JPWO2019181124A1 - Dicyclopentadiene-based ring-opening polymer hydride and its production method, resin molded product, resin film, and stretched film production method. - Google Patents

Abstract

It is a dicyclopentadiene-based ring-opening polymer hydride having a syndiotacticity of 99% or more and a hydrogenation rate of 98.0% or more.

Description

The present invention relates to a dicyclopentadiene-based 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 norbornene-based ring-opening polymer hydride that can be prepared by ring-opening polymerization of a norbornene-based monomer such as dicyclopentadiene is called a "cycloolefin polymer" and is a kind of materials on the market. Such a ring-opening polymer hydride is attracting attention as a material applicable to various applications including optical applications because it is excellent in transparency, low birefringence, molding processability and the like.

Here, the ring-opening polymer hydride containing a monomer unit derived from dicyclopentadiene (hereinafter, also referred to as “dicyclopentadiene-based ring-opening polymer hydride”) is amorphous having an atactic structure. It was generally obtained as a polymer. However, the amorphous dicyclopentadiene ring-opening polymer hydride having an atactic structure may have insufficient heat resistance, mechanical strength, solvent resistance, etc., depending on its use. Therefore, as a method for improving their performance, by producing a dicyclopentadiene-based ring-opening polymer hydride having stereoregularity in the main chain, a dicyclopentadiene-based ring-opening polymer hydride having crystallinity can be obtained. Has been developed.

Therefore, a resin containing a crystalline dicyclopentadiene ring-opening polymer hydride having improved industrial handleability, and a resin molded product, a resin film, and an injection molded product obtained by using such a resin have been proposed. (See, for example, Patent Documents 1 and 2). Patent Documents 1 and 2 describe crystalline dicyclopentadiene ring-opening polymer hydrides 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.
Further, 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 products and the like are required to have both strength and ductility at a high level. However, there is room for improvement in the resin molded products and the like formed by using the polymer hydrides described in Patent Documents 1 to 3 in terms of increasing both strength and ductility.

Therefore, an object of the present invention is to provide a dicyclopentadiene-based ring-opening polymer hydride capable of forming a resin molded product or the like having both high strength and ductility, and a method for producing the same.
Furthermore, an object of the present invention is to provide a resin film and a resin molded product having both high strength and ductility.
Furthermore, an object of the present invention is to provide a method for producing a stretched film, which can satisfactorily produce a stretched film by using a resin film having both high strength and ductility.

The present inventor has conducted diligent studies for the purpose of solving the above problems. Then, the present inventor has increased the hydrogenation rate to a predetermined value or more when the syndiotacticity is remarkably increased when preparing the dicyclopentadiene-based ring-opening polymer hydride. We have found that it is possible to achieve both strength and ductility of a resin molded product containing a ring polymer hydride at a high level, and completed the present invention.

That is, the present invention aims to advantageously solve the above problems, and the dicyclopentadiene-based ring-opening polymer hydride of the present invention has a syndiotacticity of 99% or more and hydrogenation. The rate is 98.0% or more. As described above, the dicyclopentadiene-based ring-opening polymer hydride having both syndiotacticity and hydrogenation rate satisfying the above ranges has both strength and ductility of the obtained resin molded product at a high level. can do.
Here, the syndiotacticity of the dicyclopentadiene-based ring-opening polymer hydride can be determined by the method using ^{13 C-NMR described in Examples.} The hydrogenation rate of the dicyclopentadiene-based ring-opening polymer hydride can be determined by the method using ^{1 1 H-NMR described in Examples.}

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

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

Another object of the present invention is to solve the above problems advantageously, and the resin film of the present invention is characterized by containing any of the above dicyclopentadiene-based ring-opening polymer hydrides. To do. The resin film containing the dicyclopentadiene-based ring-opening polymer hydride of the present invention has high levels of both strength and ductility.

Here, in the resin film of the present invention, the amount of gas generated belonging to the mass number 18 (m / z) generated between room temperature and 300 ° C. measured by the heating generated gas mass spectrometry is the initial amount of the film. It is preferably less than 0.5% by mass, where the mass is 100% by mass. A resin film in which the amount of gas generated when measured under predetermined conditions is reduced is highly suitable as an electrical / electronic material. Here, 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. Further, the "initial mass of the film" is the mass of the resin film in the stage before starting the measurement according to the heating generated gas mass spectrometry.

［式（α）中、Ｐｈはフェニル基を示し、Ｒ¹、Ｒ²は、それぞれ独立して、炭素数１〜６の一価の直鎖状、分岐鎖状、又は環状の炭化水素基を示し；Ｘは、水素原子、ハロゲン原子、ニトロ基、アミノ基、又はシアノ基を示し、また、ｎは０〜５の整数を示すとともに、ｎが１以上の整数の場合には、複数のＸは同一であっても相異なっていても良く；Ｙは、Ｃ（Ｒ³）₂Ｒ⁴を示し（ここで、それぞれのＲ³は、独立して、−Ｒ⁵、−ＯＲ⁵、−ＳＲ⁵、−Ｎ（Ｒ⁵）_２、−ＯＣ（Ｏ）Ｒ⁵、−Ｓ（Ｏ）Ｒ⁵、−ＳＯ_２Ｒ⁵、−ＳＯ_２Ｎ（Ｒ⁵）_２、−Ｃ（Ｏ）Ｎ（Ｒ⁵）_２、−ＮＲ⁵Ｃ（Ｏ）Ｒ⁵、又は−ＮＲ⁵ＳＯ_２Ｒ⁵であり、さらにここで、それぞれのＲ⁵は、独立して、水素、炭素数1〜１２の直鎖状又は分岐鎖状アルキル基、窒素、酸素、若しくは硫黄から独立して選択される１〜３個のヘテロ原子を有する炭素数１〜１０のヘテロアルキル基、フェニル基、三〜七員の飽和若しくは一部不飽和の炭素環、六〜十員の二環式の飽和の環、一部不飽和の環、若しくはアリール環、窒素、酸素、若しくは硫黄から独立して選択される１〜４個のヘテロ原子を有する五〜六員の単環式ヘテロアリール環、窒素、酸素、若しくは硫黄から独立して選択される１〜３個のヘテロ原子を有する三〜七員の飽和若しくは一部不飽和の複素環、窒素、酸素、若しくは硫黄から独立して選択される１〜５個のヘテロ原子を有する七〜十員の二環式の飽和若しくは一部不飽和の複素環、及び、窒素、酸素、若しくは硫黄から独立して選択される１〜５個のヘテロ原子を有する八〜十員の二環式ヘテロアリール環から選択される、任意選択的に置換された基であるか、或いは、任意で、２個のＲ⁵が、介在している原子と共に任意選択的に組み合わされ、前記介在している原子に加えて、窒素、酸素、又は硫黄から独立して選択される０〜４個のヘテロ原子を有する、任意選択的に置換された三〜十員の単環式又は二環式の、飽和の環、一部不飽和の環、又はアリール環を形成してなり；Ｒ⁴は、任意選択的に置換されたフェニル基である。）；及び、Ｚは、窒素、酸素、及び硫黄からなる群より選択される１〜４個のヘテロ原子を有する５〜１４員ヘテロアリール基を示す。］Further, the present invention aims to advantageously solve the above problems, and the method for producing a dicyclopentadiene-based ring-opening polymer hydride of the present invention is represented by the following general formula (α). 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, and the dicyclopentadiene-based ring-opening polymer. It is characterized by including a hydrogenation step of hydrogenating to obtain a dicyclopentadiene-based ring-opening 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 product or the like having both high strength and ductility can be obtained. It can be manufactured well.

