) above was fed into a twin-screw extruder and molded into a strand-like molded body by hot melt extrusion molding. This molded body was shredded using a strand cutter to obtain pellets of the resin composition (D-2) containing a polymer compound (C-1) and a cyclic olefin polymer (E-2).

[0193] These pellets were dried at 80°C for 5 hours. Then, the pellets were fed into an extruder by a conventional method and melted at 250°C. The molten resin composition (D-2) was then discharged from the die onto a cooling drum to obtain a long, unstretched film with a thickness of 115 μm.

[0194] (1-8. Manufacturing of stretched film) The pre-stretched film obtained in step (1-7) above was supplied to a transverse stretcher using the tenter method, and stretched to a surface stretching ratio of 3.5 times in the width direction while adjusting the pull tension and tenter chain tension. The stretching temperature for the stretching using the transverse stretcher was 22°C higher than the glass transition temperature Tg of the resin composition (D-2) (Tg + 22°C). The obtained stretched film had a thickness d of 33 μm.

[0195] The resulting stretched film was evaluated using the method described above.

[0196] <Example 2> In the same method as in Example 1, except that the amount of cis-2-butene-1,4-diol used as a chain transfer agent in step (1-1) was changed to 7.7 parts, a terminal hydroxyl group-containing cyclic olefin polymer (A-1), a terminal hydroxyl group-containing cyclic olefin polymer (A-2) as a hydrogenated product of the terminal hydroxyl group-containing cyclic olefin polymer (A-1), a terminal aliphatic ring-containing cyclic olefin polymer (B-1), a polymer compound (C-1) as a polymer of the terminal aliphatic ring-containing cyclic olefin polymer (B-1), a resin composition (D-1) containing the polymer compound (C-1) and the cyclic olefin polymer (E-1), a resin composition (D-2) obtained by hydrogenating the cyclic olefin polymer (E-1) of the resin composition (D-1), and a stretched film containing the resin composition (D-2) were manufactured and evaluated.

[0197] <Comparative Example 1> A stretched film was manufactured and evaluated using the same method as in steps (1-7) and (1-8) of Example 1, except that a cyclic olefin polymer (Zeonor 1430R, manufactured by Nippon Zeon Co., Ltd., weight-average molecular weight 44,000, glass transition temperature 136°C) was used instead of the resin composition (D-2).

[0198] <Results> The results of the above examples and comparative examples are shown in the table below. In the table below, the meanings of the abbreviations are as follows. Also, in the table below, the hydrogenation rate in the column for resin composition (D-2) represents the hydrogenation rate of the cyclic olefin polymer (E-2) contained in the resin composition (D-2). Mw: weight-average molecular weight Tg: glass transition temperature

[0199]

[0200] 10 Polymer compound (C) 11 Ring 20 Polymer compound (C) 21-23 Ring

Claims

1. A terminal hydroxyl group-containing cyclic olefin polymer containing a cyclic olefin unit, wherein the cyclic olefin unit contains an aliphatic carbon ring, and the terminal hydroxyl group-containing cyclic olefin polymer contains a hydroxyl group at its terminal end.

2. The terminal hydroxyl group-containing cyclic olefin polymer according to claim 1, wherein the cyclic olefin unit includes a structure formed by ring-opening polymerization and hydrogenation of a cyclic olefin compound, and the hydrogenation rate of the cyclic olefin unit is 50% or more.

3. The terminal hydroxyl group-containing cyclic olefin polymer according to claim 1, wherein the terminal hydroxyl group-containing cyclic olefin polymer contains hydroxyl groups at both ends.

4. A method for producing a terminal hydroxyl group-containing cyclic olefin polymer according to claim 1, comprising the step of polymerizing a cyclic olefin compound and an olefin compound containing a hydroxyl group.

5. A terminal aliphatic ring-containing cyclic olefin polymer containing a cyclic olefin unit, wherein the cyclic olefin unit contains an aliphatic carbon ring, and the terminal aliphatic ring-containing cyclic olefin polymer contains an unsaturated cyclic aliphatic hydrocarbon group at its terminal end.

6. The terminal aliphatic ring-containing cyclic olefin polymer according to claim 5, wherein the cyclic olefin unit includes a structure formed by ring-opening polymerization and hydrogenation of a cyclic olefin compound, and the hydrogenation rate of the cyclic olefin unit is 50% or more.

7. The terminal aliphatic ring-containing cyclic olefin polymer according to claim 5, wherein the terminal aliphatic ring-containing cyclic olefin polymer contains unsaturated cyclic aliphatic hydrocarbon groups at both ends.

8. A method for producing a terminal aliphatic ring-containing cyclic olefin polymer according to claim 5, comprising reacting the terminal hydroxyl group-containing cyclic olefin polymer according to claim 1 with a cyclic olefin compound containing an unsaturated cyclic aliphatic hydrocarbon group and a carboxyl group, or a cyclic olefin compound containing an unsaturated cyclic aliphatic hydrocarbon group and an alkyl halogenate.

9. A polymer compound which is a polymer of the terminal aliphatic ring-containing cyclic olefin polymer described in claim 5.

10. A method for producing a polymer compound according to claim 9, comprising the step of polymerizing a terminal aliphatic ring-containing cyclic olefin polymer according to claim 5.

11. A resin composition comprising the polymer compound described in claim 9 and a cyclic olefin polymer.

12. A method for producing a resin composition according to claim 11, comprising the step of polymerizing a cyclic olefin compound in the presence of the polymer compound according to claim 9.

13. A method for producing a resin composition according to claim 11, comprising the step of mixing a polymer compound according to claim 9 with a cyclic olefin polymer.

14. A molded article comprising the resin composition described in claim 11.

15. A film comprising the resin composition described in claim 11.

16. A polarizing plate comprising the film described in claim 15 and a polarizer.

17. A method for producing a stretched film, comprising the steps of: forming a pre-stretched film with the resin composition described in claim 11; and stretching the pre-stretched film.

18. The method for manufacturing a stretched film according to claim 17, wherein the step of forming the pre-stretched film includes forming a long pre-stretched film, and the step of stretching the pre-stretched film includes stretching the pre-stretched film in an oblique direction.

19. The method for manufacturing a stretched film according to claim 17, wherein the step of stretching the pre-stretched film includes stretching the pre-stretched film in one or two stretching directions.

20. The method for manufacturing a stretched film according to claim 17, wherein the step of stretching the pre-stretched film includes stretching the pre-stretched film at a surface stretching ratio of 1.1 times or more.

21. A liquid crystal display device comprising the film described in claim 15.

22. An organic electroluminescent display device comprising the film described in claim 15.

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