WO2019181124A1

WO2019181124A1 - Dicyclopentadiene-based ring-opened polymer hydride, method for producing same, resin molded article, resin film, and method for producing stretched film

Info

Publication number: WO2019181124A1
Application number: PCT/JP2018/047290
Authority: WO
Inventors: 遠藤　充輝; 村田　徹; 健作藤井; 重孝早野
Original assignee: 日本ゼオン株式会社
Priority date: 2018-03-22
Filing date: 2018-12-21
Publication date: 2019-09-26
Also published as: JP7218753B2; JPWO2019181124A1

Abstract

A dicyclopentadiene-based ring-opened polymer hydride having a syndiotacticity of 99% or higher and a hydrogenation rate of 98.0% or higher.

Description

Dicyclopentadiene-based ring-opening polymer hydride and method for producing the same, resin molded product, resin film, and method for producing stretched film

The present invention relates to a dicyclopentadiene ring-opening polymer hydride and a method for producing the same, a resin molded product, a resin film, and a method for producing a stretched film.

A hydride of norbornene-based ring-opening polymer that can be prepared by ring-opening polymerization of a norbornene-based monomer such as dicyclopentadiene is called “cycloolefin polymer” and is a kind of a commercially available material. Such a ring-opened polymer hydride is attracting attention as a material applicable to various uses including optical use because it is excellent in transparency, low birefringence, molding processability and the like.

Here, the ring-opening polymer hydride containing monomer units derived from dicyclopentadiene (hereinafter also referred to as “dicyclopentadiene-based ring-opening polymer hydride”) is an amorphous structure having an atactic structure. It was common to obtain it as a polymer. However, the amorphous dicyclopentadiene ring-opening polymer hydride having an atactic structure may have insufficient heat resistance, mechanical strength, solvent resistance, and the like depending on its use. Therefore, as a technique for improving the performance, dicyclopentadiene ring-opening polymer hydride having crystallinity is produced by producing dicyclopentadiene ring-opening polymer hydride having stereoregularity in the main chain. Has been developed.

Therefore, a resin containing a crystalline dicyclopentadiene ring-opening polymer hydride with improved industrial handleability, and a resin molded product, a resin film, and an injection molded product obtained using such a resin have been proposed. (For example, see Patent Documents 1 and 2). Patent Documents 1 and 2 disclose a crystalline dicyclopentadiene ring-opened polymer hydride having a melting start temperature of 260 ° C. or higher, a melting point of less than 280 ° C., and a syndiotacticity of more than 90%. It is disclosed.
Patent Document 3 discloses a hydrogenated poly (dicyclopentadiene) polymer in which more than 80% is syndiotactic.

International Publication No. 2016/143795 International Publication No. 2016/143424 International Publication No. 2015/127192

Here, in recent years, resin molded bodies and the like are required to have both strength and ductility at a high level. However, the resin moldings and the like formed using the polymer hydrides described in Patent Documents 1 to 3 have room for improvement in terms of improving both strength and ductility.

Therefore, an object of the present invention is to provide a dicyclopentadiene ring-opening polymer hydride and a method for producing the same, which are capable of forming a resin molded body and the like that are compatible at a high strength and ductility level.
Furthermore, an object of the present invention is to provide a resin film and a resin molded body that are compatible at a high strength and ductility level.
Furthermore, an object of this invention is to provide the manufacturing method of a stretched film which can manufacture a stretched film favorably using the resin film in which the intensity | strength and ductility were compatible at a high level.

The present inventor has intensively studied for the purpose of solving the above problems. Then, when preparing the dicyclopentadiene-based ring-opening polymer hydride, the inventor increases the hydrogenation rate to a predetermined value or higher when the syndiotacticity is remarkably increased. It has been found that both strength and ductility of a resin molded article containing a cyclic polymer hydride can be achieved at a high level, and the present invention has been completed.

That is, the present invention aims to advantageously solve the above problems, and the dicyclopentadiene ring-opening polymer hydride of the present invention has a syndiotacticity of 99% or more and a hydrogenation. The rate is 98.0% or more. Thus, the dicyclopentadiene ring-opening polymer hydride satisfying both the above-mentioned ranges for both syndiotacticity and hydrogenation rate achieves both high strength and ductility of the resulting resin molded article. can do.
Here, the syndiotacticity of the dicyclopentadiene ring-opening polymer hydride can be determined by the method using ¹³ C-NMR described in Examples. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride can be determined by the method using ¹ H-NMR described in Examples.

Here, the hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride of the present invention is preferably 99.0% or more. By using a hydride of a dicyclopentadiene ring-opening polymer having a hydrogenation rate of 99.0% or more, it becomes possible to provide a resin molded article having excellent reflow resistance.

Furthermore, the present invention aims to advantageously solve the above-mentioned problems, and the resin molded product of the present invention contains any one of the above dicyclopentadiene ring-opening polymer hydrides. And The resin molded article containing the dicyclopentadiene-based ring-opening polymer hydride of the present invention has both high strength and ductility.

The present invention is also intended to advantageously solve the above problems, and the resin film of the present invention contains any one of the above dicyclopentadiene ring-opening polymer hydrides. To do. The resin film containing the dicyclopentadiene-based ring-opening polymer hydride of the present invention has both high strength and ductility.

Here, the resin film of the present invention has a gas generation amount attributed to a mass number of 18 (m / z) generated between room temperature and 300 ° C. as measured by heat generation gas mass spectrometry. The mass is preferably less than 0.5% by mass based on 100% by mass. A resin film in which the amount of gas generated when measured under predetermined conditions is highly suitable as an electric / electronic material. Here, the heat generation gas mass spectrometry (Temperature Programmed Desorption / Mass Spectrometry (TPD-MS)) can be performed according to the method described in the examples of the present specification. The definition of “room temperature” follows JIS Z 8703: 1983. Furthermore, the “initial mass of the film” is the mass of the resin film in the stage before starting the measurement according to the heat generation gas mass spectrometry.

Further, the present invention aims to advantageously solve the above-mentioned problems, and the method for producing a dicyclopentadiene ring-opening polymer hydride of the present invention is represented by the following general formula (α). Using a ring-opening polymerization catalyst, ring-opening polymerization of a monomer containing dicyclopentadiene to obtain a dicyclopentadiene-based ring-opening polymer, and the dicyclopentadiene-based ring-opening polymer And hydrogenation to obtain a dicyclopentadiene ring-opened polymer hydride having a hydrogenation rate of 98.0% or more. According to the method for producing a dicyclopentadiene-based ring-opening polymer hydride of the present invention, a dicyclopentadiene-based ring-opening polymer hydride capable of forming a resin molded body compatible with strength and ductility at a high level is obtained. It can be manufactured satisfactorily.

[In the formula (α), Ph represents a phenyl group, and R ¹ and R ² each independently represents a monovalent linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms. X represents a hydrogen atom, a halogen atom, a nitro group, an amino group, or a cyano group, and n represents an integer of 0 to 5, and when n is an integer of 1 or more, a plurality of X ^{May be} the same or different; Y represents C (R ³ ) ₂ R ⁴ (wherein each R ³ independently represents —R ⁵ , —OR ⁵ , —SR). ⁵ , —N (R ⁵ ) ₂ , —OC (O) R ⁵ , —S (O) R ⁵ , —SO ₂ R ⁵ , —SO ₂ N (R ⁵ ) ₂ , —C (O) N (R ⁵ ) ₂ , —NR ⁵ C (O) R ⁵ , or —NR ⁵ SO ₂ R ⁵ , wherein each R ⁵ is independently hydrogen or a straight chain of 1 to 12 carbon atoms. Or branched alkyl 1 to 10 heteroalkyl groups having 1 to 3 heteroatoms independently selected from the group, nitrogen, oxygen or sulfur, phenyl groups, 3 to 7-membered saturated or partially unsaturated carbons 5 to 5 having 1 to 4 heteroatoms independently selected from a ring, a 6 to 10-membered bicyclic saturated ring, a partially unsaturated ring, or an aryl ring, nitrogen, oxygen, or sulfur 6-membered monocyclic heteroaryl ring, 3- to 7-membered saturated or partially unsaturated heterocycle having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, nitrogen, oxygen Or a 7 to 10 membered bicyclic saturated or partially unsaturated heterocycle having 1 to 5 heteroatoms independently selected from sulfur, and independently from nitrogen, oxygen, or sulfur 8 to 10 members with 1 to 5 heteroatoms selected Is selected from the bicyclic heteroaryl ring, or an optionally substituted group, or, optionally, two R ^5, optionally in combination with the intervening atoms, said intervening Optionally substituted 3-10 membered monocyclic or bicyclic having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur And R ⁴ is an optionally substituted phenyl group; and Z is nitrogen, oxygen, and A 5- to 14-membered heteroaryl group having 1 to 4 heteroatoms selected from the group consisting of sulfur is shown. ]

Furthermore, this invention aims at solving the said subject advantageously, and the manufacturing method of the stretched film of this invention uses one of the dicyclopentadiene type ring-opening polymer hydrides mentioned above. It includes a stretching step of stretching the unstretched film formed at a temperature of 95 ° C. or higher and 130 ° C. or lower. According to such a method for producing a stretched film, an unstretched film having both high strength and ductility can be stretched satisfactorily, and a stretched film having excellent performance can be efficiently produced.