[In formula (α), Ph represents a phenyl group, and R ¹ and R ² independently form a monovalent linear, branched, or cyclic hydrocarbon group having 1 to 6 carbon atoms. Indicates; X represents a hydrogen atom, a halogen atom, a nitro group, an amino group, or a cyano group, n represents an integer of 0 to 5, and when n is an integer of 1 or more, a plurality of X's are indicated. ^{May be} the same or different; Y indicates C (R ³ ) ₂ R ⁴ (where each R ³ is independently -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 , where each R ⁵ is independently hydrogen, linear with 1 to 12 carbon atoms. Alternatively, a heteroalkyl group having 1 to 10 carbon atoms having 1 to 3 heteroatoms independently selected from a branched alkyl group, nitrogen, oxygen, or sulfur, a phenyl group, and a 3- to 7-membered saturated or one-membered group. 1 to 4 heteros independently selected from partially unsaturated carbocycles, 6 to 10-membered bicyclic saturated rings, partially unsaturated rings, or aryl rings, nitrogen, oxygen, or sulfur. 5- to 6-membered monocyclic heteroaryl ring with atoms, 3- to 7-membered saturated or partially unsaturated complex with 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur Seven to ten-membered bicyclic saturated or partially unsaturated heteroatoms with 1 to 5 heteroatoms independently selected from rings, nitrogen, oxygen, or sulfur, and nitrogen, oxygen, or It is an optionally substituted group selected from an 8- to 10-membered bicyclic heteroaryl ring having 1 to 5 heteroatoms selected independently of sulfur, or optionally. two R ^5, optionally in combination with the intervening atoms, in addition to said the intervening atoms, nitrogen, oxygen, or 0-4 heteroatoms independently selected from nitrogen Forming an optionally substituted three to ten-membered monocyclic or bicyclic, saturated ring, partially unsaturated ring, or aryl ring; R ⁴ is optional. (); And Z represents a 5- to 14-membered heteroaryl group having 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur. ]

Furthermore, the present invention aims to advantageously solve the above problems, and the method for producing a stretched film of the present invention uses any of the above-mentioned dicyclopentadiene-based ring-opening polymer hydrides. It is characterized by including a stretching step of stretching the unstretched film formed in the above process 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 satisfactorily stretched, and a stretched film having excellent performance can be efficiently manufactured.

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

According to the present invention, it is possible to provide a dicyclopentadiene-based ring-opening polymer hydride capable of forming a resin molded product or the like having both high strength and ductility, and a method for producing the same.
Further, according to the present invention, it is possible to provide a resin film and a resin molded product having both high strength and ductility.
According to the present invention, it is possible to provide a method for producing a stretched film, which can satisfactorily produce a stretched film by using a resin film having both high strength and ductility.

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

(Dicyclopentadiene-based ring-opening polymer hydride)
The dicyclopentadiene-based ring-opening polymer hydride of the present invention (hereinafter, also simply referred to as “HDCPD 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-based ring-opening polymer hydride of the present invention in which the syndiotacticity and the hydrogenation rate are each equal to or higher than the above lower limit values, a resin material or the like having 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 the formula (1)), the dicyclopentadiene-based ring-opening polymer hydrogen There may be stereoregularity (tacticity) in the compound. The dicyclopentadiene-based ring-opening polymer hydride of the present invention has syndiotactic stereoregularity.

In the HDCPD polymer of the present invention, the ratio of the repeating unit (1) is preferably 90% by mass or more, preferably 95% by mass or more, with 100% by mass of all the repeating units constituting the HDCPD polymer. It is more preferably 97% by mass or more, and particularly preferably 100% by mass. When the ratio of the repeating unit (1) in the HDCPD polymer is equal to or higher than the above lower limit value, the strength of the obtained resin material or the like can be further increased.

The repeating unit (1) represented by the above formula (1) is derived from dicyclopentadiene. There are two stereoisomers of dicyclopentadiene, endo and exo, both of which can be used as monomers. In preparing the HDCPD polymer, one of the endo and exo isomers may be used alone, or an isomer mixture in which the endo isomer and exo isomer are mixed at an arbitrary ratio can be used. From the viewpoint of increasing the crystallinity of the HDCPD polymer and particularly increasing the strength of the obtained resin material or the like, it is preferable to increase the proportion of one of the three isomers. Specifically, when preparing the HDCPD polymer, it is preferable to use only one of the endo-form and the exo-form as the dicyclopentadiene, and it is more preferable to use only the endo-form from the viewpoint of easiness of synthesis. When an isomer mixture of dicyclopentadiene is used in the preparation of the HDCPD polymer, the ratio of one of the endo and exo is 90% by mass or more, assuming that the entire isomer mixture is 100% by mass. Is more preferable, 95% by mass or more is more preferable, and 99% by mass or more is particularly preferable. Further, from the viewpoint of easiness 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.

Further, in the preparation of the HDCPD polymer, another cyclic olefin monomer 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, still more preferably 3% by mass or less, with 100% by mass of all the repeating units constituting the HDCPD polymer. It is preferable that 0% by mass, that is, the HDCPD polymer does not contain other cyclic olefin monomers.

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

<Method of preparing dicyclopentadiene-based ring-opening polymer hydride>
The dicyclopentadiene-based ring-opening polymer hydride of the present invention first obtains a dicyclopentadiene-based ring-opening polymer by ring-opening polymerization of the above-mentioned dicyclopentadiene and any other cyclic olefin monomer. Therefore, it can be prepared by hydrogenating the obtained ring-opening polymer.

［式（α）中、Ｐｈはフェニル基を示し、Ｒ¹、Ｒ²は、それぞれ独立して、炭素数１〜６の一価の直鎖状、分岐鎖状、又は環状の炭化水素基を示し；Ｘは、水素原子、ハロゲン原子、ニトロ基、アミノ基、又はシアノ基を示し、また、ｎは０〜５の整数を示すとともに、ｎが１以上の整数の場合には、複数のＸは同一であっても相異なっていても良く；Ｙは、Ｃ（Ｒ³）₂Ｒ⁴を示し（ここで、それぞれのＲ³は、独立して、−Ｒ⁵、−ＯＲ⁵、−ＳＲ⁵、−Ｎ（Ｒ⁵）_２、−ＯＣ（Ｏ）Ｒ⁵、−Ｓ（Ｏ）Ｒ⁵、−ＳＯ_２Ｒ⁵、−ＳＯ_２Ｎ（Ｒ⁵）_２、−Ｃ（Ｏ）Ｎ（Ｒ⁵）_２、−ＮＲ⁵Ｃ（Ｏ）Ｒ⁵、又は−ＮＲ⁵ＳＯ_２Ｒ⁵であり、さらにここで、それぞれのＲ⁵は、独立して、水素、炭素数1〜１２の直鎖状又は分岐鎖状アルキル基、窒素、酸素、若しくは硫黄から独立して選択される１〜３個のヘテロ原子を有する炭素数１〜１０のヘテロアルキル基、フェニル基、三〜七員の飽和若しくは一部不飽和の炭素環、六〜十員の二環式の飽和の環、一部不飽和の環、若しくはアリール環、窒素、酸素、若しくは硫黄から独立して選択される１〜４個のヘテロ原子を有する五〜六員の単環式ヘテロアリール環、窒素、酸素、若しくは硫黄から独立して選択される１〜３個のヘテロ原子を有する三〜七員の飽和若しくは一部不飽和の複素環、窒素、酸素、若しくは硫黄から独立して選択される１〜５個のヘテロ原子を有する七〜十員の二環式の飽和若しくは一部不飽和の複素環、及び、窒素、酸素、若しくは硫黄から独立して選択される１〜５個のヘテロ原子を有する八〜十員の二環式ヘテロアリール環から選択される、任意選択的に置換された基であるか、或いは、任意で、２個のＲ⁵が、介在している原子と共に任意選択的に組み合わされ、前記介在している原子に加えて、窒素、酸素、又は硫黄から独立して選択される０〜４個のヘテロ原子を有する、任意選択的に置換された三〜十員の単環式又は二環式の、飽和の環、一部不飽和の環、又はアリール環を形成してなり；Ｒ⁴は、任意選択的に置換されたフェニル基である。）；及び、Ｚは、窒素、酸素、及び硫黄からなる群より選択される１〜４個のヘテロ原子を有する５〜１４員ヘテロアリール基を示す。］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, the dicyclopentadiene-based ring-opening polymer hydride of the present invention can be efficiently produced by using a ring-opening polymerization catalyst that can be represented by the following general formula (α) as the ring-opening polymerization catalyst. It became clear that it could be manufactured. It is presumed that this is because the skeletal structure defined by the following general formula (α) can satisfactorily form a polymer chain having high syndiotacticity in ring-opening polymerization of dicyclopentadiene. The ring-opening polymerization catalyst, which can be 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, and a terminal oxo coordination. It is considered to be due to the composition of the child and the phosphorus-containing ligand. Specifically, in the phenyl-substituted phenoxy ligand, the alkoxy group is a substituted phenoxy group, and the phenyl group is present at the 2, 3, 5, 6 position, and the 2, 3, 5, 6 position. 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. Further, since the ring-opening polymerization catalyst has a terminal oxy ligand, a sufficient coordination space for dicyclopentadiene can be secured, and a stereo error can be suppressed.

