JP2017145409A - Production method of hydrogenated ring-opening metatheses copolymer, and hydrogenated product thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a hydrogenated ring-opening metatheses copolymer which has an extremely small amount of a residual metal component and is particularly suitable for a resist polymer for manufacturing a semiconductor.SOLUTION: A production method for producing a hydrogenated ring-opening metatheses copolymer is provided, which includes a step of hydrogenating a carbon-carbon double bond in a ring-opening metatheses copolymer by use of a hydrogenation reaction catalyst comprising ruthenium (Ru) metal and rhodium (Rh) metal deposited on carbon in the presence of hydrogen. In the production method of a hydrogenated ring-opening metatheses copolymer, it is preferable that a mass ratio Ru/Rh of Ru to Rh in the catalyst is 80/20 to 99/1; a hydrogenation percentage is 99.5 mol% or more; and the total content of metals derived from a polymerization catalyst and the hydrogenation catalyst is 1000 ppm or less.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a hydrogenated product of a ring-opening metathesis copolymer and the hydrogenated product thereof.

  In recent years, applications for optical materials such as microlenses, imaging lenses, optical elements (microlens arrays, optical waveguides, optical switching, Fresnel zone plates, binary optical elements, blaze diffractive optical elements, photonic crystals, etc.) for digital camera modules, ArF High-purity, highly transparent resin for semiconductor manufacturing process materials such as resist materials for excimer laser exposure and EUV exposure, anti-reflection filters, recording media, display materials, electronic device materials such as organic EL and liquid crystal plastic members, etc. The demand for materials is increasing, and hydrogenated products of ring-opening metathesis copolymers having excellent optical properties are being studied for wide application in these fields.

  As a method for producing a hydrogenated product of a ring-opening metathesis copolymer, a cyclic olefin monomer is polymerized using a ring-opening metathesis polymerization catalyst, followed by a ring-opening metathesis polymerization using a hydrogenation reaction catalyst (hydrogenation catalyst). A method of hydrogenating the remaining double bond later is known.

  The metal component contained in the catalyst remains in the hydrogenated product of the ring-opening metathesis copolymer, so that optical materials such as microlenses for digital camera modules, imaging lenses, and optical elements, and resist polymer materials for semiconductor manufacturing In the development of advanced semiconductor manufacturing technology applications and optical material applications, these problems may occur due to discoloration in products, deterioration of optical characteristics, adverse effects of lithography characteristics, or metal contamination within the semiconductor manufacturing process. It is a problem.

As a method for solving this problem of residual metal removal, a method for removing a residual metal component from a polymer has been proposed.
As a method for removing residual metal in a ring-opening metathesis polymer product produced using a transition metal catalyst, for example, a method of contacting a solution of a coordination copolymer of a cyclic olefin monomer and an olefin with an alkali or an acid aqueous solution, or , A method of contacting a solution of a coordination copolymer of a cyclic olefin monomer and an olefin with a filter medium such as diatomaceous earth (Patent Document 1), or a cyclic olefin polymer obtained by addition polymerization of a cyclic olefin monomer with a palladium-based catalyst Is known to reduce the palladium in the polymer from 6.0 ppm to 0.13 ppm (Patent Document 2) by treating it with an adsorbent modified with mercaptopropyltrimethoxysilane on the silica surface. It has been.

  Further, as a method for purifying a polymer obtained by a ring-opening metathesis polymerization reaction and a hydrogenation reaction, a polymer solution containing a polymerization catalyst residue is treated with an adsorbent carrying a hydrogenation reaction catalyst, and titanium derived from the polymerization catalyst is obtained. A method of obtaining a hydrogenated thermoplastic norbornene polymer having a metal content of 1 ppm or less is known (Patent Document 3).

  Patent Document 4 discloses the following method. A cyclic olefin monomer containing an ester is subjected to ring-opening metathesis polymerization with a tungsten-based catalyst, and then hydrogenated with a ruthenium-based complex catalyst to obtain a ring-opening metathesis polymer hydrogenated solution. Thereafter, the oxidizing agent or basic compound is added to the ring-opening metathesis polymer hydrogenated solution, and the operation of extracting the residual metal component is repeated to remove the metal component in the poor solvent phase. Then, tungsten in the polymer is reduced to 3 ppm and ruthenium to less than 0.1 ppm.

  Furthermore, Patent Document 5 discloses the following method. Cyclic olefin monomer having a cyano group is subjected to ring-opening metathesis polymerization with a molybdenum catalyst. Thereafter, trimethylenediamine is added and stirred, and then the polymer solution is added to methanol to precipitate a ring-opening metathesis polymer. Furthermore, after making it contact with a ring-opening metathesis polymer and an acidic compound, a metal component is reduced from 430 ppm to 30 ppm by discharging to methanol.

  Patent Document 6 discloses the following method. 3,6-Epoxy-1,2,3,6-tetrahydrophthalic anhydride is subjected to ring-opening metathesis polymerization with bis (tricyclohexylphosphine) benzylidene ruthenium chloride, which is a ring-opening metathesis catalyst. Activate. Thereby, a cyclic olefin polymer containing an oxygen atom in the main chain of the polymer is obtained. The solution containing this polymer is passed through activated alumina three times and subjected to an adsorption treatment to remove and purify the transition metal derived from the polymerization catalyst.

  Further, in Patent Document 7, after hydrogenation, a liquid containing a cyclic olefin polymer having an alkoxycarbonyl group, an alkoxyalkyloxycarbonyl group, and an alkoxycarbonylalkyloxycarbonyl group as a substituent and a metal component, a basic functional group, and an acidic group. Examples of the polymer purification method include contacting with an organic compound containing a functional group and then contacting with a basic adsorbent to remove a metal component contained in the liquid. However, since the metal component could not be removed during the hydrogenation reaction, the residual metal components derived from the polymerization catalyst and the hydrogenation reaction catalyst could not be reduced to 30 ppb or less.

  In recent years, in semiconductor manufacturing processes, miniaturization of circuit patterns in the lithography process has been advanced in order to improve the degree of integration, and logic circuits, DRAM circuits, and NAND flash memory circuits are being mass-produced in 1X nm generation. is there. These use an ArF laser with a wavelength of 193 nm, and pattern formation is performed by a double or multi-patterning technique in which the immersion technique and the exposure are repeated twice or more times. If a large amount of residual metal exists in the resist polymer material used in the lithography process, a short circuit due to a leakage current of the semiconductor circuit is caused. In recent double or multi-patterning that repeats pattern formation, a resist is repeatedly used. Therefore, residual metal is easily accumulated in a semiconductor circuit, and it has become necessary to reduce the residual metal in the resist polymer to the limit.

  In addition, in optical applications such as microlenses, imaging lenses, and optical elements for digital camera modules, when using hydrogenated ring-opening metathesis copolymer as an optical film or molded product, a film is obtained by melt molding. However, when trying to obtain a molded product by injection molding, there are disadvantages that the molding process causes yellowing or deterioration of the polymer, or appearance defects due to generation of polymer degradation products or gels. Therefore, in order not to impair the excellent transparency of the hydrogenated product of the ring-opening metathesis copolymer, it is necessary to develop a hydrogenated product of the ring-opening metathesis copolymer in which the residual metal in the polymer is reduced to the limit. It was.

JP-A-6-240511 JP 2008-101169 A JP-A-4-36312 JP-A-7-109310 JP-A-10-324737 JP 2001-163958 A Japanese Patent No. 5597643

  As described above, in recent semiconductor manufacturing processes, in order to improve the degree of integration, pattern formation is performed by a double or multi-patterning technique in which a liquid immersion technique and exposure are repeated twice or more in a lithography process. Since the multi-patterning technique repeats pattern formation, the resist polymer material used in the process is also repeatedly used. For this reason, in order to avoid a short circuit due to a leakage current caused by a residual metal in the semiconductor circuit, it is necessary to reduce the metal remaining on the circuit to the limit.

  When manufacturing the hydrogenated product of the ring-opening metathesis copolymer that is the material of the present invention, the residual metal component derived from each catalyst is set to 30 ppb or less after the hydrogenation reaction as in Patent Document 7. In contrast to the prior art that could not be achieved, the present inventors have studied as an object to provide the copolymer in which residual metal is remarkably reduced. As a result, by applying the production method of the present invention, the total metal content derived from the catalyst can be reduced to 1000 ppb or less without performing demetallization purification of the polymer, and further, by demetallizing and purifying the polymer of the present invention, It has been found that the metal component content can be 10 ppb or less.

  In addition, when the hydrogenated product of the ring-opening metathesis copolymer obtained by the production method of the present invention is heated and melt-molded, a molded product having excellent transparency that does not cause yellowing deterioration or turbidity derived from residual metal is obtained. I found out that

  The present invention is shown below.

（式中、Ｒ^１が酸不安定な炭素数４〜２０のアルコキシカルボニル基、炭素数３〜２０のアルコキシアルキルオキシカルボニル基、または炭素数４〜２０のアルコキシカルボニルアルキルオキシカルボニル基から選ばれ、ｊは、０または１である。）

（式中、Ｒ^２〜Ｒ^３はそれぞれ独立に、水素または炭素数１〜１０のアルキル基から選ばれ、Ｘ^１は−Ｏ−、または−ＣＲ^４Ｒ^５−から（Ｒ^４およびＲ^５はそれぞれ水素または炭素数１〜２０のアルキル基を表す）選ばれる。）
（２）上記（１）に記載の開環メタセシス共重合体の水素添加物の製造方法において、
上記重合触媒および水素添加反応触媒由来の金属がモリブデン、タングステン、ルテニウム、およびロジウムから選択される一種または二種以上を含む開環メタセシス共重合体の水素添加物の製造方法。
（３）上記（１）または（２）に記載の開環メタセシス共重合体の水素添加物の製造方法において、
上記カーボン担持水素添加反応触媒における上記ルテニウムと上記ロジウムの合計質量が上記開環メタセシス共重合体に対して０．０５質量％以上１．０質量％以下である開環メタセシス共重合体の水素添加物の製造方法。
（４）上記（１）乃至（３）いずれか一つに記載の開環メタセシス共重合体の水素添加物の製造方法において、
得られる上記開環メタセシス共重合体の水素添加物が、半導体製造リソグラフィープロセスで使用されるレジスト原料である開環メタセシス共重合体の水素添加物の製造方法。
（５）上記一般式（１）で表される繰返し構造単位［Ａ］と上記一般式（２）で表される繰返し構造単位［Ｂ］と下記一般式（３）で表される繰返し構造単位［Ｄ］とを含み、上記一般式（１）で表される繰返し構造単位［Ａ］と上記一般式（２）で表される繰返し構造単位［Ｂ］の合計と、下記一般式（３）で表される繰返し構造単位［Ｄ］との構成モル比が（［Ａ］＋［Ｂ］）／［Ｄ］＝９９／１〜１／９９である開環メタセシス共重合体の水素添加物を（１）乃至（３）いずれか一つに記載の方法で製造した開環メタセシス共重合体の水素添加物。

（式中、Ｒ^６〜Ｒ^９は、水素、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、炭素数２〜２０のアルコキシアルキル基、炭素数２〜２０のアルコキシカルボニル基または炭素数７〜２０のアリールオキシカルボニル基から選ばれ、Ｘ^２は−Ｏ−および−ＣＲ^１０Ｒ^１１−から（Ｒ^１０およびＲ^１１はそれぞれ水素または炭素原子数１〜２０のアルキル基を表す）選ばれ、同一でも異なってもよい。また、Ｒ^６〜Ｒ^９は、互いに結合してもよく、ｋは０または１である。）
（６）光学部品の原料である（５）に記載の開環メタセシス共重合体の水素添加物。
（７）上記（５）または（６）に記載の開環メタセシス共重合体の水素添加物を脱金属精製することによって各触媒由来の全金属成分の全含有量が、１０ｐｐｂ以下であることを特徴とする開環メタセシス共重合体の水素添加物。 (1) A production method for producing a hydrogenated product of a ring-opening metathesis copolymer,
Hydrogenating a carbon-carbon double bond of a ring-opening metathesis copolymer using a carbon-supported hydrogenation reaction catalyst of ruthenium (Ru) metal and rhodium (Rh) metal in the presence of hydrogen,
The ring-opening metathesis copolymer includes a repeating structural unit [A] represented by the following general formula (1) and a repeating structural unit [B] represented by the following general formula (2), and the structural unit [A ] And the molar ratio ([A] / [B]) of the structural unit [B] is 5/95 or more and 90/10 or less,
The ruthenium and rhodium mass ratio (Ru / Rh) in the carbon-supported hydrogenation reaction catalyst is 80/20 or more and 99/1 or less,
The hydrogenation rate of the double bond of the hydrogenated product of the obtained ring-opening metathesis copolymer is 99.5 mol% or more,
The elimination rate of the acid labile group in the structural unit [A] in the hydrogenated product of the obtained ring-opening metathesis copolymer is 1 mol% or less,
A method for producing a hydrogenated product of a ring-opening metathesis copolymer in which the total content of a polymerization catalyst and a metal derived from a hydrogenation reaction catalyst in the hydrogenated product of the obtained ring-opening metathesis copolymer is 1000 ppb or less.

Wherein R ¹ is selected from an acid labile alkoxy group having 4 to 20 carbon atoms, an alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms, or an alkoxycarbonylalkyloxycarbonyl group having 4 to 20 carbon atoms, j is 0 or 1.)

(In the formula, R ^{2 to} R ³ are each independently selected from hydrogen or an alkyl group having 1 to 10 carbon atoms, and X ¹ is —O— or —CR ⁴ R ⁵ — (R ⁴ and R ⁵ are Each represents hydrogen or an alkyl group having 1 to 20 carbon atoms).
(2) In the method for producing a hydrogenated product of the ring-opening metathesis copolymer described in (1) above,
A method for producing a hydrogenated product of a ring-opening metathesis copolymer, wherein the metal derived from the polymerization catalyst and the hydrogenation reaction catalyst includes one or more selected from molybdenum, tungsten, ruthenium, and rhodium.
(3) In the method for producing a hydrogenated product of a ring-opening metathesis copolymer according to (1) or (2) above,
Hydrogenation of a ring-opening metathesis copolymer in which the total mass of the ruthenium and rhodium in the carbon-supported hydrogenation reaction catalyst is 0.05% by mass or more and 1.0% by mass or less with respect to the ring-opening metathesis copolymer. Manufacturing method.
(4) In the method for producing a hydrogenated product of a ring-opening metathesis copolymer according to any one of (1) to (3) above,
A method for producing a hydrogenated product of a ring-opening metathesis copolymer, wherein the obtained hydrogenated product of the ring-opening metathesis copolymer is a resist material used in a semiconductor production lithography process.
(5) The repeating structural unit [A] represented by the general formula (1), the repeating structural unit [B] represented by the general formula (2), and the repeating structural unit represented by the following general formula (3) [D], the total of the repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2), and the following general formula (3) A hydrogenation product of a ring-opening metathesis copolymer having a structural molar ratio of ([A] + [B]) / [D] = 99/1 to 1/99 with the repeating structural unit [D] represented by A hydrogenated ring-opening metathesis copolymer produced by the method according to any one of (1) to (3).