Here, it is preferable that the method for producing a stretched film of the present invention further includes a heat setting treatment step of heat-treating the film that has undergone the stretching step at a temperature of 175 ° C. or more and 225 ° C. or less. By carrying out the heat setting treatment step according to the above conditions, physical properties such as dimensional stability of the stretched film obtained can be improved.

ADVANTAGE OF THE INVENTION According to this invention, the dicyclopentadiene type ring-opening polymer hydride which can form the resin molding etc. which were compatible in the level with high intensity | strength and ductility, and its manufacturing method can be provided.
Furthermore, according to the present invention, it is possible to provide a resin film and a resin molded body that are compatible at a high level of strength and ductility.
And according to this invention, the manufacturing method of a stretched film which can manufacture a stretched film satisfactorily can be provided using the resin film in which intensity | strength and ductility were compatible in the high level.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the dicyclopentadiene ring-opening polymer hydride of the present invention is suitably used when preparing a resin film and a resin molded body. In addition, the resin film and the resin molded body of the present invention are characterized by containing the dicyclopentadiene ring-opening polymer hydride of the present invention. Moreover, the dicyclopentadiene ring-opening polymer hydride of the present invention can be favorably produced by the method for producing a dicyclopentadiene ring-opening polymer hydride of the present invention.

(Dicyclopentadiene ring-opening polymer hydride)
The dicyclopentadiene ring-opening polymer hydride of the present invention (hereinafter also simply referred to as “HDDCD polymer”) has a syndiotacticity of 99% or more and a hydrogenation rate of 98.0% or more. It is characterized by. By using the dicyclopentadiene ring-opening polymer hydride of the present invention having a syndiotacticity and a hydrogenation rate that are each equal to or higher than the lower limit, a resin material that has both high strength and ductility can be obtained. Can be formed.

The HDCPD polymer contains a repeating unit derived from dicyclopentadiene (hereinafter also referred to as “repeating unit (1)”). More specifically, the repeating unit (1) can be a repeating unit of hydrogenated dicyclopentadiene represented by the following formula (1).

In the above formula (1), since the carbon represented by (1,4) is an asymmetric carbon (indicated by adding “*” in formula (1)), the dicyclopentadiene ring-opening polymer hydrogen There may be stereoregularity (tacticity) in the compound. The dicyclopentadiene ring-opening polymer hydride of the present invention has syndiotactic stereoregularity.

In the HDCPD polymer of the present invention, the proportion of the repeating unit (1) is preferably 90% by mass or more, preferably 95% by mass or more, based on 100% by mass of all repeating units constituting the HDCPD polymer. More preferably, it is more preferably 97% by mass or more, and particularly preferably 100% by mass. If the ratio of the repeating unit (1) in the HDCPD polymer is not less than the above lower limit, the strength of the obtained resin material and the like can be further increased.

The repeating unit (1) represented by the above formula (1) is derived from dicyclopentadiene. Dicyclopentadiene has two stereoisomers, an endo isomer and an exo isomer, both of which can be used as monomers. In preparing the HDDCD polymer, one of the endo isomer and the exo isomer may be used alone, or an isomer mixture in which the endo isomer and the exo isomer are mixed at an arbitrary ratio can be used. From the viewpoint of increasing the crystallinity of the HDDCD polymer and particularly increasing the strength of the resin material obtained, it is preferable to increase the ratio of one stereoisomer. Specifically, at the time of preparing the HDDCD polymer, it is preferable to use only one of an endo isomer and an exo isomer as dicyclopentadiene, and it is more preferable to use only an endo isomer from the viewpoint of ease of synthesis. In addition, when an isomer mixture of dicyclopentadiene is used at the time of preparing the HDCPD polymer, the total isomer mixture is 100% by mass, and one of the endo isomer and the exo isomer is 90% by mass or more. Is more preferable, it is more preferable that it is 95 mass% or more, and it is especially preferable that it is 99 mass% or more. Furthermore, from the viewpoint of ease of synthesis, it is preferable that the ratio of the endo isomer is higher than the ratio of the exo isomer in the isomer mixture.

Also, when preparing the HDDCD polymer, other cyclic olefin monomers copolymerizable with dicyclopentadiene can be used in combination. The amount of the other cyclic olefin monomer used is preferably 10% by mass or less, more preferably 5% by mass or less, and still more preferably 3% by mass or less, based on 100% by mass of all repeating units constituting the HDCPD polymer. And 0% by mass, that is, the HDCPD polymer preferably contains no other cyclic olefin monomer.

Other cyclic olefin monomers copolymerizable with dicyclopentadiene are not particularly limited, and examples thereof include known cyclic olefin monomers disclosed in International Publication No. 2016/143795.

<Preparation Method of Dicyclopentadiene-Based Ring-Opening Polymer Hydride>
The dicyclopentadiene ring-opening polymer hydride of the present invention is obtained by first ring-opening polymerizing the above-mentioned dicyclopentadiene and any other cyclic olefin monomer to obtain a dicyclopentadiene ring-opening polymer. Thus, the obtained ring-opening polymer can be prepared by hydrogenation.

The ring-opening polymer is not particularly limited, and is prepared by ring-opening polymerization of dicyclopentadiene and any other cyclic olefin monomer as described above using a ring-opening polymerization catalyst. be able to. According to the study by the present inventors, by using a ring-opening polymerization catalyst that can be represented by the following general formula (α) as the ring-opening polymerization catalyst, the dicyclopentadiene-based ring-opening polymer hydride of the present invention can be efficiently produced. It became clear that it could be manufactured. This is presumed to be due to the fact that the skeleton structure defined by the following general formula (α) can satisfactorily form a polymer chain having high syndiotacticity in the ring-opening polymerization of dicyclopentadiene. This is because the ring-opening polymerization catalyst represented by the general formula (α) is an alkylidene ligand, a 5- to 14-membered heteroaryl ligand represented by Z, a phenyl-substituted phenoxy ligand, a terminal oxo coordination. This is thought to be due to the fact that it consists of a child and a phosphorus-containing ligand. Specifically, in the phenyl-substituted phenoxy ligand, the alkoxy group is a substituted phenoxy group, and has a phenyl group at the 2, 3, 5, and 6 positions, and the 2, 3, 5, and 6 positions. It is presumed that when the substituent X of the phenyl group is small, the steric effect on dicyclopentadiene is optimized and stereo error can be suppressed. In addition, since the ring-opening polymerization catalyst has a terminal oxy ligand, a sufficient coordination space for dicyclopentadiene can be secured, and stereo errors can be suppressed.

Halogen atoms that can be X include F, Cl, Br, and I. Especially, when X is a halogen atom, it is preferable that it is Br.
N is preferably 0.

The linear or branched hydrocarbon group having 1 to 6 carbon atoms, which is R ¹ or R ² , is not particularly limited, but is a methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl. A straight chain or branched chain alkyl group having 1 to 6 carbon atoms such as a tert-butyl group, a pentyl group, a hexyl group and an isohexyl group, and a cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group. Can be mentioned. In addition, the cyclic hydrocarbon group having 1 to 6 carbon atoms which can be R ¹ and R ² is not particularly limited, and is a cyclic aliphatic group such as cyclopropyl group, cyclobutyl group, cyclopentyl group, and cyclohexyl group. Hydrocarbon groups; and aromatic hydrocarbon groups such as phenyl groups. Of these, R ¹ and R ² are preferably methyl groups.

Examples of the linear or branched alkyl group having 1 to 12 carbon atoms which may be R ³ include a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, an isobutyl group, a tert-butyl group, a pentyl group, Examples include a hexyl group, a heptyl group, an octyl group, and a nonyl group. Among them, it is preferable that R ³ is a methyl group.
Other examples of the group that may be R ³ include various groups listed as the group “R” in International Publication No. 2015/127192 (for example, International Publication No. 2015/127192, paragraph). See 0201-0222). Further, among these groups, examples of the substituent bonded to the substitutable carbon atom of the optionally substituted group include various substituents described in International Publication No. 2015/127192 ( For example, see International Publication No. 2015/127192, paragraphs 0058-0064).