[In formula (α), Ph represents a phenyl group, and R ¹ and R ² independently form a monovalent linear, branched, or cyclic hydrocarbon group having 1 to 6 carbon atoms. Indicates; X represents a hydrogen atom, a halogen atom, a nitro group, an amino group, or a cyano group, n represents an integer of 0 to 5, and when n is an integer of 1 or more, a plurality of X's are indicated. ^{May be} the same or different; Y indicates C (R ³ ) ₂ R ⁴ (where each R ³ is independently -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 , where each R ⁵ is independently hydrogen, linear with 1 to 12 carbon atoms. Alternatively, a heteroalkyl group having 1 to 10 carbon atoms having 1 to 3 heteroatoms independently selected from a branched alkyl group, nitrogen, oxygen, or sulfur, a phenyl group, and a 3- to 7-membered saturated or one-membered group. 1 to 4 heteros independently selected from partially unsaturated carbocycles, 6 to 10-membered bicyclic saturated rings, partially unsaturated rings, or aryl rings, nitrogen, oxygen, or sulfur. 5- to 6-membered monocyclic heteroaryl ring with atoms, 3- to 7-membered saturated or partially unsaturated complex with 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur Seven to ten-membered bicyclic saturated or partially unsaturated heteroatoms with 1 to 5 heteroatoms independently selected from rings, nitrogen, oxygen, or sulfur, and nitrogen, oxygen, or It is an optionally substituted group selected from an 8- to 10-membered bicyclic heteroaryl ring having 1 to 5 heteroatoms selected independently of sulfur, or optionally. two R ^5, optionally in combination with the intervening atoms, in addition to said the intervening atoms, nitrogen, oxygen, or 0-4 heteroatoms independently selected from nitrogen Forming an optionally substituted three to ten-membered monocyclic or bicyclic, saturated ring, partially unsaturated ring, or aryl ring; R ⁴ is optional. (); And Z represents a 5- to 14-membered heteroaryl group having 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur. ]

Halogen atoms that can be X include F, Cl, Br, and I. Above all, when X is a halogen atom, it is preferably Br.
Further, it is preferable that n is 0.

The ^{linear or branched hydrocarbon group having 1 to 6 carbon atoms, which are R 1} and R ² , is not particularly limited, and is a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, and an isobutyl. A linear or branched alkyl group having 1 to 6 carbon atoms such as a group, a tert-butyl group, a pentyl group, a hexyl group, and an isohexyl group, as well as a cyclic aliphatic hydrocarbon group and an aromatic hydrocarbon group. Can be mentioned. The cyclic hydrocarbon group having 1 to 6 carbon atoms, which can be R ¹ or R ² , is not particularly limited, and is a cyclic aliphatic group such as a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group. Hydrocarbon groups; and aromatic hydrocarbon groups such as phenyl groups can be mentioned. 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 can 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 and a pentyl group. Examples include a hexyl group, a heptyl group, an octyl group, a nonyl group and the like. Of these, ^{it is preferable that R 3} is a methyl group.
In addition ^{, examples of the group that can 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. 0201 to 0222). Among these groups, examples of the substituent bonded to the substitutable carbon atom of the arbitrarily substituted group include various substituents described in International Publication No. 2015/1271992 (for example, various substituents described in International Publication No. 2015/127192). See, for example, International Publication No. 2015/127192, paragraphs 0058-0064).

In the 5- to 14-membered heteroaryl group of Z, it is preferable that at least one heteroatom is N. Further, it is more preferable that Z is bonded to W via at least one nitrogen atom. For example, Z can be a group represented by any of the following general formulas (Z-1) to (Z-6). Here, Z is a five-membered heteroaryl having 1 to 4 heteroatoms independently selected from N, O, and S, and it is particularly preferable that at least one heteroatom is nitrogen. .. Among them, Z is preferably a group represented by the following formulas (Z-1), (Z-2), (Z-3), and (Z-6), and is represented by the following formula (Z-6). It is particularly preferable that the group is an integer. Since Z is a five-membered heteroaryl, at least one heteroatom is nitrogen, and the substituent at the 2nd and 5th positions is a hydrogen atom or a methyl group, the catalytic structure is stable and stereo error is small. Become.

The ring-opening polymerization catalyst as shown by the above formula (α) is not particularly limited, and is, for example, International Publication No. 2015/127192, International Publication No. 2016/14311, and Benjamin Autenrieth et al., "Stereospecific". It can be synthesized according to the method disclosed in Ring-Opening Metathesis Polymerization (ROMP) of endo-Dicyclopentadiene by Molybdenum and Tungsten Catalysts, Macromolecules, 2015, 48, p.2480-2492.

In 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, and is 0. More preferably, it is 0.05 parts by mass or more and 0.30 parts by mass or less. By setting the amount of the catalyst used within the above range, the ring-opening polymerization reaction can be sufficiently promoted. The polymerization time is usually 1 minute or more and 100 hours or less, preferably 30 minutes or more and 5 hours or less. Further, the polymerization temperature can be usually −30 ° C. or higher and 200 ° C. or lower, preferably 0 ° C. or higher and 180 ° C. or lower.
Further, in the ring-opening polymerization, a known molecular weight modifier or the like, which may 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 carried out in a solvent-free system, but is preferably carried out in an organic solvent. The organic solvent is 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. Any organic solvent can be used. For example, examples of the organic solvent include aliphatic hydrocarbons such as pentane, hexane and heptane; cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, etc. Hexahydroindene Alicyclic hydrocarbons such as cyclohexane and cyclooctane; aromatic hydrocarbons such as benzene, toluene and xylene; halogen-based aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; chlorobenzene, dichlorobenzene and the like Halogen-based aromatic hydrocarbons; nitrogen-containing hydrocarbons such as nitromethane, nitrobenzene and acetonitrile; ethers such as diethyl ether and tetrahydrofuran; aromatic ethers such as anisole and phenetol can be mentioned. These can be used alone or in combination 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 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 molded products.
The molecular weight distribution (Mw / Mn) of the dicyclopentadiene ring-opening polymer is not particularly limited, but is usually 4.0 or less, preferably 3.5 or less. The 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-based ring-opening polymer are standard polystyrene-equivalent 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 is carried out by (a) adding a hydrogenating agent as a hydrogen source and then heating and reacting, or (b) adding a hydrogenation catalyst to a system in which a dicyclopentadiene-based ring-opening polymer is present. Then, hydrogen gas as a hydrogen source is added to hydrogenate the unsaturated bond existing in the dicyclopentadiene-based ring-opening polymer. Among these, from the viewpoint of industrial production, it is preferable to adopt the hydrogenation method (b). In other words, it is preferable to carry out the hydrogenation reaction of the dicyclopentadiene ring-opening polymer using a hydrogenation catalyst and hydrogen gas.