(Wherein R ^{6 to} R ⁹ are hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, X ² is selected from an alkoxycarbonyl group having 2 to 20 carbon atoms or an aryloxycarbonyl group having 7 to 20 carbon atoms, and X ² is —O— and —CR ¹⁰ R ¹¹ — (R ¹⁰ and R ¹¹ are each a hydrogen atom or a carbon atom. (Represents an alkyl group of 1 to 20), which may be the same or different, and R ^{6 to} R ⁹ may be bonded to each other, and k is 0 or 1.)
(6) The hydrogenated product of the ring-opening metathesis copolymer according to (5), which is a raw material for optical components.
(7) The total content of all metal components derived from each catalyst is 10 ppb or less by demetallizing the hydrogenated product of the ring-opening metathesis copolymer described in (5) or (6) above. A hydrogenated ring-opening metathesis copolymer.

  According to the present invention, it is possible to provide a resist polymer for semiconductor production having an extremely low amount of residual metal component, and a hydrogenated ring-opening metathesis copolymer particularly suitable for optical components obtained by heat-melt molding. it can. Therefore, it can be expected to eliminate a short circuit due to a leakage current of a semiconductor circuit due to a residual metal component, and to obtain a molded body having high transparency inherent in resin without coloring yellowing in heat-melt molding.

  Embodiments of the present invention will be described below. In addition, “A to B” in the numerical range represents A or more and B or less unless otherwise specified.

  A method for producing a hydrogenated product of a ring-opening metathesis copolymer of the present invention is a method for producing a hydrogenated product of a ring-opening metathesis copolymer, comprising: a ruthenium (Ru) metal in the presence of hydrogen; A step of hydrogenating the carbon-carbon double bond of the ring-opening metathesis copolymer using a rhodium (Rh) metal-supported hydrogenation reaction catalyst. The ring-opening metathesis copolymer includes a repeating structural unit [A] represented by the following general formula (1) and a repeating structural unit [B] represented by the following general formula (2), and the structural unit [A ] And the structural unit [B] in a molar ratio ([A] / [B]) of 5/95 or more and 90/10 or less, and a mass ratio of the ruthenium and the rhodium in the carbon-supported hydrogenation reaction catalyst. (Ru / Rh) is 80/20 or more and 99/1 or less, and the hydrogenation rate of the double bond of the hydrogenated product of the obtained ring-opening metathesis copolymer is 99.5 mol% or more, and thus obtained. In the hydrogenated product of the ring-opening metathesis copolymer, the elimination rate of the acid labile group in the structural unit [A] in the hydrogenated product of the ring-opening metathesis copolymer is 1 mol% or less. Gold from polymerization catalyst and hydrogenation reaction catalyst The total content of at most 1000 ppb.

（式中、Ｒ^１が酸不安定な炭素数４〜２０のアルコキシカルボニル基、炭素数３〜２０のアルコキシアルキルオキシカルボニル基、または炭素数４〜２０のアルコキシカルボニルアルキルオキシカルボニル基から選ばれ、ｊは、０または１である。）

Wherein R ¹ is selected from an acid labile alkoxy group having 4 to 20 carbon atoms, an alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms, or an alkoxycarbonylalkyloxycarbonyl group having 4 to 20 carbon atoms, j is 0 or 1.)

（式中、Ｒ^２〜Ｒ^３はそれぞれ独立に、水素または炭素数１〜１０のアルキル基から選ばれ、Ｘ¹は−Ｏ−、または−ＣＲ^４Ｒ^５−から（Ｒ^４、Ｒ^５は水素、炭素数１〜２０のアルキル基を表す）選ばれる。）

(Wherein R ^{2 to} R ³ are each independently selected from hydrogen or an alkyl group having 1 to 10 carbon atoms, X ¹ is —O—, or —CR ⁴ R ⁵ — (R ⁴ , R ⁵ are Represents hydrogen, an alkyl group having 1 to 20 carbon atoms).

  Furthermore, the hydrogenated product of the ring-opening metathesis copolymer of the present embodiment may contain a repeating structural unit [D] represented by the following general formula (3), and a repeating structure represented by the general formula (1) The constituent molar ratio between the sum of the unit [A] and the repeating structural unit [B] represented by the general formula (2) and the repeating structural unit [D] represented by the general formula (3) is, for example, ([ A] + [B]) / [D] = 99/1 to 1/99.

（式中、Ｒ^６〜Ｒ^９は、水素、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、炭素数２〜２０のアルコキシアルキル基、炭素数２〜２０のアルコキシカルボニル基または炭素数７〜２０のアリールオキシカルボニル基から選ばれ、Ｘ^２は−Ｏ−および−ＣＲ^１０Ｒ^１１−から（Ｒ^１０およびＲ^１１はそれぞれ水素または炭素原子数１〜２０のアルキル基を表す）選ばれ、同一でも異なってもよい。また、Ｒ^６〜Ｒ^９は、互いに、結合してもよく、ｋは０または１である。）

(Wherein R ^{6 to} R ⁹ are hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, X ² is selected from an alkoxycarbonyl group having 2 to 20 carbon atoms or an aryloxycarbonyl group having 7 to 20 carbon atoms, and X ² is —O— and —CR ¹⁰ R ¹¹ — (R ¹⁰ and R ¹¹ are each a hydrogen atom or a carbon atom. (Represents an alkyl group of 1 to 20), which may be the same or different, and R ^{6 to} R ⁹ may be bonded to each other, and k is 0 or 1.)

(Method for producing ring-opening metathesis copolymer)
The hydrogenated product of the ring-opening metathesis copolymer in the present embodiment is a cyclic olefin monomer corresponding to the repeating structural unit [A] represented by the general formula (1), and a repeating structure represented by the general formula (2). It is obtained by copolymerizing a cyclic olefin monomer corresponding to the unit [B] with a ring-opening metathesis catalyst and hydrogenating it under a hydrogenation reaction catalyst.

  Furthermore, the cyclic olefin monomer corresponding to the repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2), and the repeating represented by the general formula (3) What is obtained by copolymerizing a cyclic olefin monomer corresponding to the structural unit [D] as a third component with a ring-opening metathesis catalyst and hydrogenating it under the hydrogenation reaction catalyst in this embodiment It is.

In this embodiment, R ¹ of the repeating structural unit [A] represented by the general formula (1) of the ring-opening metathesis copolymer having a carbon-carbon double bond is an acid labile tertiary or quaternary. And an alkoxycarbonyl group having 4 to 20 carbon atoms, an alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms, or an alkoxycarbonylalkyloxycarbonyl group having 4 to 20 carbon atoms.

More specifically, in the general formula (1), R ¹ is an acid generated by exposure from an acid generator as a resist polymer used in ArF exposure lithography for semiconductor production, and an ester decomposition reaction by generating an electronically stable carbocation. Is an acid labile ester substituent having a tertiary or quaternary alkoxy group induced. The hydrogenation product of the ring-opening metathesis copolymer in the present embodiment is a carboxylic acid generated from R ¹ of the repeating structural unit [A] by acid decomposition, for example, an alkali such as tetramethylammonium hydroxide (TMAH) aqueous solution It is used as a resist polymer that forms a pattern by dissolving and developing in a developer.

On the other hand, propylene glycol monomethyl ether acetate (PGMEA) is generally used as the organic solvent of the resist solution used in lithography, and the generation of carboxylic acid in the polymer for photoresist is caused by dissolution of the polymer in solvents such as PGMEA. Worsens sex.
That is, at the time of varnish production, there is no carboxylic acid in the polymer and it must be dissolved in a specific solvent, and a material that generates carboxylic acid by an acid generated from an acid generator is preferably used only at the time of semiconductor production exposure.

In the ring-opening metathesis copolymer in the present embodiment, the acid labile R ¹ in the repeating structural unit [A] represented by the general formula (1) includes an alkoxycarbonyl group having 4 to 20 carbon atoms, and a carbon number 3 It is selected from an alkoxyalkyloxycarbonyl group having -20 carbon atoms, or an alkoxycarbonylalkyloxycarbonyl group having 4-20 carbon atoms.

  Examples of the alkoxycarbonyl group having 4 to 20 carbon atoms include isopropoxycarbonyl, tert-butoxycarbonyl, cyclopentyloxycarbonyl, cyclohexyloxycarbonyl, cyclooctyloxycarbonyl, norbornyloxycarbonyl, 1-methylcyclopentyloxycarbonyl, 1- Ethylcyclopentyloxycarbonyl, 1-methylnorbornyloxycarbonyl, 1-ethylnorbornyloxycarbonyl, tetrahydrofuran-2-yloxycarbonyl, tetrahydropyran-2-yloxycarbonyl, 1-adamantyloxycarbonyl, and 2-adamantyloxycarbonyl Etc.

  Examples of the alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms include methoxymethyloxycarbonyl, ethoxymethyloxycarbonyl, n-propoxymethyloxycarbonyl, isopropoxymethyloxycarbonyl, n-butoxymethyloxycarbonyl, tert- Butoxymethyloxycarbonyl, cyclopentyloxymethyloxycarbonyl, cyclohexyloxymethyloxycarbonyl, cyclooctyloxymethyloxycarbonyl, norbornyloxymethyloxycarbonyl, 1-methylcyclopentyloxymethyloxycarbonyl, 1-ethylcyclopentyloxymethyloxycarbonyl, 1 -Methylnorbornyloxymethyloxycarbonyl, 1-ethylnorbornyloxymethyloxycal Nyl, 1-ethoxypropyloxymethyloxycarbonyl, 1-ethoxy-1-methylethyloxymethyloxycarbonyl, tetrahydrofuran-2-yloxymethyloxycarbonyl, tetrahydropyran-2-yloxymethyloxycarbonyl, 1-adamantyloxymethyl Examples include oxycarbonyl and 2-adamantyloxymethyloxycarbonyl.

  Further, examples of the alkoxycarbonylalkyloxycarbonyl group having 4 to 20 carbon atoms include methoxycarbonylmethyloxycarbonyl, ethoxycarbonylmethyloxycarbonyl, n-propoxycarbonylmethyloxycarbonyl, isopropoxycarbonylmethyloxycarbonyl, n-butoxycarbonyl. Methyloxycarbonyl, tert-butoxycarbonylmethyloxycarbonyl, cyclopentyloxycarbonylmethyloxyisocarbonyl, cyclohexyloxycarbonylmethyloxycarbonyl, cyclooctyloxycarbonylmethyloxycarbonyl, norbornyloxycarbonylmethyloxycarbonyl, 1-methylcyclopentyloxycarbonylmethyl Oxycarbonyl, 1-ethylcyclopen Ruoxycarbonylmethyloxycarbonyl, 1-methylnorbornyloxycarbonylmethyloxycarbonyl, 1-ethylnorbornyloxycarbonylmethyloxycarbonyl, 1-ethoxypropyloxycarbonylmethyloxycarbonyl, 1-ethoxy-1-methylethyloxycarbonylmethyl Examples include oxycarbonyl, tetrahydrofuran-2-yloxycarbonylmethyloxycarbonyl, tetrahydropyran-2-yloxycarbonylmethyloxycarbonyl, 1-adamantyloxycarbonylmethyloxycarbonyl, and 2-adamantyloxycarbonylmethyloxycarbonyl.

Furthermore, R ^{2 to} R ³ in the repeating structural unit [B] represented by the general formula (2) are each independently selected from hydrogen or an alkyl group having 1 to 10 carbon atoms.
X ¹ is selected from —O— or —CR ⁴ R ⁵ — (R ⁴ and R ⁵ each represent hydrogen or an alkyl group having 1 to 20 carbon atoms).
In the general formula (2), R ^{2 to} R ³ are each independently hydrogen, methyl having 1 to 10 carbons, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, It is an alkyl group such as 1-ethylcyclopentyl or 1-ethylcyclohexyl, which may be the same or different.
X ¹ is selected from —O— or —CR ⁴ R ⁵ — (R ⁴ and R ⁵ each represent hydrogen or alkyl having 1 to 20 carbon atoms), and R ⁴ and R ⁵ are methyl, ethyl, isopropyl, Examples thereof include alkyl groups having 1 to 20 carbon atoms such as tert-butyl and cyclohexyl.

Here, the structural unit [B] represented by the general formula (2) has a higher polarity, suppresses water repellency, and can be designed to have a lower water contact angle as a resist polymer material. X ^{1 of} [B] is preferably —O—.

Furthermore, R ^{6 to} R ⁹ in the repeating structural unit [D] represented by the general formula (3) are hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, or 1 to 20 carbon atoms. Selected from an alkoxy group having 2 to 20 carbon atoms, an alkoxycarbonyl group having 2 to 20 carbon atoms having a primary or secondary alkoxy group, or an aryloxycarbonyl group having 7 to 20 carbon atoms. May be different.

X ² is selected from —O— and —CR ¹⁰ R ¹¹ — (R ¹⁰ and R ¹¹ each represent hydrogen or an alkyl group having 1 to 20 carbon atoms), and may be the same or different. R ^{6 to} R ⁹ may be bonded to each other.

  Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, pentyl, cyclopentyl, hexyl, cyclohexyl, octyl, cyclooctyl, and menthyl. Examples of the aryl group having ˜20 include phenyl, naphthyl, anthracenyl, o-tolyl, m-tolyl, p-tolyl, biphenyl and the like, and examples of the alkoxy group having 1 to 20 carbon atoms include methoxy, ethoxy, n -Propoxy, n-butoxy, tert-butoxy, n-pentoxy, cyclopentoxy, cyclohexyloxy, cyclooctyloxy, alkoxyalkyl groups having 2 to 20 carbon atoms include methoxymethyl, methoxyethyl, ethoxymethyl, ethoxyethyl , N-propoxy Methyl, iso-propoxymethyl, n- butoxymethyl, iso-butoxymethyl, tert- butoxymethyl, cyclopentyloxymethyl, cyclohexyloxymethyl, cyclooctyl oxymethyl, and the like. Examples of the alkoxycarbonyl group having 2 to 20 carbon atoms include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl, isobutoxycarbonyl, n-pentoxycarbonyl, n-hexoxycarbonyl, 3-methylbutoxycarbonyl , 2-methylpentoxycarbonyl, 3-methylpentoxycarbonyl, 4-methylpentoxycarbonyl and the like. Examples of the aryloxycarbonyl group having 6 to 20 carbon atoms include phenoxycarbonyl, benzyloxycarbonyl, 4-methylphenoxy Examples include carbonyl, 3,4-dimethylphenoxycarbonyl, 1-naphthoxycarbonyl, 2-naphthoxycarbonyl, 1-anthracenoxycarbonyl and the like.

R ^{6 to} R ⁹ may be bonded to each other. More specifically, at least two of R ^{6 to} R ⁹ may be bonded to form a ring structure, and in this case, —O—, —C—, —N—, or —S— It may be via a combination of Examples thereof include a cyclic ether structure, an epoxy structure, an oxetane structure, an acid anhydride structure, a cyclic hydrocarbon bond structure, an imide structure, and a cyclic thioether structure.

  In this embodiment, the structural molar ratio [A] / [B] of the structural unit [A] represented by the general formula (1) and the structural unit [B] represented by the general formula (2) is 5/95. It is -90/10, Preferably it is 10 / 90-80 / 20, More preferably, it is 20 / 80-70 / 30, Especially preferably, it is 30 / 70-70 / 30.

  In this embodiment, the total of the repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2) and the repeating represented by the general formula (3) The structural molar ratio with the structural unit [D] is ([A] + [B]) / [D] = 99/1 to 1/99, preferably 95/5 to 5/95, more preferably 90 /. It is 10-10 / 90, Most preferably, it is 90 / 10-20 / 80.

  By adding a repeating structural unit [D] to form a copolymer, in the lithography process in the semiconductor manufacturing process, the carboxylic acid generation efficiency generated by acid decomposition of the acid labile group is maintained, and multi-patterning is performed. Thus, it is possible to improve the resistance to repeated exposure. Furthermore, it can also be used as a lower layer film as an underlayer of a photoresist in a lithography process.

  In addition, in optical applications such as microlenses for digital camera modules, imaging lenses, and optical elements including MEMS, when the hydrogenated ring-opening metathesis copolymer is used as an optical film or molded product, in the melt molding process It is possible to suppress yellowing, deterioration and turbidity of the polymer as a molded product, or to suppress appearance defects due to generation of polymer decomposition products and gels, and decrease in transparency at a specific wavelength.

  As a specific cyclic olefin monomer of the ring-opening metathesis copolymer in which j = 0 in the repeating structural unit [A] represented by the general formula (1) in this embodiment, 5-isopropoxycarbonyl-bicyclo [ 2.2.1] Hept-2-ene, 5- (tert-butoxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5-cyclopentyloxycarbonyl-bicyclo [2.2.1] hept 2-ene, 5-cyclohexyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyclooctyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-norbol Nyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- (1-methylcyclopentyloxycarbonyl) -bicyclo [2.2.1] hept 2-ene, 5- (1-ethylcyclopentyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1-methylnorbornyloxycarbonyl) -bicyclo [2.2.1] ] Hept-2-ene, 5- (1-ethylnorbornyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1-ethoxypropyloxyoxycarbonyl) -bicyclo [2. 2.1] Hept-2-ene, 5- (1-ethoxy-1-methylethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (tetrahydrofuran-2-yloxycarbonyl) -Bicyclo [2.2.1] hept-2-ene, 5- (tetrahydropyran-2-yloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1-ada Nyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (2-adamantyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5-methoxymethyloxycarbonyl -Bicyclo [2.2.1] hept-2-ene, 5-ethoxymethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- (n-propoxymethyloxycarbonyl) -bicyclo [2 2.1] hept-2-ene, 5-isopropoxymethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- (n-butoxymethyloxycarbonyl) -bicyclo [2.2. 1] hept-2-ene, 5- (2-methyl-propoxymethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (tert-but Xymethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5-cyclopentyloxymethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxymethyloxycarbonyl- Bicyclo [2.2.1] hept-2-ene, 5-cyclooctyloxymethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-norbornyloxymethyloxycarbonyl-bicyclo [2 2.1] hept-2-ene, 5- (1-methylcyclopentyloxymethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1-ethylcyclopentyloxymethyloxycarbonyl) -Bicyclo [2.2.1] hept-2-ene, 5- (1-methylnorbornyloxymethylo Cicarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1-ethylnorbornyloxymethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- ( 1-ethoxypropyloxymethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1-ethoxy-1-methylethyloxymethyloxycarbonyl) -bicyclo [2.2.1] hept 2-ene, 5- (tetrahydrofuran-2-yloxymethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (tetrahydropyran-2-yloxymethyloxycarbonyl) -bicyclo [2 2.1] hept-2-ene, 5- (1-adamantyloxymethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene 5- (2-adamantyloxymethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- Ethoxycarbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- (n-propoxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5-isopropoxy Carbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- (n-butoxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (tert- Butoxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5-cyclopentyl Xoxycarbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyclooctyloxycarbonylmethyl Oxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-norbornyloxycarbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- (1-methylcyclopentyloxycarbonyl Methyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1-ethylcyclopentyloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- ( 1-methylnorbornyloxycarbonylmethyloxycarbonyl) -bishi Chlo [2.2.1] hept-2-ene, 5- (1-ethylnorbornyloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1-ethoxy Propyloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1-ethoxy-1-methylethyloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept- 2-ene, 5- (tetrahydrofuran-2-yloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (tetrahydropyran-2-yloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1-adamantyloxycarbonylmethyloxycarbonyl) Bicyclo [2.2.1] hept-2-ene, 5- (2-adamantyloxycarbonyl methyloxy carbonyl) - bicyclo [2.2.1] hept-2-ene, and the like.

Further, as described above, as a specific cyclic olefin monomer of the ring-opening metathesis copolymer in which j = 1 in the repeating structural unit [A] represented by the general formula (1), 8-isopropoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tert-butoxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclopentyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclohexyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclooctyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-norbornyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-methylcyclopentyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethylcyclopentyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-methylnorbornyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethylnorbornyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethoxypropyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethoxy-1-methylethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydrofuran-2-yloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydropyran-2-yloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-adamantyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (2-adamantyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methoxymethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxymethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-propoxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropoxymethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-butoxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tert-butoxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclopentyloxymethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclohexyloxymethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclooctyloxymethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-norbornyloxymethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-methylcyclopentyloxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethylcyclopentyloxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-methylnorbornyloxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethylnorbornyloxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethoxypropyloxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethoxy-1-methylethyloxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydrofuran-2-yloxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydropyran-2-yloxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-adamantyloxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (2-adamantyloxymethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methoxycarbonylmethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxycarbonylmethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-propoxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropoxycarbonylmethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-butoxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tert-butoxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclopentyloxycarbonylmethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclohexyloxycarbonylmethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclooctyloxycarbonylmethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-norbornyloxycarbonylmethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-methylcyclopentyloxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethylcyclopentyloxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-methylnorbornyloxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethylnorbornyloxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethoxypropyloxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethoxy-1-methylethyloxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydrofuran-2-yloxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydropyran-2-yloxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-adamantyloxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (2-adamantyloxycarbonylmethyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyano-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyanomethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyanoethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyanopropyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like.

On the other hand, in the repeating structural unit [B] represented by the general formula (2) in the present embodiment, X ¹ is —O— or —CR ⁴ R ⁵ — (R ⁴ and R ⁵ are each hydrogen or C 1-20. As a specific cyclic olefin monomer of the ring-opening metathesis copolymer represented by, for example, methyl, ethyl, propyl, etc., 4-oxatricyclo [5.2.1.0 ^{2 , 6} ] dec-8-en-3-one, 4-oxa-5,5-dimethyltricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 4-oxa- 2,6-dimethyltricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 4-oxa-2,5,5,6-tetramethyltricyclo [5.2. 1.0 ^2,6] dec-8-en-3-one, 4,10-dioxatricyclo [ .2.1.0 ^2,6] dec-8-en-3-one, 4,10-dioxa-5,5-dimethyl tricyclo [5.2.1.0 ^2,6] dec-8-ene -3-one, 4,10-dioxa-2,6-dimethyltricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 4,10-dioxa-2,5 5,6-tetramethyltricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one and the like can be mentioned.

In the repeating structural unit [D] represented by the general formula (3) in this embodiment, X ² represents —CR ¹⁰ R ¹¹ — (R ¹⁰ and R ¹¹ each represent hydrogen or an alkyl group having 1 to 20 carbon atoms. In the case where R ^{6 to} R ⁹ are alkyl groups, the specific cyclic olefin monomer of the ring-opening metathesis copolymer in which k = 0 in formula (5) is 5-methyl-bicyclo [2.2.1] hept-2 -Ene, 5-ethyl-bicyclo [2.2.1] hept-2-ene, 5-propyl-bicyclo [2.2.1] hept-2-ene, 5-isopropyl-bicyclo [2.2.1]. ] Hept-2-ene, 5- (n-butyl) -bicyclo [2.2.1] hept-2-ene, 5-isobutyl-bicyclo [2.2.1] hept-2-ene, 5- ( tert-butyl) -bicyclo [2.2.1] hept 2-ene, 5-cyclohexyl-bicyclo [2.2.1] hept-2-ene, 5-cyclooctyl-bicyclo [2.2.1] hept-2-ene, 5-norbornyl-bicyclo [2. 2.1] hept-2-ene and the like. When R ^{6 to} R ⁹ are an aryl group, 5-phenyl-bicyclo [2.2.1] hept-2-ene, 5-naphthyl-bicyclo [2.2.1] hept-2-ene, 5- (O-Tolyl) -bicyclo [2.2.1] hept-2-ene, 5-biphenyl-bicyclo [2.2.1] hept-2-ene and the like can be mentioned. When R ^{6 to} R ⁹ are alkoxy groups, 5-methoxy-bicyclo [2.2.1] hept-2-ene, 5-ethoxy-bicyclo [2.2.1] hept-2-ene, 5- ( n-butoxy) -bicyclo [2.2.1] hept-2-ene, 5-isobutoxy-bicyclo [2.2.1] hept-2-ene and the like. When R ^{6 to} R ⁹ are alkoxyalkyl groups, 5-methoxymethyl-bicyclo [2.2.1] hept-2-ene, 5-ethoxymethyl-bicyclo [2.2.1] hept-2-ene, 5- (n-propoxymethyl) -bicyclo [2.2.1] hept-2-ene, 5- (n-butoxymethyl) -bicyclo [2.2.1] hept-2-ene, 5-isobutoxy And methyl-bicyclo [2.2.1] hept-2-ene. When R ^{6 to} R ⁹ are alkoxycarbonyl groups, 5-methoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- (n-propoxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (n-butoxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5-isobutoxy Examples include carbonyl-bicyclo [2.2.1] hept-2-ene. When R ^{6 to} R ⁹ are an aryloxycarbonyl group, 5-phenyl-bicyclo [2.2.1] hept-2-ene, 5-naphthyl-bicyclo [2.2.1] hept-2-ene and the like Can be mentioned.

Further, in the same manner as above, in the repeating structural unit [D] represented by the general formula (3), X ² is —CR ¹⁰ R ¹¹ — (R ¹⁰ and R ¹¹ are each hydrogen or an alkyl group having 1 to 20 carbon atoms. As a specific cyclic olefin monomer of the ring-opening metathesis copolymer in which k = 1, when R ^{6 to} R ⁹ are alkyl groups, 8-methyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-propyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-butyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isobutyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tert-butyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclohexyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like. When R ^{6 to} R ⁹ are an aryl group, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (o-tolyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-biphenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like. When R ^{6 to} R ⁹ are alkoxy groups, 8-methoxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-butoxy) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isobutoxy-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like. When R ^{6 to} R ⁹ are alkoxyalkyl groups, 8-methoxymethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxymethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-propoxymethyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-butoxymethyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isobutoxymethyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like. When R ^{6 to} R ⁹ are alkoxycarbonyl groups, 8-methoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-propoxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-butoxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isobutoxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like. When R ^{6 to} R ⁹ are aryloxycarbonyl groups, 8-phenyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-naphthyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene and the like.

  The catalyst used for the polymerization reaction of the cyclic olefin monomer represented by the general formula (1), the general formula (2) and the general formula (3) is particularly a catalyst capable of ring-opening metathesis polymerization of the cyclic olefin monomer. Without limitation, for example, an organic transition metal alkylidene complex catalyst such as molybdenum (Mo), tungsten (W), ruthenium (Ru) or the like, or a combination of an organic transition metal complex and a Lewis acid as a cocatalyst and a ring-opening metathesis A catalyst is mentioned.

For _{^{example, W (N-2,6-Pr}} i 2 C 6 H 3) (thf) (OBu t) 2 Cl 2, W (N-2,6-Pr i 2 C 6 H 3) (thf) (OCMe ₂ CF ₃₎ and ₂ Cl ₂ or the like of the tungsten-based halogen _{^{complex, Mo (N-2,6-Pr}} i 2 C 6 H 3) (thf) (OBu t) 2 Cl 2, Mo (N-2,6- _{^{Pr i 2 C 6 H 3)}} (thf) (OCMe 2 CF 3) in 2 Cl ₂ (wherein, Pr ⁱ is iso- propyl group, Bu ^t is tert- butyl, thf represents a tetrahydrofuran.) molybdenum such Ring-opening metathesis catalyst comprising an organic halogen complex and an organoaluminum compound, organotin compound or organometallic compound such as lithium, sodium, magnesium, zinc, cadmium, boron, etc. as a cocatalyst; amine compound Ester compounds, and _{MoCl 6, WCl 6, ReCl 5} , TiCl 4, RuCl 3, IrCl inorganic transition metal halogen compound such as ₃ in the presence of an electron donor compound an ether compound such as, in the previously described Lewis acids as a co-catalyst A ring-opening metathesis catalyst based on a combination of these can be used.