In the 5- to 14-membered heteroaryl group that is Z, it is preferable that at least one heteroatom is N. Further, it is more preferable that Z is bonded to W through at least one nitrogen atom. For example, Z may be a group represented by any one of the following general formulas (Z-1) to (Z-6). Here, Z is a 5-membered heteroaryl having 1 to 4 heteroatoms independently selected from N, O and S, and it is particularly preferred that at least one heteroatom is nitrogen. . Among them, Z is preferably a group represented by the following formula (Z-1), (Z-2), (Z-3), or (Z-6), and is represented by the following formula (Z-6). Particularly preferred is a group. Z is 5-membered heteroaryl, at least one heteroatom is nitrogen, and the substituents at the 2- and 5-positions are a hydrogen atom or a methyl group, thereby stabilizing the catalyst structure and reducing stereo errors. Become.

The ring-opening polymerization catalyst represented by the above formula (α) is not particularly limited. For example, International Publication No. 2015/127192, International Publication No. 2016/14311, Benjamin Autenrieth et al., “Stereospecific Ring-Opening に従って Metathesis Polymerization (ROMP) of endo-Dicyclopentadiene by Molybdenum and Tungsten Catalysts ”, Macromolecules, 2015, 48, p. 2480-2492.

In the ring-opening polymerization, the amount of the ring-opening polymerization catalyst used is preferably 0.01 parts by mass or more and 0.50 parts by mass or less with respect to 100 parts by mass of the monomer containing dicyclopentadiene. It is more preferable that the content be 0.05 parts by mass or more and 0.30 parts by mass or less. By making the usage-amount of a catalyst into the said range, ring-opening polymerization reaction can fully be accelerated | stimulated. The polymerization time is usually from 1 minute to 100 hours, preferably from 30 minutes to 5 hours. Furthermore, the polymerization temperature can usually be −30 ° C. or higher and 200 ° C. or lower, preferably 0 ° C. or higher and 180 ° C. or lower.
In addition, in the ring-opening polymerization, a known molecular weight regulator that can be a vinyl group-containing compound such as 1-hexene can be added in a general blending amount.

The ring-opening polymerization reaction can be performed in a solvent-free system, but is preferably performed in an organic solvent. The organic solvent is not particularly limited as long as it can dissolve or disperse the dicyclopentadiene-based ring-opening polymer obtained by the ring-opening polymerization reaction and does not adversely affect the ring-opening polymerization reaction. And any organic solvent can be used. For example, organic solvents include aliphatic hydrocarbons such as pentane, hexane, heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, Hexahydroindene cyclohexane, cyclooctane and other alicyclic hydrocarbons; benzene, toluene, xylene and other aromatic hydrocarbons; dichloromethane, chloroform, 1,2-dichloroethane and other halogenated aliphatic hydrocarbons; chlorobenzene, dichlorobenzene, etc. Halogen-containing aromatic hydrocarbons; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; aniso , And aromatic ethers such as phenetole. These can be used singly or as a mixture of two or more. Among these, aromatic hydrocarbons, aliphatic hydrocarbons, alicyclic hydrocarbons, ethers, and aromatic ethers are preferable, and aromatic hydrocarbons are more preferable.

Here, the weight average molecular weight (Mw) of the obtained dicyclopentadiene-based ring-opening polymer is not particularly limited, but is usually 10,000 to 1,000,000, preferably 10,000 to 500,000. . Such a polymer having a weight average molecular weight is preferably used as a material for various resin moldings.
The molecular weight distribution (Mw / Mn) of the dicyclopentadiene-based ring-opening polymer is not particularly limited, but is usually 4.0 or less, preferably 3.5 or less. A hydride obtained by subjecting a polymer having such a molecular weight distribution to a hydrogenation reaction described later is excellent in molding processability.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of the dicyclopentadiene ring-opening polymer are standard polystyrene conversion values measured by gel permeation chromatography (GPC) using tetrahydrofuran as a developing solvent. is there.

Then, the obtained ring-opening polymer is subjected to a hydrogenation reaction. The hydrogenation reaction can be performed by adding (a) a hydrogenating agent as a hydrogen source to the system in which the dicyclopentadiene-based ring-opening polymer is present, and then heating and reacting, or (b) adding a hydrogenation catalyst. Then, hydrogen gas can be added as a hydrogen source to hydrogenate unsaturated bonds present in the dicyclopentadiene-based ring-opening polymer. Among these, it is preferable to employ the hydrogenation method (b) from the viewpoint of industrial production. In other words, it is preferable to perform a hydrogenation reaction of the dicyclopentadiene ring-opening polymer using a hydrogenation catalyst and hydrogen gas.

The method (a) includes a hydrazine-containing compound known as a hydrogenating agent (hydrogen source) for a hydrogen transfer hydrogenation reaction, and is included in a dicyclopentadiene-based ring-opening polymer. The method of hydrogenating an unsaturated bond is mentioned. The hydrogenating agent is not particularly limited, and examples thereof include hydrazine and paratoluenesulfonyl hydrazide. Among them, paratoluenesulfonyl hydrazide is preferable.

As the hydrogenation catalyst used in the method (b), a conventionally known hydrogenation catalyst for a ring-opening polymer can be used. Specific examples thereof include RuHCl (CO) (PPh ₃ ) ₃ , RuHCl (CO) [P (p-Me-Ph) ₃ ] ₃ , RuHCl (CO) (PCy ₃ ) ₂ , RuHCl (CO) [P ( n-Bu) ₃ ] ₃ , RuHCl (CO) [P (i-Pr) ₃ ] ₂ , RuH ₂ (CO) (PPh ₃ ) ₃ , RuH ₂ (CO) [P (p-Me-Ph) ₃ ] ₃ , RuH ₂ (CO) (PCy ₃ ) ₃ , RuH ₂ (CO) [P (n-Bu) ₃ ] ₃ RuH (OCOCH ₃ ) (CO) (PPh ₃ ) ₂ , RuH (OCOPh) (CO) (CO) ( PPh ₃ ) ₂ , RuH (OCOPh-CH ₃ ) (CO) (PPh ₃ ) ₂ , RuH (OCOPh-OCH ₃ ) (CO) (PPh ₃ ) ₂ , RuH (OCOPh) (CO) (PCy ₃ ) ₂ , Raneynicke , Nickel diatomaceous earth, nickel acetate, palladium acetate, PdCl ₂ , RhCl (PPh) _{3 and the} like. Among these, carbonylchlorohydridotris (triphenylphosphine) ruthenium [RuHCl (CO) (PPh ₃ ) ₃ ] is preferable.

The hydrogenation reaction is usually performed in an inert organic solvent. Examples of inert organic solvents that can be used include cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindenecyclohexane, and cyclooctane. Alicyclic hydrocarbons; Aromatic hydrocarbons such as benzene, toluene and xylene; Halogenous aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; Halogenous aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; Diethyl And ethers such as ether and tetrahydrofuran; aromatic ethers such as anisole and phenetole; and the like. These can be used singly or as a mixture of two or more. Of these, alicyclic hydrocarbons and aromatic hydrocarbons are preferred.

Moreover, hydrogenation reaction conditions, such as hydrogenation reaction temperature, can be suitably set according to the hydrogenating agent to be used and a hydrogenation catalyst. For example, the hydrogenation reaction temperature is usually −20 ° C. or higher and 250 ° C. or lower, preferably 50 ° C. or higher and 220 ° C. or lower, more preferably 100 ° C. or higher and 200 ° C. or lower, and further preferably 160 ° C. or higher and 200 ° C. or lower. If the hydrogenation temperature is too low, the reaction rate may be too slow, and if it is too high, the side reaction may occur and the hydrogenation rate may be reduced. Moreover, the hydrogenation rate of the HDDCD polymer obtained can be made into a desired value by adjusting the hydrogenation temperature within an appropriate range.
In particular, in the case of the hydrogenation method according to the above (b), the hydrogen pressure can be usually 0.01 to 20 MPa, preferably 0.05 to 15 MPa, more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may be too slow, and if it is too high, there will be restrictions on the apparatus in that a high pressure reactor is required.
Furthermore, the hydrogenation reaction time is not particularly limited as long as the desired hydrogenation rate can be obtained, but it can usually be 0.1 to 10 hours.
And after the hydrogenation reaction according to arbitrary methods is complete | finished, what is necessary is just to collect | recover dicyclopentadiene type ring-opening polymer hydrides according to a conventional method. In the recovery of the dicyclopentadiene ring-opening polymer hydride, the catalyst residue can be removed by a known method such as centrifugation and filtration.

<Hydrogenation rate of HDPDD polymer>
The dicyclopentadiene ring-opening polymer hydride of the present invention must have a hydrogenation rate of 98.0% or more, preferably 99.0% or more, and preferably 99.2% or more. More preferred. If a hydrogenation rate is more than the said lower limit, the intensity | strength and reflow tolerance of the resin material obtained can be improved further. Here, “reflow resistance” means resistance when the printed circuit board material is heated according to a reflow method commonly used when soldering a component to a printed circuit board or the like. The temperature profile of heating according to the reflow method is defined, for example, in J-STD-020C. In addition, a hydrogenation rate shows the ratio of the hydrogenated unsaturated bond among all the unsaturated bonds contained in the principal chain and side chain of the dicyclopentadiene ring-opening polymer hydride. Further, the hydrogenation rate is a value based on ¹ H-NMR measurement, and is a value on a molar basis.