The method (a) is included in a dicyclopentadiene-based ring-opening polymer using a hydrazine-containing compound known as a hydrogenating agent (hydrogen source) for hydrogen transfer hydrogenation. A method of hydrogenating an unsaturated bond can be 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), conventionally known hydrogenation catalysts can be used as the hydrogenation catalyst of the ring-opening polymer. 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) ( 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 , Raney nickel, nickel diatomaceous earth, nickel acetate, palladium acetate, PdCl ₂ , RhCl (PPh) _{3, and the} like can be mentioned. Of these, carbonylchlorohydridotris (triphenylphosphine) ruthenium [RuHCl (CO) (PPh ₃ ) ₃ ] is preferred.

The hydrogenation reaction is usually carried out in an inert organic solvent. Examples of the inert organic solvent that can be used include cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane, trimethylcyclohexane, ethylcyclohexane, diethylcyclohexane, decahydronaphthalene, bicycloheptane, tricyclodecane, hexahydroindencyclohexane, cyclooctane and the like. Aromatic hydrocarbons; aromatic hydrocarbons such as benzene, toluene and xylene; halogen-based aliphatic hydrocarbons such as dichloromethane, chloroform and 1,2-dichloroethane; halogen-based aromatic hydrocarbons such as chlorobenzene and dichlorobenzene; diethyl Examples include ethers such as ethers and tetrahydrofurans; aromatic ethers such as anisole and phenetol; and the like. These can be used alone or in combination of two or more. Of these, alicyclic hydrocarbons and aromatic hydrocarbons are preferable.

Further, the hydrogenation reaction conditions such as the hydrogenation reaction temperature can be appropriately set according to the hydrogenating agent to be used and the 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 become too slow, and if it is too high, a side reaction may occur and the hydrogenation rate may decrease. Further, by adjusting the hydrogenation temperature in an appropriate range, the hydrogenation rate of the obtained HDCPD polymer can be set to a desired value.
Further, 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, and more preferably 0.1 to 10 MPa. If the hydrogen pressure is too low, the hydrogenation rate may become too slow, and if it is too high, there are restrictions on the device in that a high withstand voltage reactor is required.
Furthermore, the hydrogenation reaction time is not particularly limited as long as it can be a desired hydrogenation rate, but can usually be 0.1 to 10 hours.
Then, after the hydrogenation reaction according to an arbitrary method is completed, the dicyclopentadiene-based ring-opening polymer hydride may be recovered according to a conventional method. In the recovery of the dicyclopentadiene-based ring-opening polymer hydride, the catalyst residue can be removed by a known method such as centrifugation and filtration.

<Hydrogenation rate of HDCPD polymer>
The dicyclopentadiene-based ring-opening polymer hydride of the present invention needs to have a hydrogenation rate of 98.0% or more, preferably 99.0% or more, and preferably 99.2% or more. More preferred. When the hydrogenation rate is at least the above lower limit value, the strength and reflow resistance of the obtained resin material can be further improved. Here, "reflow resistance" means resistance when the printed circuit board material is heated according to a reflow method commonly used when soldering parts to a printed circuit board or the like. The temperature profile of heating according to the reflow method is defined in, for example, J-STD-020C. The hydrogenation rate indicates the ratio of hydrogenated unsaturated bonds among all unsaturated bonds contained in the main chain and side chains of the dicyclopentadiene ring-opening polymer hydride. The hydrogenation rate is ^{a value based on 1 1} H-NMR measurement and is a value based on a molar value.

<Syndio tacticity of HDCPD polymer>
The dicyclopentadiene-based ring-opening polymer hydride of the present invention needs to have a syndiotacticity of 99% or more. Here, syndiotacticity is the ratio of racemodiad to the total abundance of isotactic diad (mesodiad) and racemodiad present in a polymer chain having stereoregularity (hereinafter, simply, "ratio of racemodiad"). May be referred to as). In particular, the dicyclopentadiene-based ring-opening polymer hydride of the present invention preferably has a syndiotacticity of 99.5% or more, more preferably 100%. When the syndiotacticity is at least the above lower limit value, the crystallinity of the dicyclopentadiene-based ring-opening polymer hydride is sufficiently high, and the strength of the obtained resin material or the like can be sufficiently increased. The syndiotacticity ^{is a value based on 13} C-NMR measurement and is a value based on a molar value.

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

<Glass transition temperature of HDCPD polymer>
The glass transition temperature of the dicyclopentadiene-based ring-opening polymer hydride of the present invention is preferably 80 ° C. or higher, more preferably 90 ° C. or higher. When the glass transition temperature of the dicyclopentadiene-based ring-opening polymer hydride is within the range, the heat resistance is good, and for example, the deflection temperature under load of the obtained resin molded product or the like is high, which is suitable. The upper limit of the glass transition point is not particularly limited, but is approximately 120 ° C.

<Melting point of HDCPD 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. Is particularly preferred. When the melting point of the HDCPD polymer is at least the above lower limit value, a resin material having excellent heat resistance can be provided. Further, when the melting point of the HDCPD polymer is equal to or less than the above upper limit value, it is not necessary to excessively raise the processing temperature when processing the obtained resin material, and the deterioration of the resin material due to the excessively high processing temperature is eliminated. It can be avoided.

(Resin material)
The resin material containing the dicyclopentadiene-based ring-opening polymer hydride of the present invention described above has high levels of both strength and ductility. The resin material may contain an arbitrary component in addition to the dicyclopentadiene-based ring-opening polymer hydride of the present invention. Such optional components are not particularly limited, and include, for example, the inorganic filler disclosed in International Publication No. 2016/143795, and antioxidants, ultraviolet absorbers, light stabilizers, near-infrared absorbers, and plasticizers. Examples thereof include additives such as agents, antistatic agents, acid trapping agents, flame retardants, and flame retardant aids.

The blending amount of the inorganic filler and the additive can be arbitrarily set according to the purpose. For example, the blending 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. The blending amount of the additive may be 0.01 part by mass or more and 10 parts by mass or less with respect to 100 parts by mass of the dicyclopentadiene ring-opening polymer hydride of the present invention. In other words, the content ratio of the dicyclopentadiene-based ring-opening polymer hydride of the present invention in the resin material can be 30% by mass or more, assuming that the entire resin material is 100% by mass. Of course, the resin material may not contain any component, and substantially 100% by mass may be composed of the dicyclopentadiene-based ring-opening polymer hydride of the present invention. In the present specification, "substantially 100% by mass" may contain, for example, 0.05% by mass or less of unavoidable impurities such as a polymerization solvent that may be mixed due to the purification limit at the time of production. Means that.

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

(Resin molded product)
The resin molded product of the present invention contains the above-mentioned dicyclopentadiene-based ring-opening polymer hydride of the present invention. Since the resin molded product of the present invention contains the dicyclopentadiene-based ring-opening polymer hydride of the present invention, both strength and ductility are at high levels. The resin molded product may be a molded product obtained by molding the above-mentioned resin material into an arbitrary shape. Therefore, the resin molded product may also contain various optional components that can be blended in the resin material in the above proportions. Further, the resin molded body may be composed of the dicyclopentadiene-based ring-opening polymer hydride of the present invention in an amount of 30% by mass or more, assuming that the total mass of the resin molded body is 100% by mass. It does not contain any component, and substantially 100% by mass may be composed of the dicyclopentadiene-based ring-opening polymer hydride of the present invention.