  In this embodiment, in particular, a catalyst capable of copolymerizing a highly polar cyclic olefin monomer containing a hetero atom can be efficiently removed. For example, when an organic transition metal alkylidene complex such as tungsten, molybdenum or ruthenium is used as a ring-opening metathesis polymerization catalyst, a highly polar cyclic olefin monomer can be efficiently copolymerized.

Furthermore, the ring-opening metathesis polymerization catalyst of organic transition metal alkylidene complex, ^{_{specifically, W (N-2,6-Pr}} i 2 C 6 H 3) (CHBu t) (OBu t) 2, W (N- ^{_{2,6-Pr i 2 C 6 H}} 3) (CHBu t) (OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) ^{_{2) 2, W (N-}} 2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 _{Ph) (OCMe 2 CF 3)} 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, W (N-2,6-Pr ^{_{i 2 C 6 H 3) (}} CHCMe 2 Ph) (OC (CF 3) 3) 2 _{W (N-2,6-Me 2} C 6 H 3) (CHCMe 2 Ph) (OC (CF 3) 3) 2 (Pr i is iso- propyl group in the formula, Bu ^t is tert- butyl group, Me Represents a methyl group, Ph represents a phenyl group, and the like, a tungsten-based alkylidene catalyst such as W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OBu ^t ) ₂ (PMe ₃ ), W (N _{-2,6-Me 2 C 6 H 3} ) (CHCHCMe 2) (OBu t) 2 (PMe 3), W (N-2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OBu t) 2 (PMe ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OCMe ₂ (CF ₃ )) ₂ (PMe ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCCMe ₂ ) (OCMe _{2 (CF 3)) 2 (} PMe 3), W (N-2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OCMe 2 (CF 3)) 2 (PMe 3), W (N-2 , 6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OCMe (CF ₃ ) ₂ ) ₂ (PMe ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OCMe ( _{CF 3) 2) 2 (PMe} 3), W (N-2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OCMe (CF 3) 2) 2 (PMe 3), W (N-2, ^{_{6-Pr i 2 C 6 H}} 3) (CHCHCMePh) (OCMe 2 (CF 3)) 2 (PMe 3), W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OCMe (CF _{3) 2) 2 (PMe 3} ), W (N- ^{_{, 6-Pr i 2 C 6}} H 3) (CHCHCMePh) (OPh) 2 (PMe 3), (Pr i is iso- propyl group in the formula, Bu ^t is tert- butyl group, Me represents a methyl group, Ph refers to a Represents a phenyl group. ) Tungsten-based, such as alkylidene ^{_{catalyst, Mo (N-2,6-Pr}} i 2 C 6 H 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H 3) ^{_{(CHBu t) (OCMe 2 CF}} 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, Mo (N-2,6- ^{_{Pr i 2 C 6 H 3)}} (CHBu t) (OC (CF 3) 3) 2, Mo (N-2,6- Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2, Mo ^{_{(N-2,6-Pr i 2}} C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) ( _{OCMe (CF 3) 2) 2} , Mo (N-2,6-Pr i 2 C 6 _{3) (CHCMe 2 Ph) (} OC (CF 3) 3) 2, Mo (N-2,6- Me 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2, Mo (N-2,6 _{-Me 2 C 6 H 3) (} CHCMe 2 Ph) (OCMe 2 CF 3) 2, Mo (N-2,6-Me 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 _{, Mo (N-2,6-Me} 2 C 6 H 3) (CHCMe 2 Ph) (OC (CF 3) 3) 2 (Pr i is iso- propyl group in the formula, Bu ^t is tert- butyl group, Mo-based alkylidene catalysts such as Me represents a methyl group and Ph represents a phenyl group), Ru (P (C ₆ H ₁₁ ) ₃ ) ₂ (CHPh) Cl ₂ (Ph in the formula represents a phenyl group), etc. Ruthenium-based alkylidene catalysts It is. The above ring-opening metathesis polymerization catalysts may be used alone or in combination of two or more.

  Examples of the polymerization catalyst metal component for synthesizing the ring-opening metathesis copolymer of the present embodiment include transition metals such as molybdenum, tungsten, rhenium, iridium, tantalum, ruthenium, vanadium, titanium, palladium, and rhodium. Preferred are molybdenum, tungsten, ruthenium and rhodium, and more preferred are molybdenum and tungsten.

  In the polymerization reaction, the molar ratio of the cyclic olefin monomer to the ring-opening metathesis polymerization catalyst of the organic transition metal alkylidene complex is from 10 equivalents to 50000 equivalents, preferably from 50 equivalents to 1 mole of the cyclic olefin monomer. It is 30000 equivalent, More preferably, it is 100 equivalent-20000 equivalent.

  The polymerization reaction may be solventless or use a solvent. Examples of the solvent include ethers such as tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatic hydrocarbons such as pentane, hexane and heptane, cyclohexane Aliphatic cyclic hydrocarbons such as pentane, cyclohexane, methylcyclohexane, dimethylcyclohexane or decalin, halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene or trichlorobenzene, esters such as methyl acetate or ethyl acetate, etc. Two or more of these may be used in combination.

  The polymerization reaction may be performed in the presence of a chain transfer agent such as olefins and dienes. Examples of the olefin used as the chain transfer agent include α-olefins such as ethylene, propylene, butene, pentene, hexene, octene, and vinyltrimethylsilane, allyltrimethylsilane, allyltriethylsilane, allyltriisopropylsilane. And silicon-containing olefins such as Examples of the diene include non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, and 1,6-heptadiene. Furthermore, these olefins or dienes may be used alone or in combination of two or more.

  The amount of the olefin or diene used is preferably in the range of 0.001 to 1000 equivalents, more preferably 0.01 to 100 equivalents, with respect to 1 mol of the cyclic olefin monomer. Further, the olefin or diene is preferably in the range of 0.1 equivalent to 2000 equivalent, more preferably 1 equivalent to 1000 equivalent, relative to 1 mol of the ring-opening metathesis polymerization catalyst. By arbitrarily setting these ratios, the size of the molecular weight can be set, and the use of a chain transfer agent reduces the amount of ring-opening metathesis polymerization catalyst used in the polymerization reaction, thereby reducing the metal removal efficiency. Will increase.

  The monomer concentration of the polymerization reaction varies depending on the reactivity of the cyclic olefin monomer and the solubility in the polymerization solvent, and is not uniform, but the concentration of the cyclic olefin monomer relative to 1 kg of the solvent is usually 0.001 kg / kg to 3 kg / kg. kg, preferably 0.01 kg / kg to 2 kg / kg, more preferably 0.02 kg / kg to 1 kg / kg. The reaction temperature varies depending on the type and amount of the cyclic olefin monomer and the ring-opening metathesis catalyst, but is usually a reaction temperature of -30 ° C to 150 ° C, preferably 0 ° C to 120 ° C, more preferably 15 ° C to 100 ° C. Temperature. The reaction time is usually 1 minute to 10 hours, preferably 5 minutes to 8 hours, and more preferably 10 minutes to 6 hours.

  After the polymerization reaction, the reaction can be stopped with aldehydes such as butyraldehyde, ketones such as acetone, alcohols such as methanol, and the like to obtain a ring-opening metathesis copolymer solution. At that time, the polymerization rate of the cyclic olefin monomer is at least 90% or more, preferably 95% or more, and more preferably 100%. If the polymerization rate is low, it can be easily estimated that unpolymerized monomers remain in the ring-opening metathesis copolymer and the performance of the resist and optical material for lithography is reduced.

In this embodiment, a polymer having a double bond in the main chain obtained by the ring-opening metathesis copolymerization can be hydrogenated using a hydrogenation reaction catalyst under hydrogen.
As described above, the content of each metal component derived from the polymerization catalyst and the hydrogenation reaction catalyst is naturally limited due to advances in semiconductor manufacturing technology in response to the recent trend toward ultrafine wiring. The amount of residual metal contained in the hydrogenated product of the ring-opening metathesis copolymer obtained in the example of the polymer purification method of Patent Document 7 is not at a satisfactory level, and it is necessary to further reduce residual metal contamination. is there. This is because the residual metal contamination can easily cause a short circuit due to the leakage current of the semiconductor circuit.

  In this embodiment, in order to make the polymer metal removal purification method function more efficiently, in the hydrogenation reaction, the amount of the metal component derived from the polymerization catalyst and the hydrogenation reaction catalyst is reduced to 1000 ppb or less. The inventors invented that the total content of each metal component in the hydrogenated product of the ring metathesis copolymer can be 10 ppb or less.

A method for producing a hydrogenated product of a ring-opening metathesis copolymer of the present embodiment is a production method for producing a hydrogenated product of a ring-opening metathesis copolymer, comprising ruthenium (Ru) metal in the presence of hydrogen. And hydrogenation of the carbon-carbon double bond of the ring-opening metathesis copolymer using a carbon-supported hydrogenation reaction catalyst of rhodium (Rh) metal. The ring-opening metathesis copolymer includes a repeating structural unit [A] represented by the general formula (1) and a repeating structural unit [B] represented by the general formula (2), and the structural unit [A ] And the structural unit [B] in a molar ratio ([A] / [B]) of 5/95 or more and 90/10 or less, and a mass ratio of the ruthenium and the rhodium in the carbon-supported hydrogenation reaction catalyst. (Ru / Rh) is 80/20 or more and 99/1 or less, and the hydrogenation rate of the double bond of the hydrogenated product of the obtained ring-opening metathesis copolymer is 99.5 mol% or more, and thus obtained. In the hydrogenated product of the ring-opening metathesis copolymer, the elimination rate of the acid labile group in the structural unit [A] in the hydrogenated product of the ring-opening metathesis copolymer is 1 mol% or less. Polymerization catalyst and metal from hydrogenation reaction Yes amount is equal to or less than the 1000ppb.
Conventionally, in order to achieve the above hydrogenation rate, a large amount of hydrogenation reaction catalyst must be used, resulting in an increase in the amount of residual metal, resulting in a high elimination rate of the acid labile group. The transparency may be reduced. On the other hand, according to the production method of the present invention, a high hydrogenation rate can be achieved due to the effects described later, the amount of residual metal can be reduced, and the elimination rate of the acid labile group can be kept low.

  Furthermore, the hydrogenated product of the ring-opening metathesis copolymer of the present embodiment may contain the repeating structural unit [D] represented by the general formula (3), and the repeating structural unit represented by the general formula (1). The structural molar ratio between the total of [A] and the repeating structural unit [B] represented by the general formula (2) and the repeating structural unit [D] represented by the general formula (3) is, for example, ([A ] + [B]) / [D] = 99/1 to 1/99.

  In this hydrogenation reaction, an electron donating compound such as amine or alcohol may be used in combination.

According to the study by the present inventors, it has been found that the Ru metal carbon-supported catalyst alone may not achieve a hydrogenation rate of 99.5 mol% or more of the double bond of the copolymer. On the other hand, it has been found that the carbon-supported catalyst of Rh metal generates acidic protons during the hydrogenation reaction. More specifically, when only a carbon-supported catalyst of Rh metal is used, Rh metal generates a protonic acid in the presence of hydrogen, and acid instability of R ¹ of the repeating structural unit [A] represented by the general formula (1) It has been found that acid labile substituents can be eliminated from simple esters and converted to carboxylic acid structures. It has also been found that this carboxylic acid structure causes turbidity by coordinating with residual metal or agglomeration of polymers due to hydrogen bonding during molding such as heat-melt molding, thereby degrading the performance as an optical material. It was.
Based on this, the present inventors proceeded with intensive studies, and by using a Ru metal carbon supported catalyst and a Rh metal carbon supported catalyst in combination, as described later, the hydrogenation rate can be increased, and the acid instability The present inventors have found that an optical material excellent in transparency can be provided with the group leaving rate being kept low, and the present invention has been achieved.

  Furthermore, according to the study by the present inventors, a hydrogenated product of a ring-opening metathesis copolymer using the repeating structural unit [D] represented by the general formula (3) as a third component can be obtained. In the lithography process in the production process, it is possible to improve the resistance to repeated exposure such as multi-patterning while maintaining the generation efficiency of the carboxylic acid generated by acid decomposition of the acid labile group. In addition, in optical applications such as microlenses for digital camera modules, imaging lenses, and optical elements including MEMS, when the hydrogenated ring-opening metathesis copolymer is used as an optical film or molded product, in the melt molding process It has also been found that it is possible to suppress yellowing, deterioration, and turbidity of the polymer as a molded product, or to suppress appearance defects due to generation of polymer decomposition products and gels, and decrease in transparency at a specific wavelength. It was.

The present inventors perform the hydrogenation reaction of the ring-opening metathesis copolymer according to the present embodiment with a carbon-supported hydrogenation reaction catalyst of ruthenium (Ru) metal and rhodium (Rh) metal in the presence of hydrogen. Has found that the elimination rate of the acid labile group of the repeating structural unit [A] represented by the general formula (1) satisfies 1 mol% or less.
These metal mass ratios are 80/20 to 99/1 in Ru / Rh, preferably 85/15 to 98/2 in Ru / Rh, and more preferably 90/10 to 97 / in Ru / Rh. 3. As a result, the amount of Rh metal used is reduced so as not to generate free protonic acid from the carbon-supported hydrogenation reaction catalyst of Rh metal as much as possible, while suppressing generation of carboxylic acid due to elimination of acid labile groups. And the hydrogenation rate of this copolymer can be achieved to 99.5 mol% or more.

  In addition, according to the method for producing a hydrogenated product of a ring-opening metathesis copolymer according to the present embodiment, the residual amount of metal considered to be derived from the polymerization catalyst tends to be unexpectedly low after the hydrogenation reaction. It is considered that the combined use of a Ru metal and Rh metal carbon-supported catalyst may exhibit a deashing action of the polymerization catalyst metal component. In addition, the elution of metal components derived from the hydrogenation reaction catalyst is suppressed, and the ability of the hydrogenation reaction catalyst can be maintained high, so that the total metal component amount can be 1000 ppb or less while exhibiting a high hydrogenation rate. It is preferably 900 ppb or less, more preferably 850 ppb or less, and it is obvious that the lower the lower limit value of the total metal component amount, the better. In view of the reaction rate and the like of each reaction step, a preferable lower limit is 100 ppb, 150 ppb, or 200 ppb.