<Syndiotacticity of HDPDD polymer>
The dicyclopentadiene ring-opening polymer hydride of the present invention needs to have a syndiotacticity of 99% or more. Here, syndiotacticity is the ratio of racemodyad to the total abundance of isotactic dyad (mesodyad) and racemodyad present in the polymer chain having stereoregularity (hereinafter simply referred to as “racemodyad ratio”). May be referred to). In particular, the dicyclopentadiene ring-opening polymer hydride of the present invention preferably has a syndiotacticity of 99.5% or more, more preferably 100%. If the syndiotacticity is at least the above lower limit, the crystallinity of the dicyclopentadiene ring-opening polymer hydride is sufficiently high, and the strength of the resulting resin material and the like can be sufficiently increased. The syndiotacticity is a value based on ¹³ C-NMR measurement, and is a value on a molar basis.

Here, in the present invention, the syndiotacticity of the dicyclopentadiene-based ring-opening polymer hydride is adjusted as appropriate using the specific catalyst as described above, and various conditions during polymerization, including polymerization time and polymerization temperature. By doing so, it can be increased to a desired value.

<Glass transition temperature of HDPDD polymer>
The glass transition temperature of the dicyclopentadiene ring-opening polymer hydride of the present invention is preferably 80 ° C. or higher, more preferably 90 ° C. or higher. If the glass transition temperature of the dicyclopentadiene ring-opening polymer hydride is within such a range, the heat resistance is good, and, for example, the load deflection temperature of the resulting resin molded article is high, which is preferable. The upper limit of the glass transition point is not particularly limited, but is approximately 120 ° C.

<Melting point of HDPDD polymer>
The melting point of the dicyclopentadiene ring-opening polymer hydride of the present invention is preferably 260 ° C. or higher and 300 ° C. or lower, more preferably 266 ° C. or higher and 295 ° C. or lower, and 270 ° C. or higher and 290 ° C. or lower. It is particularly preferred. If the melting point of the HDCPD polymer is not less than the above lower limit, a resin material having excellent heat resistance can be provided. Moreover, if the melting point of the HDCPD polymer is not more than the above upper limit, there is no need to excessively increase the processing temperature when processing the obtained resin material, and deterioration of the resin material due to an excessively high processing temperature is eliminated. It can be avoided.

(Resin material)
The resin material containing the above-described dicyclopentadiene ring-opening polymer hydride of the present invention has both high strength and ductility. In addition to the dicyclopentadiene ring-opening polymer hydride of the present invention, the resin material may contain an optional component. Examples of such optional components include, but are not limited to, inorganic fillers disclosed in International Publication No. 2016/143795, antioxidants, ultraviolet absorbers, light stabilizers, near infrared absorbers, plastics, and the like. And additives such as an agent, an antistatic agent, an acid scavenger, a flame retardant, and a flame retardant aid.

The blending amount of the inorganic filler and additive can be arbitrarily set according to the purpose. For example, the compounding amount of the inorganic filler may be 5 parts by mass or more and 200 parts by mass or less with respect to 100 parts by mass of the dicyclopentadiene ring-opening polymer hydride of the present invention. Moreover, the compounding quantity of an additive may be 0.01 mass part or more and 10 mass parts or less with respect to 100 mass parts of dicyclopentadiene type ring-opening polymer hydrides of this invention. In other words, the content ratio of the dicyclopentadiene-based ring-opening polymer hydride of the present invention in the resin material may be 30% by mass or more, based on 100% by mass of the entire resin material. Of course, the resin material does not contain an optional component, and substantially 100% by mass may be constituted by the dicyclopentadiene ring-opening polymer hydride of the present invention. In the present specification, “substantially 100% by mass” can contain, for example, 0.05% by mass or less of inevitable impurities such as a polymerization solvent that can be mixed due to the purification limit during production. Means that.

The resin material is not particularly limited, and can be prepared, for example, by mixing the hydride of the dicyclopentadiene-based ring-opening polymer of the present invention obtained as described above and an arbitrary component. More specifically, in mixing, the HDDCD polymer and optional components may be kneaded in a molten state. The kneading can be performed using a melt kneader such as a single screw extruder, a twin screw extruder, a Banbury mixer, a kneader, or a feeder ruder. The kneading temperature is preferably in the range of 250 ° C to 400 ° C, more preferably 260 ° C to 350 ° C. In kneading, the components may be added together and kneaded, or may be kneaded while adding in several times. Then, after kneading, the obtained kneaded material is extruded into a rod shape according to a conventional method, and cut into an appropriate length with a strand cutter, whereby a pelletized resin material can be obtained.

(Resin molding)
The resin molding of the present invention contains the above-described hydrogenated dicyclopentadiene ring-opening polymer of the present invention. Since the resin molded product of the present invention contains the dicyclopentadiene ring-opening polymer hydride of the present invention, both strength and ductility are at high levels. The resin molded body may be a molded product formed by molding the above-described resin material into an arbitrary shape. Therefore, the resin molded body may also contain various optional components that can be blended in the resin material in the above-described proportions. Further, the resin molded body may be composed of 30% by mass or more of the dicyclopentadiene ring-opening polymer hydride of the present invention, with the total mass of the resin molded body being 100% by mass. No component is contained, and substantially 100% by mass may be constituted by the dicyclopentadiene ring-opening polymer hydride of the present invention.

As a molding method for forming the resin molded body, a melt molding method is preferable. Examples of the melt molding method include extrusion molding methods, injection molding methods, melt spinning molding methods, press molding methods, blow molding methods, and calendar molding methods. The molding method can be appropriately selected according to the shape of the target resin molding.

(Resin film)
The resin film of the present invention contains the dicyclopentadiene ring-opening polymer hydride of the present invention described above. The resin film of the present invention is a kind of the above-described resin molded body of the present invention and contains the hydrogenated dicyclopentadiene ring-opening polymer of the present invention, so that both strength and ductility are at a high level. The resin film of the present invention may be a molded product formed by molding the above-described resin material into a film shape. Therefore, the resin film may also contain various optional components that can be blended in the resin material in the above-described proportions. Further, the resin film may be composed of 100% by mass of the total mass of the resin film, and 30% by mass or more of the hydride of the dicyclopentadiene ring-opening polymer of the present invention. Not contained, and substantially 100% by mass may be constituted by the dicyclopentadiene ring-opening polymer hydride of the present invention.

An example of the melt molding method that can be suitably used for producing a resin film that is a kind of resin molded body is an extrusion molding method. When producing a resin film by an extrusion method, a known method can be used as appropriate. For example, the resin material is put into an extruder, melted and kneaded, and then a molten resin is continuously extruded into a film form from a T die connected to the extruder, and then cooled to obtain a resin film. it can.

<Gas generation amount of resin film>
In the resin film of the present invention, the amount of a gas attributed to a mass number of 18 (m / z) generated between room temperature and 300 ° C. measured by heat generation gas mass spectrometry is 100% of the mass of the resin film. The mass% is preferably less than 0.5 mass%. Here, the gas belonging to the mass number 18 (m / z) is specifically H ₂ O. If the gas generation amount of the resin film is less than the above upper limit, the amount of moisture that can be released when heated when the resin film is used in a desired application is sufficiently small. High suitability. Note that H ₂ O generated from the film during the measurement is mainly moisture adsorbed on the film.

The thickness of the resin film is not particularly limited, but is usually 1 to 300 μm, preferably 2 to 200 μm.

The resin film obtained by molding may be subjected to a known stretching process or a heat setting process as described in International Publication No. 2016/143795.
By performing the stretching treatment, a resin film having a high degree of crystallinity and superior strength can be obtained. Moreover, the resin film with a small heat shrinkage rate is obtained by performing a heat setting process.

Furthermore, the laminated film which laminated | stacked the metal layer on the both surfaces or single side | surface of this invention by the well-known method can be used suitably as a flexible printed circuit board material. As a method for producing a laminated film, a method in which a resin film and a metal foil for forming a metal layer are hot-pressed and heated to a temperature close to the melting point of the resin film, and a resin film and a metal layer are formed. For example, a method of adhering a metal foil to the resin film via an adhesive layer, and a method of forming a metal layer on both sides or one side of the resin film by sputtering or plating the resin film.
As a metal layer, the layer containing metals, such as copper, gold | metal | money, silver, aluminum, nickel, and chromium, is mentioned. Among these, copper is preferable because a laminated film useful as a flexible printed circuit board material can be obtained. The adhesive layer can be formed of a commercially available adhesive sheet such as an epoxy film.