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

(Resin film)
The resin film of the present invention contains the above-mentioned dicyclopentadiene-based ring-opening polymer hydride of the present invention. Since the resin film of the present invention is a kind of the above-mentioned resin molded product of the present invention and contains the dicyclopentadiene-based ring-opening polymer hydride of the present invention, both strength and ductility are at a high level. The resin film of the present invention can be a molded product obtained by molding the above-mentioned resin material into a film. Therefore, the resin film may also contain various optional components that can be blended in the resin material in the above proportions. Further, the resin film may be composed of the dicyclopentadiene-based ring-opening polymer hydride of the present invention in an amount of 30% by mass or more, assuming that the total mass of the resin film is 100% by mass. It may be contained, and substantially 100% by mass may be composed of the dicyclopentadiene-based ring-opening polymer hydride of the present invention.

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

<Gas generated by resin film>
In the resin film of the present invention, the amount of gas generated belonging to the mass number 18 (m / z) generated between room temperature and 300 ° C. measured by the heating generated gas mass spectrometry is 100% of the mass of the resin film. The mass% is preferably less than 0.5% by mass. Here, the gas belonging to the mass number 18 (m / z) is specifically H ₂ O. If the amount of gas generated by the resin film is less than the above upper limit, the amount of water that can be released when the resin film is heated when it is used for a desired purpose is sufficiently small, so that it is particularly used as an electrical / electronic material. Is highly suitable. _{The H 2} O generated from the film during the above measurement is mainly the water 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 treatment or heat fixing treatment as described in International Publication No. 2016/143795.
By performing the stretching treatment, a resin film having a high crystallinity and more excellent strength can be obtained. Further, by performing the heat fixing treatment, a resin film having a small heat shrinkage rate can be obtained.

Further, a laminated film in which a metal layer is laminated on both sides or one side of the resin film of the present invention by a known method can be suitably used as a flexible printed circuit board material. As a method for producing the laminated film, a method of hot-pressing the resin film and the metal foil for forming the metal layer and heating the resin film to near the melting point to fuse the resin film and the metal layer is formed. Examples thereof include a method of adhering the metal foil for the purpose through 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.
Examples of the metal layer include layers containing metals such as copper, gold, silver, aluminum, nickel, and chromium. Among these, copper is preferable because a laminated film useful as a flexible printed circuit board material can be obtained. Further, the adhesive layer can be formed by 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.

(Manufacturing method of stretched film)
The method for producing a stretched film of the present invention includes a stretching step of stretching an unstretched film formed by using a dicyclopentadiene-based 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-mentioned resin film of the present invention that has not been stretched. Further, the method for producing a stretched film of the present invention preferably further includes a heat fixing treatment step. Hereinafter, each step will be described in detail.

<Stretching 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-based ring-opening polymer hydride of the present invention has high levels of both syndiotacticity and hydrogenation rate. The unstretched film formed by using the dicyclopentadiene-based ring-opening polymer hydride of the present invention has high crystallinity and high strength, but haze is likely to occur when the stretch treatment is performed according to the conventional method. In some cases, a stretched film with high transparency could not be obtained. Therefore, as a result of diligent studies by the present inventors, by setting the temperature during the stretching treatment to 95 ° C. or higher and 130 ° C. or lower, the cloudiness (that is, haze) value of the stretched film is prevented from becoming excessively high. However, it was clarified that the 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 to be stretched during stretching, which prevents the film from breaking and deteriorates productivity. Can be suppressed. Further, 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 step and to prevent the obtained film from easily expanding thermally. be able to. Further, from the viewpoint of further enhancing these effects on haze and thermal expansion, the temperature during the stretching treatment is preferably 125 ° C. or lower, more preferably 115 ° C. or lower. Whether or not the film easily expands thermally can be quantitatively expressed by the coefficient of linear expansion. The coefficient of linear expansion is expressed as the rate at which the length changes with a temperature change of 1 ° C. (unit: ppm / ° C.).

The stretching treatment is not particularly limited and can be carried out according to a known method. Specifically, a uniaxial stretching method such as a method of uniaxial stretching in the vertical direction using the difference in peripheral speed between rolls and a method of uniaxial stretching in the horizontal direction using a tenter stretching machine; Simultaneous biaxial stretching method in which the guide rail is stretched in the horizontal direction depending on the spread angle of the guide rail at the same time as the stretching in the vertical direction, and the stretching in the vertical direction using the difference in peripheral speed between the rolls, and then both ends thereof are stretched. 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 feeding force, a tensile force, or a pulling force having different speeds in the lateral or vertical direction can be applied. Examples thereof include a method of continuously diagonally stretching the film in a direction of an arbitrary angle θ with respect to the width direction of the film by using the tenter stretching machine described above. Above all, the biaxial stretching method is preferable.

The stretching ratio in the stretching 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. When the draw ratio is at least the above lower limit value, it is possible to prevent the obtained film from becoming excessively susceptible to thermal expansion. Further, when the draw ratio is not more than the above upper limit value, the occurrence of haze can be suppressed. When various biaxial stretching methods are adopted as the stretching method, the stretching ratio is defined by the product of the longitudinal and horizontal stretching ratios.

Further, the stretching speed in the stretching step is preferably adjusted according to the stretching temperature. More specifically, the higher the stretching temperature, the faster the progress of crystallization in the film. Therefore, from the viewpoint of efficiently and satisfactorily carrying out the stretching step, it is preferable to increase the stretching rate.

<Heat fixing process>
In the heat fixing treatment step, the film that has undergone the stretching step is heat-treated at a temperature of 175 ° C. or higher and 225 ° C. or lower. By subjecting the film that has undergone the stretching step to a heat-fixing treatment, the film obtained through the heat-fixing treatment step is likely to undergo thermal expansion, and haze is more effectively suppressed from occurring in the film. Can be done. In particular, the fact that the film does not easily expand thermally means that the dimensional stability of the film is high. Further, the heat fixing temperature in the heat fixing treatment step is preferably 190 ° C. or higher, more preferably 205 ° C. or higher, from the viewpoint of further better suppressing the tendency of the film to expand thermally.

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

The heat treatment time (heat fixing 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, still more preferably 2 minutes or less. In particular, when the heat fixing time is not more than the above upper limit, it is possible to more effectively suppress the occurrence of haze in the obtained film.

Hereinafter, the present invention will be specifically described based on examples, but the present invention is not limited to these examples. In the following description, "%" and "part" representing quantities are based on mass unless otherwise specified. The pressure is a gauge pressure.
The measurement and evaluation in each example were carried out 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), the number average molecular weight (Mn), and the 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 HDCPD polymer>
Using a differential scanning calorimeter (DSC), differential scanning calorimetry was performed under the condition that the heating rate was 10 ° C./min, and the melting point of the HDCPD polymer was measured.

<Hydrogenation rate of HDCPD polymer>
¹ Based on 1 H-NMR measurement, the hydrogenation rate of unsaturated bonds in the HDCPD polymer was determined.

<Syndio tacticity of HDCPD polymer>
Orthodichlorobenzene-d ₄ / 1,2,4-trichlorobenzene (TCB) -d ₃ (mixing ratio (mass basis) 1/2) was used as a solvent, and the inverse-gated decoding method was applied at 200 ° C. ¹³ C. -NMR measurement was performed to determine the proportion of racemodiad in the dicyclopentadiene-based ring-opening polymer hydride. Specifically, based on the intensity ratio of the signal of 43.35 ppm derived from mesodiad and the signal of 43.43 ppm derived from racemodiad, using the peak of 127.5 ppm of orthodichlorobenzene-d _{4 as a reference shift, racemodiad.} The ratio (%) of was calculated.