  By making the total metal component amount of the above-mentioned copolymer after the hydrogenation reaction within the above range, there is no yellowing at the time of heating of the polymer due to heat oxidation deterioration of the residual metal, and a melt-molded article having excellent optical characteristics. Found that you can get. These materials can be used as a display member such as a MEMS-related member, an organic EL, or a liquid crystal equipped with an optical lens represented by a microlens, a lenticular lens, a Fresnel lens, and the like.

  Furthermore, a metal component derived from a polymerization catalyst and a hydrogenation reaction catalyst is contained in the polymer by combining the hydrogenated product of the above copolymer with the method for producing a hydrogenated product described in the present invention and a demetallation purification method. Can be removed almost completely, and the ring-opening metathesis copolymer having a content of all metal components derived from each catalyst of 10 ppb or less can be obtained.

  As the solvent for the hydrogenation reaction, the polymerization reaction solution may be used as it is, or a different solvent may be used. In addition, the total supported metal mass of the carbon-supported hydrogenation reaction catalyst of Ru metal and Rh metal used for hydrogenation of the double bond of the ring-opening metathesis copolymer is preferably 0.00 with respect to the ring-opening metathesis copolymer. It is 05 mass%-1.0 mass%, More preferably, it is 0.1 mass%-0.8 mass%, More preferably, it is 0.1 mass%-0.6 mass%. In general, the carbon-supported catalyst is a hydrous metal-supported catalyst, and the amount of the supported metal with respect to carbon is preferably 1% by mass to 15% by mass, and more preferably 5% by mass to 10% by mass.

  The polymer concentration of the hydrogenation reaction varies depending on the composition ratio of the ring-opening metathesis copolymer, the type of the solvent, etc., but the concentration of the copolymer relative to 1 kg of the solvent is usually 0.001 kg / kg to 3 kg / kg. The range is preferably 0.01 kg / kg to 2 kg / kg, more preferably 0.02 kg / kg to 1 kg / kg.

  The hydrogenation reaction of the copolymer is carried out at a hydrogen pressure of usually from normal pressure to 30 MPa, preferably from 0.5 MPa to 20 MPa, particularly preferably from 2 MPa to 15 MPa, and the reaction temperature is usually from 0 ° C. to 200 ° C. The temperature is preferably from room temperature to 150 ° C, particularly preferably from 50 ° C to 120 ° C. The reaction time is usually 30 minutes to 50 hours, preferably 1 hour to 30 hours, more preferably 1 hour to 20 hours.

  The hydrogenated product subjected to the hydrogenation reaction under the above conditions has a hydrogenation rate measured by NMR spectrum analysis of 99.5 mol% or more, preferably 99.7 mol% or more, more preferably 100 mol%.

The hydrogenated ring-opening metathesis copolymer of the present invention has a polystyrene-concentrated weight average molecular weight (Mw) measured by gel permeation chromatography (GPC) at a sample concentration of 3.0 to 9.0 mg / ml. Usually, it is 3,000 to 1,000,000, preferably 5,000 to 300,000. When the weight average molecular weight (Mw) is 3,000 or more, various lithography photoresist characteristics such as coating properties and resolution performance as a resist material can be obtained. Moreover, it can have the fluidity | liquidity which can be melt-molded and melt-stretched as it is 1,000,000 or less. Moreover, molecular weight distribution (Mw / Mn) which is ratio of a weight average molecular weight (Mw) and a number average molecular weight (Mn) is the range of 1.0-5.0 normally.
For example, in order to obtain heat moldability, the molecular weight distribution is preferably wide, and is preferably 1.2 to 5.0, and more preferably 1.5 to 4.0.

  In the present embodiment, the method for obtaining the hydrogenated ring-opening metathesis copolymer from the polymer solution after hydrogenation is not particularly limited after filtering the polymer solution after hydrogenation and separating the metal-supported catalyst. However, for example, a method of discharging the reaction solution to a poor solvent under stirring, a method of depositing a polymer by a method such as steam stripping in which steam is blown into the reaction solution, or a method of evaporating and removing the solvent from the reaction solution by heating or the like And the like.

  In addition, a catalyst component having a large particle size is precipitated in a polymer solution in advance by a method such as decantation or centrifugation, and a supernatant is collected. A polymer hydrogenated product may be obtained. In particular, it is suitable to microfilter the catalyst component, and the opening of the filter is usually 0.01 μm to 50 μm, preferably 0.02 μm to 20 μm, more preferably 0.05 μm to 10 μm, and the pore size Filtration may be performed in multiple stages using different filtration filters.

  Although the material of the filtration filter to be used is not particularly limited, cellulose fiber, hydrocarbon polymer fiber, or the like can be selected depending on the type of catalyst, the performance of the filter medium, and the like. As the filter material for cellulose fibers, filter paper is preferable, and as the filter material for hydrocarbon polymer fibers, polypropylene and polytetrafluoroethylene are preferable. The filter medium may be washed and used again. Examples of the filtration method include pressure filtration and vacuum filtration, and any method is not particularly limited.

In the case of pressure filtration, the pressure is preferably 1 × 10 ² Pa or more, more preferably 1 × 10 ³ Pa to 1 × 10 ⁶ Pa to perform filtration, and the pressurized gas uses nitrogen or air. There is no particular restriction.

  In the case of vacuum filtration, the degree of vacuum is not particularly limited as long as it is less than atmospheric pressure. The pore diameter of the filter medium is usually 0.01 μm to 50 μm, preferably 0.02 μm to 20 μm, and more preferably 0.05 μm to 10 μm.

(Further metal removal purification method of the hydrogenated ring-opening metathesis copolymer obtained by this embodiment)
A further purification method of the hydrogenated product of the ring-opening metathesis copolymer obtained according to this embodiment may be carried out with reference to the following demetallation purification method.
More specifically, an organic compound containing basic and acidic functional groups is added to the liquid of the hydrogenated product of the ring-opening metathesis copolymer of this embodiment containing a metal component derived from the polymerization catalyst and the hydrogenation reaction catalyst. Contacting the metal component and the basic functional group of the organic compound to form an association product by coordination or charge transfer interaction (pre-process), and bringing the liquid into contact with a basic adsorbent The aggregate is brought into contact with the basic adsorbent, and the acidic functional group derived from the organic compound of the aggregate and the basic adsorbent are adsorbed by a physical interaction such as ionic bond or hydrogen bond. The total content of the catalyst metal component for each production of the hydrogenated ring-opening metathesis copolymer obtained by this embodiment by these two steps including removal of the metal component (post-process) is 10 ppb. It can be further removed to the bottom. Further, as shown in the data shown in the examples, it can be seen that the total content of the catalytic metal component is less than 5 ppb.

  Here, the liquid containing the hydrogenated product of the ring-opening metathesis copolymer, and the metal component derived from the polymerization catalyst and the hydrogenation reaction catalyst, the hydrogenated product of the ring-opening metathesis copolymer and the metal component are contained in the liquid. It may be dissolved, and the hydrogenated product or metal component of the ring-opening metathesis copolymer may not be dissolved.

  The basic functional group of the organic compound containing a basic functional group and an acidic functional group is a functional group that donates electrons, that is, an electron donor, and has any one of π electrons, unshared electron pairs, and anions. It is an organic compound containing a basic functional group.

  The basic functional group is preferably a conjugated double bond carbon having at least π electrons, or a functional group containing nitrogen, oxygen, phosphorus and / or sulfur atoms having unpaired electrons. Nitrogen-containing condensed heterocyclic functional groups such as enyl group, amino group, pyridine and phenanthroline, ether group, cyano group, hydroxyl group, ester group, carbonyl group, phosphine, phosphate and other phosphorus-containing functional groups, thioether group, thiol group, Examples thereof include functional groups such as sulfonyl groups, and particularly nitrogen-containing condensed heterocyclic functional groups such as pyridine and phenanthroline are preferable from the viewpoint of the strength of association with metal components.

  Furthermore, the acidic functional group of the organic compound is a functional group that gives a proton, that is, a proton donor, and is a phenol hydroxyl group, phosphoric acid, boric acid, carboxylic acid, sulfonic acid (phosphoric acid group, boric acid group, carboxyl group). , Sulfo group), etc., and any functional group that needs to be capable of adsorbing with a basic adsorbent by physical interaction such as ionic bond or hydrogen bond, particularly from the viewpoint of adsorption power Carboxylic acid and sulfonic acid are preferred.

  Specific examples of organic compounds containing these basic and acidic functional groups include 2-cyclopentadienylethyltrimethylammonium chloride, 2-methoxyethylcyclopentadiene, 2-dimethylaminoethylcyclopentadiene, N, N- Dimethyl-N′-2-cyclopentadienylethylhydrazine, 2-cyclopentadienylethanecarboximide, 3- (2-cyclopentadienylethyl) pyridine, 5- (2-cyclopentadienylethyl) 1, 10-phenanthroline, 2-cyclopentadienylethyldimethylphosphine, 2-cyclopentadienylethyltrimethylphosphonium chloride, 2-cyclopentadienylethyldimethylphosphate, p- (2-cyclopentadienylethyl) hydroxybenze 2-cyclopentadienyl ethane phosphoric acid, 2-cyclopentadienyl ethane boric acid, 2-cyclopentadienyl ethyl dimethylborane, 3-cyclopentadienyl propionic acid, 3-cyclopentadienyl ethyl propionic anhydride , 2-cyclopentadienylethyl mercaptan, 2-cyclopentadienylethanesulfonic acid, 2-aminoethyltrimethylammonium chloride, 2-aminoethylmethyl ether, diethylenetriamine, triethylenetetramine, hexamethylenediamine, N, N- Dimethyl-N ′-(2-aminoethyl) hydrazine, 2-aminoethanecarboximide, 4-dimethylaminopyridine, 5-amino-1,10-phenanthroline, 2-aminoethyldimethylphosphine, 2-aminoethyltri Tylphosphonium chloride, 2-aminoethyldimethylphosphate, o-aminophenol, m-aminophenol, p-aminophenol, 2-aminoethanephosphoric acid, 2-aminoethaneboric acid, 2-aminoethyldimethylborane, alanine, 2 -Aminoethyl mercaptan, 2-aminoethanesulfonic acid, 4-methoxypyridine, 2-hydrazinopyridine, 3-pyridinecarboximide, bipyridine, 5- (4-pyridine) -1,10-phenanthroline, 2- (4- Pyridyl) ethyldimethylphosphine, 2- (2-pyridine) ethyldimethylphosphate, 3-hydroxypyridine, 2- (2-pyridine) ethyl phosphate, 4-pyridyldimethylborane, nicotinic acid, isonicotinic acid, picolinic acid, 4- Pyridinecarboxylic acid, 2, 4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,2 ′ -Bipyridine-4,4'-dicarboxylic acid, nicotinic anhydride, 4-mercaptopyridine, 3-pyridinesulfonic acid, 2- (2-pyridine) ethanesulfonic acid, 2- (4-pyridine) ethanesulfonic acid, 5 -Methoxy-1,10-phenanthroline, 5-hydrazino-1,10-phenanthroline, 5- (1,10-phenanthroline) carboximide, 5-dimethylphosphino-1,10-phenanthroline, 5-hydroxy-1,10 -Phenanthroline, 5- (1,10-phenanthroline) phosphate, 5- (1,10-phenant) Lilin) borane, 5-carboxy-1,10-phenanthroline, 5-carboxy-1,10-phenanthroline anhydride, 5-mercapto-1,10-phenanthroline, 5- (1,10-phenanthroline) sulfonic acid, 2- Methoxyethyltrimethylammonium chloride, 1,4-dimethoxybutane, 2-methoxyethylhydrazine, 2-methoxyethylcarboximide, 2-methoxyethyldimethylphosphine, 2-methoxyethyltrimethylphosphonium chloride, 2-methoxyethyldimethylphosphate, p- Methoxyphenol, 2-methoxyethanephosphoric acid, 2-methoxyethaneboric acid, 2-methoxyethylborane, 3-methoxypropionic acid, 3-methoxypropionic anhydride, 2-methoxyethyl mercaptan 2-methoxyethanesulfonic acid, 2-cyanoethyltrimethylammonium chloride, 2-methoxypropionitrile, 2-aminopropionitrile, 2-hydrazinoethylpropionitrile, 2-cyanoethylcarboximide, 3-cyanopyridine, 5- Cyano-1,10-phenanthroline, 2-cyanoethyldimethylphosphine, 2-cyanoethyltrimethylphosphonium chloride, 2-cyanoethyldimethylphosphate, p-cyanophenol, 2-cyanoethanephosphoric acid, 2-cyanoethaneboric acid, 2-cyanoethylborane 3-cyanopropionic acid, 3-cyanopropionic anhydride, 2-cyanoethyl mercaptan, 2-cyanoethanesulfonic acid, 2-hydroxyethyltrimethylammonium chloride, ethylene glycol Cole monomethyl ether, ethanolamine, 2-hydroxyethylhydrazine, 2-hydroxyethylcarbodiimide, 3-hydroxypyridine, 5-hydroxy-1,10-phenanthroline, 2-hydroxyethyldimethylphosphine, 2-hydroxyethyltrimethylphosphonium chloride, 2 -Hydroxyethyldimethylphosphate, 2-hydroxyethanephosphoric acid, 2-hydroxyethaneboric acid, 2-hydroxyethylborane, hydroxyacetic acid, 2-hydroxyethylmercaptan, 2-hydroxyethanesulfonic acid, 2-ethoxycarbonylethyltrimethylammonium chloride Ethyl 3-methoxypropionate, ethyl 3-aminopropionate, ethyl 3-hydrazinopropionate, 2-ethoxycarbonylethyl Carboximide, ethyl 3-pyridinecarboxylate, 5-ethoxycarbonyl-1,10-phenanthroline, ethyl 3-dimethylphosphinopropionate, 2-ethoxycarbonylethyltrimethylphosphonium chloride, 2-ethoxycarbonyldimethylphosphate, p- Ethyl hydroxybenzoate, 2-ethoxycarbonylethanephosphoric acid, 2-ethoxycarbonylethaneboric acid, 2-ethoxycarbonylethylborane, ethyl 3-mercaptopropionate, 2-ethoxycarbonylethanesulfonic acid, 2-methylcarbonylethyltrimethylammonium Chloride, 1-methoxy-3-butanone, 1-amino-3-butanone, 1-hydrazino-3-butanone, 2-acetylethylcarboximide, 3-acetylpyridine, -Acetyl-1,10-phenanthroline, 1-dimethylphosphino-3-butanone, 2-acetylethyltrimethylphosphonium chloride, 2-acetylethyldimethylphosphate, p-acetylphenol, 2-acetylethanephosphoric acid, 2-acetylethane Boric acid, 2-acetylethylborane, 3-acetylpropionic acid, 3-acetylpropionic anhydride, 1-mercapto-3-butanone, 2-acetylethanesulfonic acid, 2-carboxyethyltrimethylammonium chloride, 3-hydrazino Propionic acid, 2-carboxyethylcarbomide, 3-dimethylphosphinopropionic acid, 2-carboxyethyltrimethylphosphonium chloride, 2-carboxyethyldimethylphosphate, p-hydroxybenzoic acid, 2-carboxyl Ruboxyethanephosphoric acid, 2-carboxyethaneboric acid, 2-carboxyethylborane, succinic acid, 3-mercaptopropionic acid, 2-carboxyethanesulfonic acid, 2-dimethylphosphinoethyltrimethylammonium chloride, 2-hydrazinodimethyl Phosphine, 2-dimethylphosphinoethylcarboximide, 1,3-bisdimethylphosphinopropane, 2-dimethylphosphinoethyldimethylphosphate, p-dimethylphosphinohydroxybenzene, 2-dimethylphosphinoethane phosphate, 2-dimethyl Phosphinoethaneboric acid, 2-dimethylphosphinoborane, 3-dimethylphosphinopropionic anhydride, 2-mercaptoethyldimethylphosphine, 2-dimethylphosphinoethanesulfonic acid, p-hydroxypheny Dimethyl phosphate, 2-mercaptoethyltrimethylammonium chloride, 2-hydrazinoethyl mercaptan, 2-mercaptoethylcarboximide, 2-mercaptoethyltrimethylphosphonium chloride, p-hydroxythiophenol, 2-mercaptoethane phosphate, 2- Mercaptoethylboric acid, 2-mercaptoethylborane, 3-mercaptopropionic anhydride, hexamethylenedithiol, 2-mercaptoethanesulfonic acid, 2-methylthioethyl-2-trimethylammonium chloride, 2-methoxyethylmethyl sulfide, 2- Aminoethyl methyl sulfide, 2-methylthioethyl hydrazine, 2-methylthioethyl carboximide, 3-methylthiopyridine, 5-methylthio-1,10-phenyl Introline, 2-methylthioethyldimethylphosphine, 2-methylthioethyltrimethylphosphonium chloride, 2-methylthioethyldimethylphosphate, 3-hydroxyphenylmethyl sulfide, 2-methylthioethanephosphoric acid, 2-methylthioethaneboric acid, 2-methylthioethylborane , 3-methylthiopropionic acid, 3-methylthiopropionic anhydride, 2-methylthioethyl mercaptan, 3-hydroxybenzenesulfonic acid, 2-sulfonylethylcarboximide and the like.