The thickness of the metal layer is not particularly limited and can be appropriately determined according to the purpose of use of the laminated film. The thickness of the metal layer is usually 1 to 35 μm, preferably 3 to 18 μm.

(Method for producing stretched film)
The method for producing a stretched film of the present invention includes a stretching step of stretching an unstretched film formed using the dicyclopentadiene ring-opening polymer hydride according to the present invention at a temperature of 95 ° C. or higher and 130 ° C. or lower. It is characterized by. The “unstretched film” refers to the above-described resin film of the present invention that has not been stretched. Furthermore, it is preferable that the manufacturing method of the stretched film of this invention further includes the heat setting process process. Hereinafter, each process is explained in full detail.

<Extension process>
In the stretching step, the predetermined unstretched film is stretched at a temperature of 95 ° C. or higher and 130 ° C. or lower. Here, the dicyclopentadiene ring-opening polymer hydride of the present invention has both high levels of syndiotacticity and hydrogenation rate. Such an unstretched film formed using the dicyclopentadiene-based ring-opening polymer hydride of the present invention has high crystallinity and high strength, while being prone to haze when subjected to a stretching treatment according to a conventional method, A stretched film with high transparency could not be obtained. Therefore, as a result of intensive studies by the present inventors, by setting the temperature during the stretching treatment to 95 ° C. or higher and 130 ° C. or lower, the haze value (ie, haze) of the stretched film is prevented from becoming excessively high. However, it was revealed that an unstretched film can be stretched satisfactorily. More specifically, by setting the temperature during the stretching treatment to 95 ° C. or higher, the unstretched film is too hard at the time of stretching and it is difficult to stretch and the film is prevented from breaking, and the productivity is deteriorated. Can be suppressed. In addition, by setting the temperature during the stretching treatment to 130 ° C. or lower, it is possible to suppress the occurrence of haze in the film obtained through the stretching process and to suppress the resulting film from being easily thermally expanded. be able to. Furthermore, from the viewpoint of further enhancing these effects relating to haze and thermal expansion, the temperature during the stretching treatment is preferably 125 ° C. or less, and more preferably 115 ° C. or less. Note that whether or not the film is likely to thermally expand can be quantitatively expressed by a linear expansion coefficient. The linear expansion coefficient is represented by a rate (unit: ppm / ° C.) in which the length changes with a temperature change of 1 ° C.

The stretching process is not particularly limited and can be performed according to a known method. Specifically, a uniaxial stretching method such as a method of uniaxially stretching in the longitudinal direction using a difference in peripheral speed between rolls and a method of uniaxially stretching in the transverse direction using a tenter stretching machine; Simultaneously stretching in the longitudinal direction using the simultaneous biaxial stretching method that stretches in the transverse direction according to the spread angle of the guide rail, and the difference in peripheral speed between the rolls, and then extending both ends of the longitudinal direction. A biaxial stretching method such as a sequential biaxial stretching method in which a clip is gripped and stretched in the lateral direction using a tenter stretching machine; and a feed force, a pulling force, or a pulling force at different speeds can be applied in the lateral or longitudinal direction. Examples thereof include a method of continuously and obliquely stretching in the direction of an arbitrary angle θ with respect to the width direction of the film using the tenter stretching machine. Among these, the biaxial stretching method is preferable.

Further, the draw ratio in the drawing step is preferably 1.2 times or more, more preferably 1.5 times or more, preferably 10 times or less, and more preferably 5 times or less. If a draw ratio is more than the said lower limit, it can suppress that the film obtained becomes easy to thermally expand too much. Moreover, if a draw ratio is below the said upper limit, generation | occurrence | production of a haze can be suppressed. When various biaxial stretching methods are employed as the stretching method, the stretching ratio is defined by the product of the vertical and horizontal stretching ratios.

Further, the stretching speed in the stretching step is preferably adjusted according to the stretching temperature. More specifically, since the progress of crystallization is promoted in the film as the stretching temperature increases, it is preferable to increase the stretching speed from the viewpoint of performing the stretching step efficiently and satisfactorily.

<Heat setting process>
In the heat setting treatment step, the film that has undergone the stretching step is heat-treated at a temperature of 175 ° C. or more and 225 ° C. or less. By subjecting the film that has undergone the stretching process to heat setting treatment, the film obtained through the heat setting process step is more likely to thermally expand, and the generation of haze in the film is more effectively suppressed. Can do. In particular, the fact that the film is difficult to thermally expand means that the dimensional stability of the film is high. Furthermore, the heat setting temperature in the heat setting treatment step is preferably 190 ° C. or higher, and more preferably 205 ° C. or higher, from the viewpoint of further favorably suppressing the film from being easily thermally expanded.

The heat treatment method in this step is not particularly limited, and examples thereof include blowing hot air into a heat treatment oven and heating by radiant heat using a heat source such as an infrared heater.

The heat treatment time (heat setting time) in this step is preferably 10 seconds or more, more preferably 20 seconds or more, preferably 10 minutes or less, more preferably 5 minutes or less, and even more preferably 2 minutes or less. In particular, if the heat setting time is not more than the above upper limit, it is possible to more effectively suppress the occurrence of haze in the obtained film.

EXAMPLES Hereinafter, although this invention is demonstrated concretely based on an Example, this invention is not limited to these Examples. In the following description, “%” and “part” representing amounts are based on mass unless otherwise specified. The pressure is a gauge pressure.
Measurement and evaluation in each example were performed by the following methods.

<Weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) of ring-opening polymer>
Gel permeation chromatography (GPC) was performed at 40 ° C. using tetrahydrofuran as a solvent, and the weight average molecular weight (Mw), number average molecular weight (Mn), and molecular weight distribution (Mw / Mn) were determined as polystyrene equivalent values. .
Measuring device: Gel permeation chromatography (GPC) system “HLC-8320” (manufactured by Tosoh Corporation)
Column: “H type column” (manufactured by Tosoh Corporation)

<Melting point of HDPDD polymer>
Using a differential scanning calorimeter (DSC), differential scanning calorimetry was carried out at a temperature rising rate of 10 ° C./min, and the melting point of the HDCPD polymer was measured.

<Hydrogenation rate of HDPDD polymer>
^{Based on the 1} H-NMR measurement, the hydrogenation rate of the unsaturated bond in the HDCPD polymer was determined.

<Syndiotacticity of HDPDD polymer>
By applying the inverse-gate decoupling method at 200 ° C. using ortho-dichlorobenzene-d ₄ / 1,2,4-trichlorobenzene (TCB) -d ₃ (mixing ratio (mass basis) 1/2) as a solvent, ¹³ C -NMR measurement was performed to determine the ratio of racemodyad of dicyclopentadiene ring-opening polymer hydride. Specifically, based shift the peak of 127.5ppm orthodichlorobenzene -d _4, a signal 43.35ppm from meso-diad, based on the intensity ratio of signals 43.43ppm from Rasemodaiaddo, Rasemodaiaddo The ratio (%) was obtained.

<Strength and ductility of resin film (non-stretched film and stretched film)>
The unstretched films obtained in Examples 1 to 9 and Comparative Examples 1 and 2 and the stretched films obtained in Examples 10 to 15 were formed in the MD direction (MD in the shape of test piece type 1B of JIS K7127: 1999 standard). : Machine Direction) to produce a sample for a tensile test. The obtained sample was subjected to a tensile test with a universal material testing machine (“Instron”, Model 5582) at a test speed of 100 m / min, and tensile strength (strength) and elongation at break (ductility) were measured. The test result was an average value of 5 samples.

<Reflow resistance of resin film>
The stretched films, which are the resin films obtained in Examples 1 to 9 and Comparative Examples 1 and 2, were cut out at 5 cm square and a 0.8 mm thick copper-clad laminate (manufactured by Panasonic Corporation, “R- 1766 ") and affixed four sides with polyimide tape to obtain a test piece. Appearance of the test piece after putting it in a small reflow furnace (manufactured by Antom, “HAS-6116H”) according to J-STD-020C and setting the peak temperature at 260 ° C. Was visually evaluated. Evaluation was performed on three test pieces for each example, and evaluation was performed according to the following criteria.
A: There is no deformation in any of the three test pieces.
B: There are deformations in 1 to 2 test pieces.
C: All three specimens are deformed.

<Gas generation amount of resin film>
0.5 mg of the stretched film, which is the resin film obtained in Examples 1 to 9 and Comparative Examples 1 and 2, was allowed to stand in a constant temperature and humidity chamber at 23 ° C. and 60% humidity for 24 hours or more, and then weighed. Thus, an initial mass W0 was obtained. Then, the stretched film was analyzed from a room temperature to 300 ° C. at a temperature rising rate of 10 ° C./min under a helium stream with a heat generation gas mass spectrometer (temperature desorption gas analyzer). When the initial mass of the resin film was 100% by mass, the proportion of the component having a mass number of 18 (m / z) derived from water was calculated and evaluated according to the following criteria.
A: Less than 0.5% by mass B: 0.5% by mass or more

<Haze (cloudiness)>
A 50 mm × 50 mm square thin film sample was cut out from the stretched films obtained in Examples 10 to 15, and the haze (Nippon Denshoku Industries Co., Ltd., “NDH5000”) was used to measure the haze (scattered light / total light transmission). Light x 100 (%)) value was obtained.