<Strength and ductility of resin films (non-stretched films and stretched films)>
The non-stretched film obtained in Examples 1 to 9 and Comparative Examples 1 and 2 and the stretched film obtained in Examples 10 to 15 were subjected to the MD direction (MD) in the shape of the test piece type 1B of JIS K7127: 1999 standard. : Machine Direction) was punched to prepare a sample for tensile test. The obtained sample was subjected to a tensile test at a test speed of 100 m / min using a universal material testing machine (“Instron”, type 5582), 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 film, which is the resin film obtained in Examples 1 to 9 and Comparative Examples 1 and 2, was cut into 5 cm squares and cut into 10 cm squares with a 0.8 mm thick copper-clad laminate (manufactured by Panasonic Corporation, "R-". 1766 ") was attached to a test piece with its four sides fixed with polyimide tape. Appearance of the test piece after being put into a small reflow furnace (manufactured by Antom, "HAS-6116H") having a peak temperature of 260 ° C. once in accordance with J-STD-020C and taken out. Was visually evaluated. Evaluation was performed on 3 test pieces in each case, and evaluation was performed according to the following criteria.
A: None of the three test pieces is deformed.
B: One or two test pieces are deformed.
C: All three test pieces are deformed.

<Gas generated by 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 a temperature of 23 ° C. and a humidity of 60% for 24 hours or more, and then weighed. The initial mass W0 was obtained. Then, the stretched film was analyzed by a heating generated gas mass spectrometer (heating and desorption gas analyzer) under a helium stream at a heating rate of 10 ° C./min from room temperature to 300 ° C. Assuming that the initial mass of the resin film was 100% by mass, the ratio of the amount 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 film obtained in Examples 10 to 15, and the degree of cloudiness (scattered light / total light transmission) was cut out using a haze meter (manufactured by Nippon Denshoku Kogyo Co., Ltd., “NDH5000”). The value of light × 100 (%)) was obtained.

<Coefficient of linear expansion>
From the stretched film obtained in Examples 10 to 15, a rectangular thin film sample having an MD (Machine Direction) direction of 20 mm × a TD (Transverse Direction) direction of 4 mm was cut out, and then TMA (“TMASS7100” manufactured by Hitachi High-Tech Science Co., Ltd.) was used. Using, the linear expansion coefficient (ppm / ° C = μm / ° C / m) in the temperature range of 40 ° C. to 80 ° C. and 120 ° C. to 160 ° C. was measured, respectively.

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

To 667 parts of the obtained solution containing the dicyclopentadiene ring-opening polymer, 1.1 parts of 2-propanol was added as a terminator to terminate the polymerization reaction.
When the molecular weight of the dicyclopentadiene ring-opening polymer was measured using a part of this solution, 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>
The reaction solution containing the obtained dicyclopentadiene-based ring-opening polymer was transferred to a metal pressure-resistant container equipped with a stirrer and a temperature control jacket, and then 330 parts of toluene and carbonylchlorohydridotris (triphenylphosphine) as a hydrogenation catalyst. ) 0.027 part of ruthenium was added. Next, while stirring the whole volume at a rotation speed of 64 rpm, the hydrogen pressure is raised and raised to 2.0 MPa and 120 ° C., and further raised and raised to 4.0 MPa at 0.03 MPa / min and 180 ° C. at 1 ° C./min. After that, a hydrogenation reaction was carried out for 6 hours. The reaction solution after cooling was a slurry solution in which solid content was precipitated.
The reaction solution was centrifuged to separate the solid content from the solution, and the solid content was dried under reduced pressure at 120 ° C. for 24 hours to obtain 90 parts of a dicyclopentadiene-based ring-opening polymer hydride.
The obtained dicyclopentadiene-based ring-opening polymer hydride had a hydrogenation rate of 99.5%, a melting point of 276 ° C., and a rate of racemodiad (that is, syndiotacticity) of 100%. Further, using a differential scanning calorimeter (DSC), it was confirmed that the glass transition temperature of the obtained dicyclopentadiene-based ring-opening polymer hydride was 90 ° C. or higher and 120 ° C. or lower.

<Preparation of resin material>
An antioxidant (tetrakis [methylene-3- (3', 5'-di-t-butyl-4'-hydroxyphenyl)] was added to 20 parts of the dicyclopentadiene-based ring-opening polymer hydride obtained as described above. ) Propionate] After mixing 0.16 parts of methane, product name "Irganox (registered trademark) 1010", manufactured by BASF Japan, Ltd., the mixture is put into a twin-screw extruder (TEM-37B, manufactured by Toshiba Machine Co., Ltd.). , A strand-shaped polymer was obtained by hot melt extrusion molding. Then, the strand-shaped molded product was shredded with a strand cutter to obtain pellets which are resin materials containing a dicyclopentadiene-based ring-opening polymer hydride.
The operating conditions of the twin-screw extruder are shown below.
-Barrel set temperature: 280 to 290 ° C
-Die set temperature: 260 ° C
・ Screw rotation speed: 145 rpm
・ Feeder rotation speed: 50 rpm

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

<Manufacturing of resin film (stretched)>
The resin film (non-stretched film) obtained in accordance with the above is cut into 120 mm square pieces, and simultaneously subjected to biaxial stretching treatment and heat fixing treatment with a multi-tank biaxially stretched double refractive orientation axis measuring device (manufactured by Eto). To obtain a stretched film of a dicyclopentadiene-based ring-opening polymer hydride, which is a resin film containing a dicyclopentadiene-based ring-opening polymer hydride having a thickness of 25 μm.
The operating conditions of the multi-tank biaxially stretched birefringence orientation axis measuring device are shown below.
-Stretching speed: 15 mm / sec
-Stretching temperature: 130 ° C
-Stretching ratio: 2 times in MD (Machine Direction) direction, 2 times in TD (Transverse Direction) direction-Heat fixing temperature: 220 ° C
・ Heat fixing time: 60 seconds

(Example 2)
27.2 parts of a dicyclopentadiene-based ring-opening polymer hydride was obtained in the same manner as in Example 1 except that the hydrogenation reaction in the <hydrogenation of ring-opening polymer> step was carried out at 185 ° C.
The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99.2%, the melting point was 272 ° C., and the ratio of racemodiad (syndiotacticity) was 100%. Further, using a differential scanning calorimeter (DSC), it was confirmed that the glass transition temperature of the obtained dicyclopentadiene-based ring-opening polymer hydride was 90 ° C. or higher and 120 ° C. or lower.
The obtained dicyclopentadiene-based ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain pellets, unstretched film, and stretched film of the dicyclopentadiene-based ring-opening polymer hydride. Then, various measurements and evaluations were carried out 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 carried out 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 racemodiad (syndiotacticity) was 100%. Further, using a differential scanning calorimeter (DSC), it was confirmed that the glass transition temperature of the obtained dicyclopentadiene-based ring-opening polymer hydride was 90 ° C. or higher and 120 ° C. or lower.
Then, the obtained dicyclopentadiene-based ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain pellets, unstretched film, and stretched film of the dicyclopentadiene-based ring-opening polymer hydride. Then, 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> A solution containing the dicyclopentadiene-based ring-opening polymer, which was carried out in the same manner as in Example 1 except that the ring-opening polymerization reaction was carried out at 25 ° C. for 5 hours. Got When the molecular weight of the dicyclopentadiene ring-opening polymer was measured using a part of this solution, 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 following steps were carried out to obtain 26.9 parts of a dicyclopentadiene-based 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 racemodiad (syndiotacticity) was 100%. Further, using a differential scanning calorimeter (DSC), it was confirmed that the glass transition temperature of the obtained dicyclopentadiene-based ring-opening polymer hydride was 90 ° C. or higher and 120 ° C. or lower.
Then, the obtained dicyclopentadiene-based ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain pellets, unstretched film, and stretched film of the dicyclopentadiene-based ring-opening polymer hydride. Then, 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> A solution containing the dicyclopentadiene-based ring-opening polymer, which was carried out in the same manner as in Example 1 except that the ring-opening polymerization reaction was carried out at 80 ° C. for 1 hour. Got When the molecular weight of the dicyclopentadiene ring-opening polymer was measured using a part of this solution, 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 following steps were carried out to obtain 26.9 parts of a dicyclopentadiene-based ring-opening polymer hydride. The hydrogenation rate of the dicyclopentadiene ring-opening polymer hydride was 99.5%, the melting point was 276 ° C., and the ratio of racemodiad (syndiotacticity) was 100%. Further, using a differential scanning calorimeter (DSC), it was confirmed that the glass transition temperature of the obtained dicyclopentadiene-based ring-opening polymer hydride was 90 ° C. or higher and 120 ° C. or lower.
Then, the obtained dicyclopentadiene-based ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain pellets, unstretched film, and stretched film of the dicyclopentadiene-based ring-opening polymer hydride. Then, 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, the polymerization catalyst No. 1 shown in Table 2 was added. A ring-opening polymerization reaction was carried out using 0.100 parts of the tungsten complex of No. 2 in the same manner as in Example 1 to obtain a solution containing a dicyclopentadiene-based ring-opening polymer. When the molecular weight of the dicyclopentadiene ring-opening polymer was measured using a part of this solution, 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, coagulated, filtered off and dried to obtain 99 parts of a dicyclopentadiene ring-opening polymer.