  Among these organic compounds containing basic and acidic functional groups, aromatic carboxylic acids having a nitrogen atom, sulfonic acids, phosphoric acids, boric acids and phenols, specifically, o-aminophenol, m -Aminophenol, p-aminophenol, 2-aminoethanephosphoric acid, 2-aminoethaneboric acid, 2-aminoethanesulfonic acid, 2- (2-pyridine) ethylphosphoric acid, nicotinic acid, isonicotinic acid, picolinic acid, 4-pyridinecarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 2,3- Pyridine dicarboxylic acid, 2,2′-bipyridine-4,4′-dicarboxylic acid, 3-pyridinesulfonic acid, 2- (2-pyridine Ethanesulfonic acid, 2- (4-pyridine) ethanesulfonic acid and the like, and further contains an electron-withdrawing substituent such as fluorine or an electron-donating substituent such as t-butoxy group and silyl group. May be.

  Particularly preferred are aromatic carboxylic acids and sulfonic acids having a nitrogen atom, specifically nicotinic acid, isonicotinic acid, picolinic acid, 4-pyridinecarboxylic acid, 2,4-pyridinedicarboxylic acid, 2,5- Pyridine dicarboxylic acid, 3,4-pyridine dicarboxylic acid, 3,5-pyridine dicarboxylic acid, 2,6-pyridine dicarboxylic acid, 2,3-pyridine dicarboxylic acid, 2,2′-bipyridine-4,4′-dicarboxylic acid , 3-pyridinesulfonic acid and the like.

  Of these, nicotinic acid, isonicotinic acid, picolinic acid, 4-pyridinecarboxylic acid, 2,2'-bipyridine-4,4'-dicarboxylic acid, and 3-pyridinesulfonic acid are preferable from the viewpoint of removing the metal component.

  In this embodiment, when a solution containing a hydrogenated product of a ring-opening metathesis copolymer is brought into contact with an organic compound containing a basic functional group and an acidic functional group, an organic compound containing a basic functional group and an acidic functional group is used. The compound may be in a state of being uniformly dissolved in the solvent or in a state of being dispersed as a solid in the solvent.

  Further, the organic compound containing a basic functional group and an acidic functional group may be added as it is to a liquid containing a hydrogenated product of a ring-opening metathesis copolymer, or may be added in a state dispersed or dissolved in a solvent, In order to increase the solubility of the organic compound, an alcohol such as methanol and ethanol, a highly polar solvent such as DMF or water may be mixed.

  The concentration of the hydrogenated product of the ring-opening metathesis copolymer when the organic compound containing the basic functional group and the acidic functional group is contacted with the liquid containing the hydrogenated product of the ring-opening metathesis copolymer is determined depending on the opening used. The concentration of the hydrogenated product of the ring-opening metathesis copolymer with respect to 1 kg of the solvent is preferably 0.001 kg / kg to 3 kg, although it varies depending on the type of the hydrogenated product of the ring metathesis copolymer and the solvent and is not uniform. / Kg, more preferably 0.01 kg / kg to 2 kg / kg, and still more preferably 0.02 kg / kg to 1 kg / kg. The amount of the organic compound containing the basic functional group and the acidic functional group is preferably 0.01 equivalent to 10000 equivalent, more preferably 0.1 equivalent to 1000, relative to 1 mol of the metal component to be contacted. Is equivalent. The contact temperature is preferably −30 ° C. to 300 ° C., more preferably 25 ° C. to 200 ° C. The contacting pressure is preferably atmospheric pressure to 10 MPa. The contact time is usually 1 minute to 50 hours, preferably 10 minutes to 20 hours, and more preferably 30 minutes to 10 hours.

In the method for further metal removal purification of the hydrogenated product of the ring-opening metathesis copolymer of the present embodiment, a liquid containing the hydrogenated product of the ring-opening metathesis copolymer, an organic compound containing a basic functional group and an acidic functional group In order to remove insoluble matter at any stage, contact may be performed before contact with the base material, after contact with the base adsorbent, and after contact with the basic adsorbent. In addition, they may be filtered in multiple stages using filter media having different pore diameters. Generally, it is difficult to highly purify a metal from a polymer as compared with the purification of an organic compound. In the present invention, since the above-mentioned requirements are satisfied, there is a tendency that the metal is easily desorbed even if the following known purification method is used.
Although the filter medium to be used is not particularly limited, cellulose fibers, hydrocarbon polymer fibers, and the like can be selected depending on the type of insoluble components, the performance of the filter medium, and the like.

  As the filter material for cellulose fibers, filter paper is preferable, and as the filter material for hydrocarbon polymer fibers, polypropylene and polytetrafluoroethylene are preferable. The filter medium may be washed and used again. Examples of the filtration method include pressure filtration and vacuum filtration, and any method is not particularly limited.

In the case of pressure filtration, the pressure is preferably 1 × 10 ² Pa or more, more preferably 1 × 10 ³ Pa to 1 × 10 ⁶ Pa to perform filtration, and the pressurized gas uses nitrogen or air. There is no particular restriction.

  In the case of vacuum filtration, the degree of vacuum is not particularly limited as long as it is less than atmospheric pressure. The pore diameter of the filter medium is usually 0.01 μm to 50 μm, preferably 0.02 μm to 20 μm, and more preferably 0.05 μm to 10 μm.

  In further purification of the hydrogenated product of the ring-opening metathesis copolymer obtained by the present embodiment, an association product of a metal component and an organic compound containing a basic functional group or an acidic functional group is subjected to basic adsorption in a subsequent step. The residual metal component is removed from the polymer solution by contacting with the agent and adsorbing the associated product on the basic adsorbent.

The basic functional group contained in the basic adsorbent is preferably a functional group containing nitrogen and / or phosphorus, and more preferably an amino group. The basic adsorbent is preferably insoluble in a solvent, and the basic adsorbent may be an inorganic compound or an organic compound.
The basic adsorbent has adsorbability for a compound having an acidic functional group.

Examples of the basic adsorbent used in the further purification of the hydrogenated product of the ring-opening metathesis copolymer obtained according to this embodiment include an anion exchange resin and an amphoteric ion exchange resin. For example, a styrene ion exchange resin having —N ⁺ (CH ₃ ) ₃ OH ^— , a styrene ion exchange resin having —N (CH ₃ ) ₂ (C ₂ H ₄ OH) OH ^— , —NH (CH ₂ CH ₂ NH) _n H (n = 1 to 10) styrene ion exchange resin, -N (CH ₃ ) ₂ styrene ion exchange resin, -N (CH ₂ COONa) ₂ styrene ion exchange resin , A styrene ion exchange resin having —N (CH ₂ COOH) ₂ , a styrene ion exchange resin having a pyridine ring, an acrylic ion exchange resin having —N (CH ₃ ) ₂ , and a styrene system having a thiourea residue Ion exchange resin, styrene ion exchange resin having —N (CH ₃ ) CH ₂ [CH (OH)] ₄ CH ₂ OH, —P (═O) (OCH ₂ NH ₂ ) Styrene ion exchange resin having ₃ , polystyrene ion exchange resin impregnated with di-2-ethylhexyl phosphate, epoxy ion exchange having —NH (CH ₂ CH ₂ NH) _n H (n = 1 to 20) Examples thereof include resins. Even if the compound having these functional groups may be grafted or copolymerized on a synthetic resin and crosslinked to form a solid insoluble in a solvent, the molecular weight of these synthetic resins is increased so as to be insoluble in the solvent. May be.

Among these adsorbents containing basic functional groups, styrene-based ion exchange resins having —NH (CH ₂ CH ₂ NH) _n H (n = 1 to 10) and styrene-based having —N (CH ₃ ) ₂ An ion exchange resin having an amino group such as an ion exchange resin or a styrene ion exchange resin having a pyridine ring is preferred.

  The particle size of the basic adsorbent is preferably 10 μm to 5000 μm, more preferably 100 μm to 3000 μm. The use amount of the basic adsorbent is preferably 0.01 to 1 and more preferably 0.05 to 1 as a volume ratio, assuming that the volume of the hydrogenated product of the ring-opening metathesis copolymer solution is 1. 0.5. The basic adsorbent may be washed with a solvent to remove impurities eluted from the adsorbent. The washing solvent may be a solvent used for the synthesis of the hydrogenated product of the ring-opening metathesis copolymer, or methanol. Or an alcohol such as ethanol, or a solvent such as water. The method for washing the basic adsorbent is not particularly limited. For example, the basic adsorbent may be placed in a tower and washed with a washing solvent, or the basic adsorbent and the washing solvent may be placed in a container. May be mixed and washed by filtration or decantation.

  Furthermore, an acidic adsorbent may be used in combination for the purpose of removing a basic component eluted from the basic adsorbent. The acidic adsorbent is preferably insoluble in a solvent in order to adsorb and remove basic components, and may be an inorganic compound or an organic compound.

Examples of the acidic functional group contained in the acidic adsorbent include a sulfonyl group, a carboxyl group, a hydroxyl group-containing compound, and the like, for example, a styrene ion exchange resin having —SO ₃ H, a styrene ion exchange resin having —COOH, Examples include acrylic ion exchange resins having -COOH, methacrylic ion exchange resins having -COOH, and phenol ion exchange resins. Even if the compound having these functional groups may be grafted or copolymerized on a synthetic resin and crosslinked to form a solid insoluble in a solvent, the molecular weight of these synthetic resins is increased so as to be insoluble in the solvent. May be. Styrene-based ion exchange resin having -SO 3 _H Of these acidic adsorbents are preferred. The acidic adsorbent may be used after washing, like the basic adsorbent.

  The acidic adsorbent may be mixed with the basic adsorbent, or may be contacted with the solution after the contact treatment with the basic adsorbent. The amount of the acidic adsorbent used is preferably 0.01 to 1 and more preferably 0.1 to 0.5 as a volume ratio when the volume of the basic adsorbent is 1.

  Furthermore, in the subsequent step of the demetallation purification method of the hydrogenated product of the ring-opening metathesis copolymer obtained by this embodiment, the metal component and an organic compound containing a basic functional group and an acidic functional group are used. The liquid phase of the liquid containing the association product is brought into contact with the solid phase of the basic adsorbent. At this time, the basic adsorbent may be put into a packed tower, and the liquid may be passed through the packed tower, or the liquid and the basic adsorbent may be stirred and mixed, and the basic adsorbent may be filtered. It may be separated by.

  The concentration of the hydrogenated product of the ring-opening metathesis copolymer at the time of contacting the associated product with the basic adsorbent varies depending on the type of the hydrogenated product of the ring-opening metathesis copolymer and the solvent used, and is not uniform. Usually, the concentration of the hydrogenated product of the ring-opening metathesis copolymer with respect to 1 kg of the solvent is preferably 0.001 kg / kg to 3 kg / kg, more preferably 0.01 kg / kg to 2 kg / kg, still more preferably 0. The range is from 0.02 kg / kg to 1 kg / kg.

  The temperature at which the association product is brought into contact with the basic adsorbent is preferably −30 ° C. to 150 ° C., more preferably 0 ° C. to 60 ° C. The contact pressure is preferably atmospheric pressure to 1 MPa. In the case of liquid contact in the packed tower, the contact speed is usually 1 to 500 (m / hour), preferably 10 to 300 (m / hour) as the linear flow rate LV. The liquid flow (space) flow rate SV is preferably 1 to 1000 (1 / hour), more preferably 10 to 500 (1 / hour). The length, thickness, volume, and shape of the packed tower depend on the amount of processing, the flow time, and the economy, but may be operated within a range satisfying these linear flow rate and liquid flow rate.