<Linear expansion coefficient>
A rectangular thin film sample of MD (Machine Direction) direction 20 mm × TD (Transverse Direction) direction 4 mm was cut out from the stretched films obtained in Examples 10 to 15, and then TMA (manufactured by Hitachi High-Tech Science Corporation, “TMASS7100”) was used. The linear expansion coefficients (ppm / ° C. = μm / ° C./m) were measured in the temperature ranges of 40 ° C. to 80 ° C. and 120 ° C. to 160 ° C., respectively.

(Example 1)
<Preparation of dicyclopentadiene-based ring-opening polymer>
In a metal pressure-resistant reaction vessel purged with nitrogen inside, 344 parts of toluene, 286 parts of a toluene solution (concentration 35% or more) of dicyclopentadiene (end content 99% or more) (100 parts as dicyclopentadiene), 1-hexene 8 parts were added and the whole was heated to 35 ° C.
On the other hand, polymerization catalyst Nos. A catalyst solution was prepared by dissolving 0.086 parts of the tungsten complex, which is the ring-opening polymerization catalyst represented by 1, in 29 parts of toluene. This catalyst solution was added to the reactor and a ring-opening polymerization reaction was performed at 35 ° C. for 1 hour to obtain a solution containing a dicyclopentadiene-based ring-opening polymer. In Table 2, “Me” represents a methyl group.

To 667 parts of the solution containing the obtained dicyclopentadiene ring-opening polymer, 1.1 parts of 2-propanol was added as a terminator to stop the polymerization reaction.
A part of this solution was used to measure the molecular weight of the dicyclopentadiene-based ring-opening polymer. The weight average molecular weight (Mw) was 24,600, the number average molecular weight (Mn) was 8,600, and the molecular weight distribution (Mw / Mn) was 2.86.

<Hydrogenation of ring-opening polymer>
After the resulting reaction solution containing the dicyclopentadiene-based ring-opening polymer was transferred to a metal pressure vessel equipped with a stirrer and a temperature control jacket, 330 parts of toluene, carbonylchlorohydridotris (triphenylphosphine) as a hydrogenation catalyst ) 0.027 part of ruthenium was added. Next, while stirring the whole volume at a rotational speed of 64 rpm, the temperature was increased to 120 MPa at a hydrogen pressure of 2.0 MPa, further increased to 4.0 MPa at 0.03 MPa / min, and increased to 180 ° C. at 1 ° C./min. Then, a hydrogenation reaction was performed for 6 hours. The reaction liquid after cooling was a slurry liquid in which a solid content was deposited.
The reaction solution was centrifuged to separate the solid content and the solution, and the solid content was dried under reduced pressure at 120 ° C. for 24 hours to obtain 90 parts of a dicyclopentadiene ring-opening polymer hydride.
The hydrogenation rate of the obtained dicyclopentadiene ring-opening polymer hydride was 99.5%, the melting point was 276 ° C., and the ratio of racemodyad (ie, syndiotacticity) was 100%. Moreover, it confirmed that the glass transition temperature of the obtained dicyclopentadiene type ring-opening polymer hydride was 90 degreeC or more and 120 degrees C or less using the differential scanning calorimeter (DSC).

<Preparation of resin material>
20 parts of the dicyclopentadiene ring-opening polymer hydride obtained as described above was added with an antioxidant (tetrakis [methylene-3- (3 ′, 5′-di-t-butyl-4′-hydroxyphenyl). ) Propionate] After mixing 0.16 parts of methane, product name “Irganox (registered trademark) 1010” (manufactured by BASF Japan), the mixture was put into a twin screw extruder (TEM-37B, manufactured by Toshiba Machine Co., Ltd.). A strand-like molded body was obtained by hot melt extrusion molding. Thereafter, the strand-shaped molded body was chopped with a strand cutter to obtain pellets which are resin materials containing a dicyclopentadiene ring-opening polymer hydride.
The operating conditions of the twin screw extruder are shown below.
・ Barrel set temperature: 280 ~ 290 ℃
・ Die setting temperature: 260 ℃
・ Screw speed: 145rpm
・ Feeder rotation speed: 50 rpm

<Manufacture of resin film (non-stretched)>
The resin material (pellet) obtained in accordance with the above was formed into a film having a width of 130 mm using a hot melt extrusion film forming machine (manufactured by Optical Control Systems, product name “Measuring Extruder Type Me-20 / 2800V3”) equipped with a T-die. Was wound on a roll at a speed of 1 m / min to obtain an unstretched film which is a resin film containing a hydrogenated dicyclopentadiene ring-opening polymer having a thickness of 100 μm.
The operating conditions of the film forming machine are shown below.
・ Barrel temperature setting: 290 ℃ ～ 300 ℃
-Die temperature: 280 ° C
-Screw rotation speed: 35rpm

<Manufacture of resin film (stretched)>
A resin film (non-stretched film) obtained in accordance with the above is cut into a 120 mm square, and simultaneously biaxially stretched and heat-fixed with a multi-tank biaxially stretched birefringence-orientation axis measuring device (manufactured by Saito) Thus, a stretched film of a dicyclopentadiene ring-opening polymer hydride, which is a resin film containing a 25 μm thick dicyclopentadiene ring-opening polymer hydride, was obtained.
The operating conditions of the multi-tank biaxial stretching birefringence orientation axis measuring device are shown below.
-Stretching speed: 15mm / sec
-Stretching temperature: 130 ° C
-Stretch ratio: MD (Machine Direction) direction double, TD (Transverse Direction) direction double-Heat setting temperature: 220 ° C
・ Heat setting time: 60 seconds

(Example 2)
<Hydrogenation of ring-opening polymer> In the same manner as in Example 1 except that the hydrogenation reaction in the step was performed at 185 ° C., 27.2 parts of a dicyclopentadiene-based ring-opening polymer hydride was obtained.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99.2%, the melting point was 272 ° C., and the ratio (syndiotacticity) of racemodyad was 100%. Moreover, it confirmed that the glass transition temperature of the obtained dicyclopentadiene type ring-opening polymer hydride was 90 degreeC or more and 120 degrees C or less using the differential scanning calorimeter (DSC).
The obtained dicyclopentadiene ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain dicyclopentadiene ring-opening polymer hydride pellets, an unstretched film, and a stretched film. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 3)
<Hydrogenation of ring-opening polymer> Step 26.9 parts of a dicyclopentadiene-based ring-opening polymer hydride was obtained in the same manner as in Example 1 except that the hydrogenation reaction was performed at 190 ° C.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 98.6%, the melting point was 269 ° C., and the ratio of racemodyad (syndiotacticity) was 100%. Moreover, it confirmed that the glass transition temperature of the obtained dicyclopentadiene type ring-opening polymer hydride was 90 degreeC or more and 120 degrees C or less using the differential scanning calorimeter (DSC).
The obtained dicyclopentadiene ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain dicyclopentadiene ring-opening polymer hydride pellets, an unstretched film, and a stretched film. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 4
<Preparation of dicyclopentadiene-based ring-opening polymer> In the step, except that the ring-opening polymerization reaction was performed at 25 ° C. for 5 hours, a solution containing the dicyclopentadiene-based ring-opening polymer was performed in the same manner as in Example 1. Got. A part of this solution was used to measure the molecular weight of the dicyclopentadiene-based ring-opening polymer. The weight average molecular weight (Mw) was 23,600, the number average molecular weight (Mn) was 8,700, and the molecular weight distribution (Mw / Mn) was 2.71. Similarly, the subsequent steps were performed to obtain 26.9 parts of a dicyclopentadiene ring-opening polymer hydride. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99.4%, the melting point was 276 ° C., and the ratio of racemodyad (syndiotacticity) was 100%. Moreover, it confirmed that the glass transition temperature of the obtained dicyclopentadiene type ring-opening polymer hydride was 90 degreeC or more and 120 degrees C or less using the differential scanning calorimeter (DSC).
The obtained dicyclopentadiene ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain dicyclopentadiene ring-opening polymer hydride pellets, an unstretched film, and a stretched film. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 5)
<Preparation of dicyclopentadiene-based ring-opening polymer> In the step, except that the ring-opening polymerization reaction was performed at 80 ° C. for 1 hour, a solution containing the dicyclopentadiene-based ring-opening polymer was performed in the same manner as in Example 1. Got. A portion of this solution was used to measure the molecular weight of the dicyclopentadiene-based ring-opening polymer. The weight average molecular weight (Mw) was 26,100, the number average molecular weight (Mn) was 8,100, and the molecular weight distribution (Mw / Mn) was 3.22. Similarly, the subsequent steps were performed to obtain 26.9 parts of a dicyclopentadiene ring-opening polymer hydride. The hydrogenation rate of the dicyclopentadiene-based ring-opening polymer hydride was 99.5%, the melting point was 276 ° C., and the ratio of racemodyad (syndiotacticity) was 100%. Moreover, it confirmed that the glass transition temperature of the obtained dicyclopentadiene type ring-opening polymer hydride was 90 degreeC or more and 120 degrees C or less using the differential scanning calorimeter (DSC).
The obtained dicyclopentadiene ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain dicyclopentadiene ring-opening polymer hydride pellets, an unstretched film, and a stretched film. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 6)
<Preparation of dicyclopentadiene-based ring-opening polymer> In the step, polymerization catalyst No. 1 shown in Table 2 was prepared. Except that the ring-opening polymerization reaction was carried out using 0.100 part of the tungsten complex of 2, a solution containing a dicyclopentadiene-based ring-opening polymer was obtained in the same manner as in Example 1. A portion of this solution was used to measure the molecular weight of the dicyclopentadiene-based ring-opening polymer. The weight average molecular weight (Mw) was 24,300, the number average molecular weight (Mn) was 8,200, and the molecular weight distribution (Mw / Mn) was 2.96. The obtained solution was mixed with 2000 parts of 2-propanol, solidified, filtered and dried to obtain 99 parts of a dicyclopentadiene ring-opening polymer.