<Hydrogenation of ring-opening polymer>
A glass flask is mixed with 30.0 parts of a dicyclopentadiene-based ring-opening polymer, 170 parts of paratoluenesulfonyl hydrazide as a hydrogenating agent, and 600 parts of paraxylene, and heated to 120 ° C. under a dry nitrogen atmosphere. It was warmed and reacted for 4 hours. The reaction solution was a slurry solution in which solid content was precipitated. The reaction solution was centrifuged to separate the solid content from the solution, and the solid content was dried under reduced pressure at 60 ° C. for 24 hours to obtain 27.0 parts of a dicyclopentadiene ring-opening polymer hydride.
The obtained dicyclopentadiene-based ring-opening polymer hydride had a hydrogenation rate of 99.4%, a melting point of 284 ° C., and a ratio of racemodiad (syndiotacticity) of 100%. Further, using a differential scanning calorimeter (DSC), it was confirmed that the glass transition temperature of the obtained dicyclopentadiene-based ring-opening polymer hydride was 90 ° C. or higher and 120 ° C. or lower.
Then, the obtained dicyclopentadiene-based ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain pellets, unstretched film, and stretched film of the dicyclopentadiene-based ring-opening polymer hydride. Then, various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 7)
The polymerization catalyst Nos. shown in Table 2 A ring-opening polymerization reaction was carried out using 0.100 parts of the tungsten complex of No. 3 in the same manner as in Example 6 to obtain a solution containing a dicyclopentadiene-based ring-opening polymer. When the molecular weight of the dicyclopentadiene ring-opening polymer was measured using a part of this solution, 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, coagulated, filtered off and dried to obtain 99 parts of a dicyclopentadiene ring-opening polymer.
Similarly, the following steps were carried out to obtain 26.9 parts of a dicyclopentadiene-based 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 racemodiad (syndiotacticity) was 99%. Further, using a differential scanning calorimeter (DSC), it was confirmed that the glass transition temperature of the obtained dicyclopentadiene-based ring-opening polymer hydride was 90 ° C. or higher and 120 ° C. or lower.
Then, the obtained dicyclopentadiene-based ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain pellets, unstretched film, and stretched film of the dicyclopentadiene-based ring-opening polymer hydride. Then, various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 8)
The polymerization catalyst Nos. shown in Table 2 A ring-opening polymerization reaction was carried out using 0.100 parts of the tungsten complex of No. 4 in the same manner as in Example 6 to obtain a solution containing a dicyclopentadiene-based ring-opening polymer. When the molecular weight of the dicyclopentadiene ring-opening polymer was measured using a part of this solution, 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, coagulated, filtered off and dried to obtain 99 parts of a dicyclopentadiene ring-opening polymer.
Similarly, the following steps were carried out to obtain 26.9 parts of a dicyclopentadiene-based 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 racemodiad (syndiotacticity) was 100%. Further, using a differential scanning calorimeter (DSC), it was confirmed that the glass transition temperature of the obtained dicyclopentadiene-based ring-opening polymer hydride was 90 ° C. or higher and 120 ° C. or lower.
Then, the obtained dicyclopentadiene-based ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain pellets, unstretched film, and stretched film of the dicyclopentadiene-based ring-opening polymer hydride. Then, various measurements and evaluations were performed in the same manner as in Example 1. The results are shown in Table 1.

(Example 9)
The polymerization catalyst Nos. shown in Table 2 A ring-opening polymerization reaction was carried out using 0.100 parts of the tungsten complex of No. 5 in the same manner as in Example 6 to obtain a solution containing a dicyclopentadiene-based ring-opening polymer. When the molecular weight of the dicyclopentadiene ring-opening polymer was measured using a part of this solution, 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, coagulated, filtered off and dried to obtain 99 parts of a dicyclopentadiene ring-opening polymer.
Similarly, the following steps were carried out to obtain 26.9 parts of a dicyclopentadiene-based 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 racemodiad (syndiotacticity) was 100%. Further, using a differential scanning calorimeter (DSC), it was confirmed that the glass transition temperature of the obtained dicyclopentadiene-based ring-opening polymer hydride was 90 ° C. or higher and 120 ° C. or lower.
Then, the obtained dicyclopentadiene-based ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain pellets, unstretched film, and stretched film of the dicyclopentadiene-based ring-opening polymer hydride. Then, 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-based ring-opening polymer hydride was obtained in the same manner as in Example 1 except that the hydrogenation reaction in the step was carried out 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 of racemodiad (syndiotacticity) was 100%.
Then, the obtained dicyclopentadiene-based ring-opening polymer hydride was treated in the same manner as in Example 1 to obtain pellets, unstretched film, and stretched film of the dicyclopentadiene-based ring-opening polymer hydride. Then, 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-based ring-opening polymer hydride having a syndiotacticity of 89% and a hydrogenation rate of 99.5% was prepared as follows.

<Preparation of dicyclopentadiene ring-opening polymer>
0.3 part of n-hexane solution of diethylaluminum ethoxide with a concentration of 19% and 0.1 part of tetrachlorotungene phenylimide (tetrahydrofuran) complex (polymerization catalyst No. 6 shown in Table 2) were dissolved in 3 parts of toluene. To obtain a catalytic solution.
On the other hand, in a metal reactor (manufactured by Sumitomo Heavy Industries, Ltd.) with a stirrer and a temperature control jacket in which the inside was sufficiently dried and replaced with nitrogen, 350 parts of cyclohexane, 6.4 parts of 1-hexene, and a concentration of 70% were added. 145 parts of a cyclohexane solution of dicyclopentadiene (endo-form content of 99% or more) was added, and the whole temperature was raised to 50 ° C. The catalyst solution was added thereto to initiate a ring-opening polymerization reaction.
After stirring for 270 minutes while keeping the whole volume at 55 ° C., 1.5 parts of methanol was added to stop the ring-opening polymerization reaction. By adding methanol to the polymerization reaction solution, the effect of insolubilizing the catalyst component can also be obtained.
The weight average molecular weight (Mw) of the dicyclopentadiene ring-opening polymer contained in the obtained polymerization reaction solution was 28,700, the number average molecular weight (Mn) was 9570, and the molecular weight distribution (Mw / Mn) was 3.0. there were.

To the obtained polymerization reaction solution, 1 part of diatomaceous earth (Radiolite # 1500 manufactured by Showa Chemical Industry Co., Ltd.) was added as a filtration aid. This suspension was filtered with a leaf filter (CFR2 manufactured by IHI Corporation), and the insolubilized catalyst component was filtered off together with diatomaceous earth to obtain a solution of a dicyclopentadiene-based ring-opening polymer.