  In the case of mixed contact, the contact time is usually 30 minutes to 48 hours, preferably 1 hour to 24 hours, and more preferably 1 hour to 12 hours. Mixing may be performed by any of stirring blades, rotation, shaking, ultrasonic waves, and the like. Moreover, you may repeat the polymer purification method of this embodiment which consists of said front process and back process several times as needed.

  In the present embodiment, each of the residual metal components is obtained by the purification method described above in which the metal component (residual metal component) derived from the production catalyst is removed from the hydrogenated product of the highly polar ring-opening metathesis copolymer containing a heteroatom. A hydrogenated ring-opening metathesis copolymer having a total content of 10 ppb or less can be produced. The hydrogenated product of this ring-opening metathesis copolymer usually has a content of each residual metal component of 10 ppb or less, preferably 5 ppb or less. The lower limit value of the residual metal component is not particularly limited, but is usually 0 ppb.

  According to the method for producing a hydrogenated product of a ring-opening metathesis copolymer according to the present embodiment, the acid of the repeating structural unit [A] represented by the general formula (1) in the hydrogenated product of the ring-opening metathesis copolymer The elimination rate of unstable groups is 1 mol% or less, the hydrogenation rate of the double bond is 99.5 mol% or more, and the hydrogenation product of the polymerization catalyst and the ring-opening metathesis copolymer derived from the hydrogenation reaction The metal content can be 1000 ppb or less. The hydrogenated product of the ring-opening metathesis copolymer can further be applied to the polymer metal removal purification method described in the present invention, and the hydrogenated product of the resulting ring-opening metathesis copolymer can be a resist composition or the like. It can be used for semiconductor materials.

A copolymer obtained through the above-described metal removal step is unlikely to be yellowed even when molded, and a molded product having high transparency can be obtained. This is a preferred copolymer embodiment of the present invention.
Such a copolymer preferably satisfies the following requirements.
The total of the repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2) and the repeating structural unit [D represented by the general formula (3) [D] ], And the copolymer has a structure in which a double bond of a copolymer having a constituent molar ratio of ([A] + [B]) / [D] = 99/1 to 1/99 is hydrogenated. It is characterized by being a ring-opening copolymer having a main chain double bond content of 0.5 mol% or less and a metal content of 30 ppb or less.

（式中、Ｒ^６〜Ｒ^９は、水素、炭素数１〜２０のアルキル基、炭素数６〜２０のアリール基、炭素数１〜２０のアルコキシ基、炭素数２〜２０のアルコキシアルキル基、炭素数２〜２０のアルコキシカルボニル基または炭素数７〜２０のアリールオキシカルボニル基から選ばれ、Ｘ^２は−Ｏ−および−ＣＲ^１０Ｒ^１１−から（Ｒ^１０およびＲ^１１はそれぞれ水素または炭素原子数１〜２０のアルキル基を表す）選ばれ、同一でも異なってもよい。また、Ｒ^６〜Ｒ^９は、互いに、結合してもよく、ｋは０または１である。）

(Wherein R ^{6 to} R ⁹ are hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, X ² is selected from an alkoxycarbonyl group having 2 to 20 carbon atoms or an aryloxycarbonyl group having 7 to 20 carbon atoms, and X ² is —O— and —CR ¹⁰ R ¹¹ — (R ¹⁰ and R ¹¹ are each a hydrogen atom or a carbon atom. (Represents an alkyl group of 1 to 20), which may be the same or different, and R ^{6 to} R ⁹ may be bonded to each other, and k is 0 or 1.)

  The above metal refers to a component called a so-called metal element belonging to Groups 1 to 16 of the periodic table. The content is 30 ppb or less, preferably 20 ppb or less, and more preferably 10 ppb or less. In the present invention, the metal content selected from Mo, W, Ru, and Rh, which is a metal element often included in the metathesis polymerization catalyst and the hydrogenation reaction catalyst among the metals, is 10 ppb or less. preferable. More preferably, it is 5 ppb or less.

The content of the main chain double bond can be defined by, for example, a value obtained by subtracting the value of hydrogenation rate (%) from 100%. In the present invention, the preferred range of the content of the main chain double bond is 0.5 mol% or less, more preferably 0.3 mol% or less.
Moreover, although the said cyclic copolymer may become a structure containing a carboxylic acid group, in this invention, the content rate of a carboxylic acid group is 1 mol% or less in the said structural unit [A]. More preferably, it is 0.8 mol% or less, More preferably, it is 0.5 mol% or less.
In the present invention, it can be said that the acid labile group elimination rate substantially refers to the content of the carboxylic acid group.

  As described above, since the double bond content of the main chain is low, the metal content is also extremely low, and preferably a group highly reactive with a metal such as a carboxylic acid group can be reduced. Yellowing or the like hardly occurs and high transparency is exhibited. For this reason, when the hydrogenated ring-opening metathesis copolymer according to the present embodiment is used for optical component applications that are not yellowed and requires high transparency, and for organic EL, liquid crystal plastic substrate or electronic material applications, etc. If necessary, modifiers such as antioxidants, surfactants, plasticizers, stabilizers such as ultraviolet absorbers and antibacterial agents, and reinforcing agents such as glass fibers and inorganic fillers may be added.

  The hydrogenation of the ring-opening metathesis copolymer according to the present embodiment is required to have high transparency without yellowing, and the hydrogenation of the ring-opening metathesis copolymer of the present embodiment is, for example, solution cast The total light transmittance of a molded product such as a film, sheet, or lens obtained by a molding method such as a method, a heat melting method, or an injection molding method is 80% or more, preferably 83% or more. More preferably, it is 85% or more, particularly preferably 90% or more.

  As a method of obtaining a film-like molded product by the solution casting method, a hydrogenated product of the ring-opening metathesis copolymer according to this embodiment is dissolved in an organic solvent to obtain a varnish, and then the varnish is used to form a film. The method of doing is mentioned.

  The organic solvent is not particularly limited, and examples thereof include ethers such as tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane, and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, and ethylbenzene, pentane, hexane, and heptane. Aliphatic hydrocarbons such as cyclopentane, cyclohexane, cyclohexane, cyclohexane, cyclohexane, dimethylcyclohexane or decalin, and other cyclic hydrocarbons, halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene or trichlorobenzene, methyl acetate or Examples include esters such as ethyl acetate. Among these, it can select in consideration of solubility and film forming property. These may be used alone or in combination of two or more.

  The concentration at which the hydrogenated product of the ring-opening metathesis copolymer according to this embodiment is dissolved is preferably 1.0 to 99.0% by mass, and more preferably 5.0 to 90.0% by mass. It is particularly preferably 10.0 to 80.0% by mass. The concentration may be selected in consideration of the solubility of the polymer, adaptability to the filtration process, film forming property, and film thickness.

  Further, in the present embodiment, the above-mentioned antioxidants, surfactants, modifiers such as plasticizers, ultraviolet absorbers, stabilizers such as antibacterial agents, glass, etc. Reinforcing agents such as fibers and inorganic fillers may be added.

  Subsequently, the varnish prepared by the above-described method is filtered through a filter. As a result, polymer insoluble matter, gel, foreign matter, and the like can be greatly reduced from the varnish. For example, the surface of the organic EL or liquid crystal display device as a substrate can be formed smoothly and uniformly.

  The opening of the filtration filter is preferably 10 μm to 0.05 μm, particularly preferably 10 μm to 0.1 μm, and further preferably 5 μm to 0.1 μm. The filtration process may be a multistage process in which the polymer solution is sent from a filter with a large pore size to a small filter, or a single process in which the varnish is sent directly to a filter with a small pore size. The material of the filter may be made of an organic material such as polytetrafluoroethylene, PP, PES, or cellulose, or may be made of an inorganic material such as glass fiber or metal, and can be selected from varnish characteristics and process adaptability.

  Moreover, as a method for sending the varnish to the filter, a method using a pressure difference or a method for sending the varnish to the filter by mechanical driving via a screw or the like may be used. Further, the filtration temperature is selected in a range considering filter performance, solution viscosity, and polymer solubility, preferably −10 to 200 ° C., more preferably 0 ° C. to 150 ° C., and room temperature to A temperature of 100 ° C. is particularly preferable.

  After filtering the varnish as described above, a film is formed from the varnish. When manufacturing by the solution cast method, the polymer is first applied to the base material on which the varnish is applied by a method such as table coat, spin coat, dip coat, die coat, spray coat, bar coat, roll coat, curtain flow coat, etc. A solution (varnish) is applied to form a film. Base materials include stainless steel, metal materials such as silicon, inorganic materials such as glass and quartz, polyimide, polyamide, polyester, polycarbonate, polyphenylene ether, polyphenylene sulfide, polyacrylate, polymethacrylate, polyacrylate, epoxy resin, silicone resin It can be selected from those made of a resin material.

  The coating film may be dried by placing the base material on which the solution has been cast on a heating plate, or by heating the base material on which the solution has been cast in a heated drying furnace. Warm air heated with a gas such as air or nitrogen may be applied to the coating film and dried, or may be dried using a process combining these. The drying temperature is preferably 10 to 250 ° C., more preferably 20 to 220 ° C., particularly preferably 30 to 200 ° C., varnish characteristics, film thickness, and heat resistance of the substrate. Selected in consideration of sex. Alternatively, the coating film may be dried by setting a multi-stage drying temperature with two or more temperature settings. The time for drying the coating film can be selected from the conditions considering the boiling point of the varnish solvent, the film thickness, and the process requirements. By these, a film is formed on the base material, and in the drying step of the coating film, the content of each residual metal component of the present embodiment is 10 ppb or less, preferably 5 ppb or less, and high without yellowing. A film having transparency can be obtained. The lower limit value of the residual metal component is not particularly limited, but is usually 0 ppb.

  Moreover, when obtaining the film which consists of a single layer film, and a sheet-like molded object, a film can be manufactured by peeling a film from a base material, for example. Peeling of the film from the substrate may be performed by applying a commercially available tape to the end of the film and applying stress to the film to peel off the liquid, such as water or a solvent, at the contact interface between the film and the support. It may be carried out by peeling the film using the difference in surface tension between the support surface and the contact surface of the film.

Examples of a method for producing other film or sheet-like molded product include a method of producing by a melt molding method. As a method for producing a film by a melt molding method, a method of forming a hydrogenated product of the ring-opening metathesis copolymer according to the embodiment exemplified above from a melt kneader through a T die, or using a heating plate Examples thereof include a method of pressing to form a film and an inflation method. In the production of a melt-extruded film using a T-die, for example, a hydrogenation of a ring-opening metathesis copolymer blended with additives as necessary is charged into an extruder, and preferably 50 ° C to 200 ° C above the glass transition temperature. It can be processed into a film by melt-kneading at a high temperature, more preferably at a temperature higher by 80 ° C. to 150 ° C., extruding from a T-die, and cooling the molten polymer with a cooling roll or the like. Moreover, the heating temperature at the time of pressing into a film using a heating plate is made equal to the temperature at the time of melt kneading.
Furthermore, additives such as an ultraviolet absorber, an antioxidant, a flame retardant, an antistatic agent, and a colorant may be added as long as the effects of the present invention are not impaired.

  The thickness of the film produced using the hydrogenated product of the ring-opening metathesis copolymer is preferably 1-1000 μm, more preferably 5-500 μm, and particularly preferably 10-200 μm. . These can be applied to transparent members of various display devices such as organic EL and liquid crystal, for example, and the film thickness is in a suitable range of these members.

  Furthermore, using the hydrogenated product of the ring-opening metathesis copolymer described above, for example, by a method such as injection molding, press molding, compression molding, injection compression molding, extrusion molding, for example, a lens member such as an imaging lens. The microlens can also be manufactured by using a mold having an uneven structure of a lens array on the surface of the mold. In this case, the melt molding temperature is preferably 350 ° C. or lower, more preferably 330 ° C. or lower, and particularly preferably 300 ° C. or lower. When the polymer is melted at a temperature in this range and the content of each residual metal component of the present embodiment is 10 ppb or less, preferably 5 ppb or less, coloring yellowing does not occur, and Thermal decomposition and generation of decomposition gas can be suppressed. Furthermore, additives such as an ultraviolet absorber, an antioxidant, a flame retardant, an antistatic agent, and a colorant may be added as long as the effects of the present invention are not impaired.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited by these. In addition, the analytical value regarding the polymer obtained in the Example was measured with the following method.

Weight average molecular weight measurement: Measured by gel permeation chromatograph (GPC). 10 mg of a polymer sample was dissolved in 2 g of tetrahydrofuran to prepare a measurement sample. The columns Shodex k-805, 804, 803, and 802.5 were calibrated with polystyrene standards at 40 ° C. and a flow rate of 1.0 ml / min using JASCO Corporation 830-RI and UVIDEC-100-VI as detectors. The weight average molecular weight (Mw) and the number average molecular weight (Mn) were measured using columns connected in series.

Polymerization rate measurement: The reaction solution was dissolved in deuterated chloroform, and the chemical shift of 270 MHz, ¹ H-NMR spectrum δ = integration of peaks attributable to hydrogen of double bond carbon in the range of 5.0 to 6.5 ppmn. Measured by value.

・ Hydrogenation rate measurement: A polymer sample was dissolved in deuterated chloroform and a chemical shift of 270 MHz, ¹ H-NMR spectrum δ = 4.0 to 6.5 ppm. Measured with integral value.

Measurement of metal content: A solution with a known sample amount was precisely weighed in a container, pyrolyzed with nitric acid in a microwave, and residual metal components were quantified with an ICP-MS apparatus of HP-4500, Agilent Technologies. Alternatively, a polymer sample of the solution was precisely weighed in a container, heated to evaporate the solvent, and then pyrolyzed with nitric acid in a microwave, and the residual metal component was quantified by the ICP-MS method.

・ Composition measurement of structural unit: A sample with a known sample amount was dissolved in deuterated tetrahydrofuran, and the structure of each peak was an integral value of peaks attributed to each carbonyl having a chemical shift of δ = 170 to 190 ppm in ¹³ C-NMR spectrum. The molar ratio of units [A], [B], and [D] and the amount of acid labile group eliminated were measured.