<Hydrogenation of ring-opening polymer>
In a glass flask, 30.0 parts of a dicyclopentadiene-based ring-opening polymer, 170 parts of paratoluenesulfonyl hydrazide as a hydrogenating agent, and 600 parts of paraxylene are mixed and heated to 120 ° C. in a dry nitrogen atmosphere. Warmed and allowed to react for 4 hours. The reaction liquid was a slurry liquid in which a solid content was deposited. The reaction solution was centrifuged to separate the solid and the solution, and the solid was dried under reduced pressure at 60 ° C. for 24 hours to obtain 27.0 parts of a dicyclopentadiene ring-opening polymer hydride.
The hydrogenation rate of the obtained dicyclopentadiene ring-opening polymer hydride was 99.4%, the melting point was 284 ° C., and the ratio of racemodyad (syndiotacticity) was 100%. Moreover, it confirmed that the glass transition temperature of the obtained dicyclopentadiene type ring-opening polymer hydride was 90 degreeC or more and 120 degrees C or less using the differential scanning calorimeter (DSC).
The obtained dicyclopentadiene ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain dicyclopentadiene ring-opening polymer hydride pellets, an unstretched film, and a stretched film. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 7)
Polymerization catalyst no. 3 was carried out in the same manner as in Example 6 except that 0.100 part of the tungsten complex 3 was used to obtain a solution containing a dicyclopentadiene ring-opening polymer. A part of this solution was used to measure the molecular weight of the dicyclopentadiene-based ring-opening polymer. The weight average molecular weight (Mw) was 25,000, the number average molecular weight (Mn) was 8,500, and the molecular weight distribution (Mw / Mn) was 2.94. The obtained solution was mixed with 2000 parts of 2-propanol, solidified, filtered and dried to obtain 99 parts of a dicyclopentadiene ring-opening polymer.
Similarly, the subsequent steps were performed to obtain 26.9 parts of a dicyclopentadiene ring-opening polymer hydride. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99.6%, the melting point was 286 ° C., and the ratio of racemodyad (syndiotacticity) was 99%. Moreover, it confirmed that the glass transition temperature of the obtained dicyclopentadiene type ring-opening polymer hydride was 90 degreeC or more and 120 degrees C or less using the differential scanning calorimeter (DSC).
The obtained dicyclopentadiene ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain dicyclopentadiene ring-opening polymer hydride pellets, an unstretched film, and a stretched film. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 8)
Polymerization catalyst no. Except that the ring-opening polymerization reaction was carried out using 0.100 part of the tungsten complex of 4, a solution containing a dicyclopentadiene-based ring-opening polymer was obtained in the same manner as in Example 6. A portion of this solution was used to measure the molecular weight of the dicyclopentadiene-based ring-opening polymer. The weight average molecular weight (Mw) was 23,900, the number average molecular weight (Mn) was 8,200, and the molecular weight distribution (Mw / Mn) was 2.91. The obtained solution was mixed with 2000 parts of 2-propanol, solidified, filtered and dried to obtain 99 parts of a dicyclopentadiene ring-opening polymer.
Similarly, the subsequent steps were performed to obtain 26.9 parts of a dicyclopentadiene ring-opening polymer hydride. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99.5%, the melting point was 285 ° C., and the ratio of racemodyad (syndiotacticity) was 100%. Moreover, it confirmed that the glass transition temperature of the obtained dicyclopentadiene type ring-opening polymer hydride was 90 degreeC or more and 120 degrees C or less using the differential scanning calorimeter (DSC).
The obtained dicyclopentadiene ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain dicyclopentadiene ring-opening polymer hydride pellets, an unstretched film, and a stretched film. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

Example 9
Polymerization catalyst no. Except that the ring-opening polymerization reaction was performed using 0.100 part of the tungsten complex of 5, a solution containing a dicyclopentadiene-based ring-opening polymer was obtained in the same manner as in Example 6. A portion of this solution was used to measure the molecular weight of the dicyclopentadiene-based ring-opening polymer. The weight average molecular weight (Mw) was 25,300, the number average molecular weight (Mn) was 8,400, and the molecular weight distribution (Mw / Mn) was 3.01. The obtained solution was mixed with 2000 parts of 2-propanol, solidified, filtered and dried to obtain 99 parts of a dicyclopentadiene ring-opening polymer.
Similarly, the subsequent steps were performed to obtain 26.9 parts of a dicyclopentadiene ring-opening polymer hydride. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99.2%, the melting point was 287 ° C., and the ratio of racemodyad (syndiotacticity) was 100%. Moreover, it confirmed that the glass transition temperature of the obtained dicyclopentadiene type ring-opening polymer hydride was 90 degreeC or more and 120 degrees C or less using the differential scanning calorimeter (DSC).
The obtained dicyclopentadiene ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain dicyclopentadiene ring-opening polymer hydride pellets, an unstretched film, and a stretched film. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 1)
<Hydrogenation of ring-opening polymer> 25.4 parts of a dicyclopentadiene ring-opening polymer hydride was obtained in the same manner as in Example 1 except that the hydrogenation reaction in the step was performed at 190 ° C. for 4 hours. . The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 97.8%, the melting point was 265 ° C., and the ratio (syndiotacticity) of racemodyad was 100%.
The obtained dicyclopentadiene ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain dicyclopentadiene ring-opening polymer hydride pellets, an unstretched film, and a stretched film. Various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Comparative Example 2)
A dicyclopentadiene ring-opening polymer hydride having a syndiotacticity of 89% and a hydrogenation rate of 99.5% was prepared as follows.

<Preparation of dicyclopentadiene-based ring-opening polymer>
Dissolve 0.3 parts of n-hexane solution of 19% diethylaluminum ethoxide and 0.1 part of tetrachlorotungstenphenylimide (tetrahydrofuran) complex (polymerization catalyst No. 6 shown in Table 2) in 3 parts of toluene. Thus, a catalyst solution was obtained.
On the other hand, 350 parts of cyclohexane, 6.4 parts of 1-hexene, and a concentration of 70% were added to a metal reactor (Sumitomo Heavy Industries, Ltd.) equipped with a stirrer and a temperature control jacket, the inside of which was sufficiently dried and replaced with nitrogen. 145 parts of a cyclohexane solution of dicyclopentadiene (endo content rate of 99% or more) was added, and the whole volume was heated to 50 ° C. The catalyst solution was added thereto to initiate a ring-opening polymerization reaction.
After stirring the whole volume at 55 ° C. for 270 minutes, 1.5 parts of methanol was added to stop the ring-opening polymerization reaction. In addition, the effect which insolubilizes a catalyst part is also acquired by adding methanol to a polymerization reaction liquid.
The weight average molecular weight (Mw) of the dicyclopentadiene ring-opening polymer contained in the obtained polymerization reaction solution is 28,700, the number average molecular weight (Mn) is 9570, and the molecular weight distribution (Mw / Mn) is 3.0. there were.

1 part of diatomaceous earth (manufactured by Showa Chemical Industry Co., Ltd., Radiolite # 1500) was added to the resulting polymerization reaction liquid as a filter aid. This suspension was subjected to filtration with a leaf filter (CFR2 manufactured by IHI), and the insolubilized catalyst was separated with diatomaceous earth to obtain a dicyclopentadiene ring-opening polymer solution.