<Hydrogenation of ring-opening polymer>
After transferring the solution of the dicyclopentadiene ring-opening polymer obtained according to the above to a reactor with a stirrer and a temperature control jacket (manufactured by Sumitomo Heavy Industries, Ltd.), the concentration of the dicyclopentadiene ring-opening polymer is 9. 600 parts of cyclohexane and 0.1 part of carbonylchlorohydridotris (triphenylphosphine) ruthenium were added so as to be%. Next, a hydrogenation reaction was carried out at a hydrogen pressure of 4 MPa and a temperature of 180 ° C. for 6 hours while stirring the whole volume at a rotation speed of 64 rpm to obtain a slurry containing particles of a dicyclopentadiene-based ring-opening polymer hydride.
By centrifuging the slurry thus obtained, the solid content and the solution were separated, and the solid content was dried under reduced pressure at 60 ° C. for 24 hours to obtain a dicyclopentadiene-based ring-opening polymer hydride 27.0. I 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 racemodiad (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 set to 270 to 280 ° C. and the die set temperature was set to 250 ° C. during the operation of the twin-screw extruder.

<Manufacturing 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. The obtained unstretched film was measured for tensile strength and elongation at break according to the above. The results are shown in Table 1.
-Barrel temperature setting: 280 ° C to 290 ° C
-Die temperature: 270 ° C
・ Screw rotation speed: 30 rpm

<Manufacturing of resin film (stretched)>
The same operation as in Example 1 was carried out to obtain a stretched film. The reflow resistance and the amount of gas generated were evaluated for the obtained stretched film. The results are shown in Table 1.

As is clear from Table 1, according to the dicyclopentadiene-based 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 or the like having both high strength and ductility. Therefore, the dicyclopentadiene-based ring-opening polymer hydride of the present invention can be suitably used for producing various resin molded products, films and the like. Further, the biaxially stretched film produced in Examples 1 to 3 containing a dicyclopentanediene-based ring-opening polymer hydride having a syndiotacticity of 100% and a hydrogenation rate of 98.0% or more It is particularly useful as an electric / electronic material because it has excellent reflow resistance and the amount of gas generated from the film is small.

(Example 10)
The unstretched resin film (unstretched film) produced in the same manner as in Example 1 was subjected to the following stretching step and heat fixing treatment step to obtain a stretched film. For the obtained stretched film, haze, tensile strength, elongation at break, and coefficient of linear expansion were measured according to the above. The results are shown in Table 3.
<Stretching process and heat fixing process>
The unstretched film obtained according to the above is cut into 120 mm squares, and the stretching step according to the following conditions and the heat fixing treatment step are performed in this order with a multi-tank biaxially stretched birefringence orientation axis measuring device (manufactured by Eto). carried out. As a result, a stretched film of a dicyclopentadiene-based ring-opening polymer hydride, which is a resin film containing a dicyclopentadiene-based ring-opening polymer hydride having a thickness of 25 μm, was obtained.
-Stretching process-Simultaneous biaxial stretching treatment-Stretching speed: 3.3 mm / sec
-Stretching temperature: 100 ° C
-Stretching ratio: 2 times in MD (Machine Direction) direction, 2 times in TD (Transverse Direction) direction-Heat fixing process-Heat fixing temperature: 220 ° C
・ Heat fixing time: 30 seconds

(Examples 11 to 15)
A stretched film was obtained and various measurements were carried out in the same manner as in Example 10 except that the stretching temperature in the stretching step, the stretching rate, and the heat fixing temperature in the heat fixing 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 by using a dicyclopentadiene-based ring-opening polymer hydride having a syndiotacticity of 100% and a hydrogenation rate of 98.0% or more was prepared. It was confirmed that the stretched film can be satisfactorily produced by the stretching treatment at a stretching temperature of 95 ° C. or higher and 130 ° C. or lower. In particular, from Table 3, it can be seen that by adjusting the stretching temperature, it is possible to effectively suppress the occurrence of haze in the obtained stretched film.

According to the present invention, it is possible to provide a dicyclopentadiene-based ring-opening polymer hydride capable of forming a resin molded product or the like having both high strength and ductility.
Further, according to the present invention, it is possible to provide a resin film and a resin molded product having both high strength and ductility.
According to the present invention, it is possible to provide a method for producing a stretched film, which can satisfactorily produce a stretched film by using a resin film having both high strength and ductility.

Claims (8)

A dicyclopentadiene-based ring-opening polymer hydride having a syndiotacticity of 99% or more and a hydrogenation rate of 98.0% or more. The dicyclopentadiene-based ring-opening polymer hydride according to claim 1, wherein the hydrogenation rate is 99.0% or more. A resin molded product containing the dicyclopentadiene-based ring-opening polymer hydride 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 generated belonging to the mass number 18 (m / z) generated between room temperature and 300 ° C. measured by the heating generated gas mass spectrometry is 0. The resin film according to claim 4, which is less than 5% by 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).
A hydrogenation step of hydrogenating the dicyclopentadiene-based ring-opening polymer to obtain a dicyclopentadiene-based ring-opening polymer hydride having a hydrogenation rate of 98.0% or more.
A method for producing a dicyclopentadiene-based ring-opening polymer hydride including.

[In formula (α), Ph represents a phenyl group, and R ¹ and R ² independently form a monovalent linear, branched, or cyclic hydrocarbon group having 1 to 6 carbon atoms. Indicates; X represents a hydrogen atom, a halogen atom, a nitro group, an amino group, or a cyano group, n represents an integer of 0 to 5, and when n is an integer of 1 or more, a plurality of X's are indicated. ^{May be} the same or different; Y indicates C (R ³ ) ₂ R ⁴ (where each R ³ is independently -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 , where each R ⁵ is independently hydrogen, linear with 1 to 12 carbon atoms. Alternatively, a heteroalkyl group having 1 to 10 carbon atoms having 1 to 3 heteroatoms independently selected from a branched alkyl group, nitrogen, oxygen, or sulfur, a phenyl group, and a 3- to 7-membered saturated or one-membered group. 1 to 4 heteros independently selected from partially unsaturated carbocycles, 6 to 10-membered bicyclic saturated rings, partially unsaturated rings, or aryl rings, nitrogen, oxygen, or sulfur. 5- to 6-membered monocyclic heteroaryl ring with atoms, 3- to 7-membered saturated or partially unsaturated complex with 1 to 3 heteroatoms independently selected from nitrogen, oxygen, or sulfur Seven to ten-membered bicyclic saturated or partially unsaturated heteroatoms with 1 to 5 heteroatoms independently selected from rings, nitrogen, oxygen, or sulfur, and nitrogen, oxygen, or It is an optionally substituted group selected from an 8- to 10-membered bicyclic heteroaryl ring having 1 to 5 heteroatoms selected independently of sulfur, or optionally. two R ^5, optionally in combination with the intervening atoms, in addition to said the intervening atoms, nitrogen, oxygen, or 0-4 heteroatoms independently selected from nitrogen Forming an optionally substituted three to ten-membered monocyclic or bicyclic, saturated ring, partially unsaturated ring, or aryl ring; R ⁴ is optional. (); And Z represents a 5- to 14-membered heteroaryl group having 1 to 4 heteroatoms selected from the group consisting of nitrogen, oxygen, and sulfur. ] A stretched film comprising a stretching step of stretching an unstretched film formed by using the dicyclopentadiene ring-opening polymer hydride according to claim 1 or 2 at a stretching temperature of 95 ° C. or higher and 130 ° C. or lower. Production method. The method for producing a stretched film according to claim 7, further comprising a heat fixing treatment step of heat-treating the film that has undergone the stretching step at a heat fixing temperature of 175 ° C. or higher and 225 ° C. or lower.