<Hydrogenation of ring-opening polymer>
After the dicyclopentadiene ring-opening polymer solution obtained in accordance with the above was transferred to a reactor equipped with a stirrer and a temperature control jacket (manufactured by Sumitomo Heavy Industries, Ltd.), the concentration of the dicyclopentadiene ring-opening polymer was 9 %, Cyclohexane 600 parts and carbonylchlorohydridotris (triphenylphosphine) ruthenium 0.1 part were added. Next, while stirring the whole volume at a rotational speed of 64 rpm, a hydrogenation reaction was performed at a hydrogen pressure of 4 MPa and a temperature of 180 ° C. for 6 hours to obtain a slurry containing dicyclopentadiene ring-opening polymer hydride particles.
The slurry thus obtained is centrifuged to separate the solid and the solution, and the solid is dried under reduced pressure at 60 ° C. for 24 hours to obtain a dicyclopentadiene ring-opening polymer hydride 27.0. Got a part.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99.5%, the melting point was 265 ° C., and the ratio of racemodyad (syndiotacticity) was 89%.

<Preparation of resin material>
Pellets were obtained in the same manner as in Example 1 except that the barrel set temperature was 270 to 280 ° C. and the die set temperature was 250 ° C. during the operation of the twin screw extruder.

<Manufacture of resin film (non-stretched)>
An unstretched film was obtained in the same manner as in Example 1 except that the operating conditions of the film forming machine were changed as shown below. About the obtained unstretched film, the tensile strength and breaking elongation were measured according to the above. The results are shown in Table 1.
・ Barrel temperature setting: 280 ℃ ～ 290 ℃
-Die temperature: 270 ° C
-Screw rotation speed: 30rpm

<Manufacture of resin film (stretched)>
The same operation as in Example 1 was performed to obtain a stretched film. About the obtained stretched film, reflow resistance and gas generation amount were evaluated. The results are shown in Table 1.

As is clear from Table 1, according to the dicyclopentadiene ring-opening polymer hydrides of Examples 1 to 3 having a syndiotacticity of 100% and a hydrogenation rate of 98.0% or more. It can be seen that it was possible to form a resin molded body and the like that are compatible at a high level of strength and ductility. Therefore, the dicyclopentadiene ring-opening polymer hydride of the present invention can be suitably used for the production of various resin molded products and films. In addition, the biaxially stretched film containing a dicyclopentanediene ring-opening polymer hydride produced in Examples 1 to 3 and having a syndiotacticity of 100% and a hydrogenation rate of 98.0% or more is In addition to being excellent in reflow resistance, the amount of gas generated from the film is small, so that it is particularly useful as an electrical / electronic material.

(Example 10)
A stretched film was obtained by subjecting an unstretched resin film (unstretched film) produced in the same manner as in Example 1 to a stretching process and a heat setting treatment process as described below. About the obtained stretched film, haze, tensile strength, breaking elongation, and linear expansion coefficient were measured according to the above. The results are shown in Table 3.
<Extension process and heat setting process>
The unstretched film obtained according to the above was cut into 120 mm squares, and a stretching process according to the following conditions and a heat setting treatment process were performed in this order using a multi-tank biaxial stretching birefringence orientation axis measuring device (manufactured by Saitoh). Carried out. As a result, a stretched film of dicyclopentadiene ring-opening polymer hydride, which is a resin film containing 25 μm thick dicyclopentadiene ring-opening polymer hydride, was obtained.
-Stretching process, simultaneous biaxial stretching process, stretching speed: 3.3 mm / sec
-Stretching temperature: 100 ° C
-Stretch ratio: MD (Machine Direction) direction double, TD (Transverse Direction) direction double-heat setting treatment process-Heat setting temperature: 220 ° C
・ Heat setting time: 30 seconds

(Examples 11 to 15)
A stretched film was obtained and subjected to various measurements in the same manner as in Example 10, except that the stretching temperature, stretching speed, and heat setting temperature in the heat setting treatment step were changed as shown in Table 3, respectively. It was. The results are shown in Table 3.

In Examples 10 to 15, an unstretched film formed using a dicyclopentadiene ring-opening polymer hydride having a syndiotacticity of 100% and a hydrogenation rate of 98.0% or more. It was confirmed that a stretched film could be produced satisfactorily by stretching at a stretching temperature of 95 ° C. or higher and 130 ° C. or lower. In particular, Table 3 shows that by adjusting the stretching temperature, it is possible to effectively suppress the occurrence of haze in the resulting stretched film.

ADVANTAGE OF THE INVENTION According to this invention, the dicyclopentadiene type ring-opening polymer hydride which can form the resin molded object etc. which were compatible in the intensity | strength and ductility high level can be provided.
Furthermore, according to the present invention, it is possible to provide a resin film and a resin molded body that are compatible at a high level of strength and ductility.
And according to this invention, the manufacturing method of a stretched film which can manufacture a stretched film satisfactorily can be provided using the resin film in which intensity | strength and ductility were compatible in the high level.

Claims

A dicyclopentadiene ring-opening polymer hydride having a syndiotacticity of 99% or more and a hydrogenation rate of 98.0% or more.
The dicyclopentadiene ring-opening polymer hydride according to claim 1, wherein the hydrogenation rate is 99.0% or more.
A resin molded article containing the hydride of the dicyclopentadiene ring-opening polymer according to claim 1 or 2.
A resin film containing the dicyclopentadiene ring-opening polymer hydride according to claim 1 or 2.
The amount of gas attributed to a mass number of 18 (m / z) generated between room temperature and 300 ° C. measured by a heat generation gas mass spectrometry method is set to 0.1%, assuming that the initial mass of the resin film is 100% by mass. The resin film of Claim 4 which is less than 5 mass%.
A ring-opening polymerization step of obtaining a dicyclopentadiene-based ring-opening polymer by ring-opening polymerization of a monomer containing dicyclopentadiene using a ring-opening polymerization catalyst represented by the following general formula (α);
Hydrogenating the dicyclopentadiene ring-opening polymer to obtain a hydrogenated dicyclopentadiene ring-opening polymer having a hydrogenation rate of 98.0% or more;
A process for producing a hydride of a dicyclopentadiene-based ring-opening polymer.

[In the formula (α), Ph represents a phenyl group, and R 1 and R 2 each independently represents a monovalent linear, branched or cyclic hydrocarbon group having 1 to 6 carbon atoms. X represents a hydrogen atom, a halogen atom, a nitro group, an amino group, or a cyano group, and n represents an integer of 0 to 5, and when n is an integer of 1 or more, a plurality of X May be the same or different; Y represents C (R 3 ) 2 R 4 (wherein each R 3 independently represents —R 5 , —OR 5 , —SR). 5 , —N (R 5 ) 2 , —OC (O) R 5 , —S (O) R 5 , —SO 2 R 5 , —SO 2 N (R 5 ) 2 , —C (O) N (R 5 ) 2 , —NR 5 C (O) R 5 , or —NR 5 SO 2 R 5 , wherein each R 5 is independently hydrogen or a straight chain of 1 to 12 carbon atoms. Or branched alkyl 1 to 10 heteroalkyl groups having 1 to 3 heteroatoms independently selected from the group, nitrogen, oxygen or sulfur, phenyl groups, 3 to 7-membered saturated or partially unsaturated carbons 5 to 5 having 1 to 4 heteroatoms independently selected from a ring, a 6 to 10-membered bicyclic saturated ring, a partially unsaturated ring, or an aryl ring, nitrogen, oxygen, or sulfur 6-membered monocyclic heteroaryl ring, 3- to 7-membered saturated or partially unsaturated heterocycle having 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur, nitrogen, oxygen Or a 7 to 10 membered bicyclic saturated or partially unsaturated heterocycle having 1 to 5 heteroatoms independently selected from sulfur, and independently from nitrogen, oxygen, or sulfur 8 to 10 members with 1 to 5 heteroatoms selected Is selected from the bicyclic heteroaryl ring, or an optionally substituted group, or, optionally, two R 5, optionally in combination with the intervening atoms, said intervening Optionally substituted 3-10 membered monocyclic or bicyclic having 0-4 heteroatoms independently selected from nitrogen, oxygen, or sulfur And R 4 is an optionally substituted phenyl group; and Z is nitrogen, oxygen, and A 5- to 14-membered heteroaryl group having 1 to 4 heteroatoms selected from the group consisting of sulfur is shown. ]
An unstretched film formed using the dicyclopentadiene-based ring-opening polymer hydride according to claim 1 or 2, comprising a stretching step of stretching at a stretching temperature of 95 ° C or higher and 130 ° C or lower. Production method.
The manufacturing method of the stretched film of Claim 7 which further includes the heat setting process process which heat-processes the film which passed through the said extending process at the heat setting temperature of 175 degreeC or more and 225 degrees C or less.