Measurement method of total light transmittance: A total light transmittance of a test piece having a thickness of 100 μm obtained by hot press molding using a mirror surface plate was evaluated with a haze meter NDH2000 manufactured by Nippon Denshoku Industries Co., Ltd.

[Example 1]
In a 5 L autoclave equipped with a magnetic stirrer under a nitrogen atmosphere, 4,10-dioxa-tricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 304 g (2 mol), 8- (1-ethylcyclopentyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 601 g (2 mol), and 1,5-hexadiene, 21 g (0.25 mol) were dissolved in 3.2 kg of tetrahydrofuran (hereinafter referred to as THF) and stirred. This ring-opening metathesis polymerization catalyst as ^{Mo (N-2,6-Pr i} 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, 612mg of (0.8 mmol) was added, 60 ° C. For 3 hours. Thereafter, 173 mg (2.4 mmol) of n-butyraldehyde was added and cooled to obtain 4.1 kg of a ring-opening metathesis copolymer solution. The polymerization rate was 100%, Mw = 6500, Mw / Mn = 1.85, and the content of Mo in the polymer precipitated with water was 75 ppm.

  To 0.5 kg separated from the ring-opening metathesis copolymer solution obtained in a 5 L autoclave, 11.46 g of 5 mass% Ru carbon having a water content of 54.4 mass% as a hydrogenation reaction catalyst (dry mass 5.23 g mass) Ratio of 95%), 50.7% by weight of 5% Rh carbon with a moisture content of 50.7% by weight (dry weight 0.28 g, 5% by weight ratio) were added, and hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and 100 ° C. for 12 hours. . Here, 5 mass% Ru carbon means a carbon supported Ru catalyst in which the amount of Ru supported is 5 mass% with respect to 100 mass% of carbon. Further, 5 mass% Rh carbon means a carbon supported Rh catalyst in which the amount of Rh supported is 5 mass% with respect to 100 mass% of carbon.

  By adding 450 g of ultrapure water to the hydrogenated product solution of the resulting ring-opening metathesis copolymer in 25 g, the hydrogenated product of the ring-opening metathesis copolymer is precipitated, separated by filtration, and then vacuum dried. A hydrogenation product of a ring-opening metathesis copolymer having a hydrogenation rate of 100% was obtained as a white powder. The Mo metal content derived from the polymerization catalyst in the hydrogenated product of the obtained ring-opening metathesis copolymer was 245 ppb, and the Ru and Rh metal content derived from the hydrogenation reaction catalyst were 455 ppb and 17 ppb, respectively. Mw = 10000, Mw / Mn = 2.05, [A] / [B] = 50/50, and there was no elimination of the 1-ethylcyclopentyl group of the structural unit [A]. The test piece with a thickness of 100 μm produced by the hot melt press was not turbid, was colorless and transparent and had a total light transmittance of 91%.

  In a 1 L glass autoclave, 503.0 g of a 20.0 wt% THF solution of the obtained ring-opening metathesis copolymer hydrogenated product, 872 mg of 4-pyridinecarboxylic acid, and a water concentration of 2.5 wt% Ultrapure water was added thereto, and the mixture was heated at 110 ° C. for 6 hours with stirring under a nitrogen atmosphere. Then, it is cooled to room temperature and mixed with 67 ml of styrene ion exchange resin Diaion CR20 (manufactured by Mitsubishi Chemical Corporation) containing amino groups and 33 ml of styrene ion exchange resin Levacit S100H (manufactured by Bayer) containing sulfonic acid groups. The mixture was contacted and precipitated with water (hereinafter abbreviated as decalcification treatment). The Mo metal content derived from the polymerization catalyst in the dry polymer was 0 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 0 ppb and 0 ppb, respectively.

[Example 2]
To 0.5 kg fractionated from the ring-opening metathesis copolymer solution obtained in the 5 L autoclave synthesized in Example 1, 6.51 g of 5 mass% Ru carbon used in Example 1 (dry mass 2.97 g mass ratio) 90%), 5 mass% Rh carbon 0.67 g (dry mass 0.33 g mass ratio 10%) was added, and hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and 95 ° C. for 12 hours.

  From the obtained hydrogenated solution of the ring-opening metathesis copolymer, a hydrogenated product of the ring-opening metathesis copolymer was precipitated in the same manner as in Example 1, and the white ring-opening metathesis copolymer having a hydrogenation rate of 100% was precipitated. A hydrogenated product of the polymer was obtained. The Mo metal content derived from the polymerization catalyst in the hydrogenated product of the obtained ring-opening metathesis copolymer was 400 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 240 ppb and 20 ppb, respectively. Mw = 9850, Mw / Mn = 2.05, [A] / [B] = 50/50, and there was no elimination of the 1-ethylcyclopentyl group of the structural unit [A].

  Further, in the same manner as in Example 1, when the deashing treatment was performed, the Mo metal content derived from the polymerization catalyst in the dry polymer was 1 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 0 ppb and 0 ppb, respectively.

[Example 3]
To 0.5 kg fractionated from the ring-opening metathesis copolymer solution obtained in the 5 L autoclave synthesized in Example 1, 3.08 g of 5 mass% Ru carbon used in Example 1 (dry mass 1.41 g mass ratio) 85%), 5% by mass Rh carbon 0.50 g (dry mass 0.25 g, mass ratio 15%) was added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and 90 ° C. for 18 hours.

  The hydrogenated product of the ring-opening metathesis copolymer was precipitated from the resulting hydrogenated solution of the ring-opening metathesis copolymer in the same manner as in Example 1, and the ring-opening in the form of a white powder having a hydrogenation rate of 99.9% A hydrogenated product of a metathesis copolymer was obtained. The Mo metal content derived from the polymerization catalyst in the hydrogenated product of the obtained ring-opening metathesis copolymer was 700 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 70 ppb and 100 ppb, respectively. Mw = 10200, Mw / Mn = 2.05, [A] / [B] = 50/50, and there was no elimination of the 1-ethylcyclopentyl group of the structural unit [A]. The test piece having a thickness of 100 μm produced by the hot melt press was not turbid and had a colorless and transparent total light transmittance of 89%.

  Further, in the same manner as in Example 1, when the deashing treatment was performed, the Mo metal content derived from the polymerization catalyst in the dry polymer was 3 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 0 ppb and 0 ppb, respectively.

[Example 4]
In an autoclave similar to Example 1, 4,10-dioxa-tricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 548 g (3.6 mol), 8- (1 -Ethylcyclopentyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, was dissolved 120 g (0.4 mol), and 1,5-hexadiene, 43 g of (0.52 mol) in THF3.2kg, Mo (N-2,6- Pr i 2 C _{6 H 3) (CHCMe 2 Ph} ) (OCMe (CF 3) 2) 2, 306mg of (0.4 mmol) was added, reacted as in example 1 to obtain a ring-opening metathesis copolymer solution 3.9kg . The polymerization rate was 100%, Mw = 6000, Mw / Mn = 1.90, and the content of Mo in the polymer precipitated with water was 35 ppm.

  To 0.5 kg separated from the obtained ring-opening metathesis copolymer solution, 5.11 g of 5 mass% Ru carbon used in Example 1 (dry mass 2.33 g, mass ratio 90%), 5 mass% Rh carbon. 0.53 g (dry mass 0.26 g, mass ratio 10%) was added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and 95 ° C. for 12 hours.

  From the obtained hydrogenated solution of the ring-opening metathesis copolymer, a hydrogenated product of the ring-opening metathesis copolymer was precipitated in the same manner as in Example 1, and the white ring-opening metathesis copolymer having a hydrogenation rate of 100% was precipitated. A hydrogenated product of the polymer was obtained. The Mo metal content derived from the polymerization catalyst in the hydrogenated product of the obtained ring-opening metathesis copolymer was 190 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 150 ppb and 10 ppb, respectively. Mw = 9850, Mw / Mn = 2.05, [A] / [B] = 10/90, and there was no elimination of the 1-ethylcyclopentyl group of the structural unit [A]. The test piece with a thickness of 100 μm produced by the hot melt press was not turbid and had a colorless and transparent total light transmittance of 91%.

  Further, in the same manner as in Example 1, when the deashing treatment was performed, the Mo metal content derived from the polymerization catalyst in the dry polymer was 3 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 0 ppb and 0 ppb, respectively.

[Example 5]
In an autoclave similar to that of Example 1, 4,10-dioxa-tricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 61 g (0.4 mol), 8- (1 -Ethylcyclopentyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, was dissolved 1082 g (3.6 mol), and 1,5-hexadiene, 43 g of (0.52 mol) in THF2.8kg, Mo (N-2,6- Pr i 2 C _{6 H 3) (CHCMe 2 Ph} ) (OCMe (CF 3) 2) 2, 306mg of (0.4 mmol) was added, reacted as in example 1 to obtain a ring-opening metathesis copolymer solution 4.3kg . The polymerization rate was 100%, Mw = 7000, Mw / Mn = 1.95, and the content of Mo in the polymer precipitated with water was 43 ppm.

  To 0.5 kg fractioned from the obtained ring-opening metathesis copolymer solution, 7.79 g of 5 mass% Ru carbon used in Example 1 (dry mass 3.55 g mass ratio 90%), 5 mass% Rh carbon 0.80 g (dry mass 0.39 g, mass ratio 10%) was added, and a hydrogenation reaction was carried out at a hydrogen pressure of 5 MPa and 100 ° C. for 12 hours.

From the obtained hydrogenated solution of the ring-opening metathesis copolymer, a hydrogenated product of the ring-opening metathesis copolymer was precipitated in the same manner as in Example 1, and the white ring-opening metathesis copolymer having a hydrogenation rate of 100% was precipitated. A hydrogenated product of the polymer was obtained. The Mo metal content derived from the polymerization catalyst in the hydrogenated product of the obtained ring-opening metathesis copolymer was 140 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 100 ppb and 8 ppb, respectively. Mw = 9850, Mw / Mn = 2.05, [A] / [B] = 90/10, and there was no elimination of the 1-ethylcyclopentyl group of the structural unit [A]. The test piece having a thickness of 100 μm produced by the hot melt press was not turbid and had a colorless and transparent total light transmittance of 92%.
Further, in the same manner as in Example 1, when the deashing treatment was performed, the Mo metal content derived from the polymerization catalyst in the dry polymer was 1 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 0 ppb and 0 ppb, respectively.

[Example 6]
In a 5 L autoclave equipped with a magnetic stirrer under a nitrogen atmosphere, 4,10-dioxa-tricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 304 g (2.0 mol) ), 8-methoxymethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene 497 g (2.0 mol), and 1,5-hexadiene, 43 g of (0.52 mol) was dissolved in THF3.2kg, W (N-2,6- Pr i 2 C 6 H ₃ ) (CHCMe ₂ Ph) (OCMe (CF ₃ ) ₂ ) ₂ , 683 mg (0.8 mmol) was added, and the mixture was reacted at 60 ° C. for 3 hours. Thereafter, 173 mg (2.4 mmol) of n-butyraldehyde was added and cooled to obtain 4.0 kg of a ring-opening metathesis copolymer solution. The polymerization rate was 100%, Mw = 7500, Mw / Mn = 1.65, and the content of W in the polymer precipitated with water was 68 ppm.

  To 0.5 kg fractioned from the obtained ring-opening metathesis copolymer solution, 5.93 g of 5 mass% Ru carbon used in Example 1 (dry weight 2.70 g mass ratio 90%), 5 mass% Rh carbon 0.61 g (dry mass 0.30 g, mass ratio 10%) was added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and 100 ° C. for 12 hours.

  From the obtained hydrogenated solution of the ring-opening metathesis copolymer, a hydrogenated product of the ring-opening metathesis copolymer was precipitated in the same manner as in Example 1, and the white ring-opening metathesis copolymer having a hydrogenation rate of 100% was precipitated. A hydrogenated product of the polymer was obtained. The W metal content derived from the polymerization catalyst in the hydrogenated product of the obtained ring-opening metathesis copolymer was 260 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 160 ppb and 20 ppb, respectively. Mw = 9850, Mw / Mn = 2.05, [A] / [B] = 50/50, and there was no elimination of the 8-methoxymethyloxy group of the structural unit [A]. The test piece with a thickness of 100 μm produced by the hot melt press was not turbid and had a colorless and transparent total light transmittance of 91%.

  Further, in the same manner as in Example 1, when the decalcification treatment was performed, the W metal content derived from the polymerization catalyst in the dry polymer was 1 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 0 ppb and 0 ppb, respectively.

[Example 7]
In an autoclave similar to that of Example 1, 4,10-dioxa-tricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 61 g (0.4 mol), 8- (1 -Ethylcyclopentyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 541 g (1.8 mol), 8- (1-methyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, was dissolved 393 g (1.8 mol) and 1,5-hexadiene, 2.9 g of (0.035 mol) in THF2.9kg, Mo (N-2,6- Pr i 2 C ₆ H ₃ ) (CHCMe ₂ Ph) (OCMe (CF ₃ ) ₂ ) ₂ , 306 mg (0.4 mmol) was added and reacted in the same manner as in Example 1 to obtain 3.9 kg of a ring-opening metathesis copolymer solution. It was. The polymerization rate was 100%, Mw = 55000, Mw / Mn = 1.91, and the content of Mo in the polymer precipitated with water was 29 ppm.

  To 0.5 kg separated from the obtained ring-opening metathesis copolymer solution, 7.42 g of 5 mass% Ru carbon used in Example 1 (dry mass 3.38 g mass ratio 90%), 5 mass% Rh carbon 0.77 g (dry mass 0.38 g, mass ratio 10%) was added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and 100 ° C. for 12 hours.

  From the obtained hydrogenated solution of the ring-opening metathesis copolymer, a hydrogenated product of the ring-opening metathesis copolymer was precipitated in the same manner as in Example 1, and the white ring-opening metathesis copolymer having a hydrogenation rate of 100% was precipitated. A hydrogenated product of the polymer was obtained. The Mo metal content derived from the polymerization catalyst in the hydrogenated product of the obtained ring-opening metathesis copolymer was 350 ppb, and the Ru and Rh metal content derived from the hydrogenation reaction catalyst were 200 ppb and 15 ppb, respectively. Mw = 82000, Mw / Mn = 2.05, [A] / [B] / [D] = 45/10/45, and no elimination of 1-ethylcyclopentyl group of structural unit [A] It was. The test piece with a thickness of 100 μm produced by the hot melt press was not turbid and had a colorless and transparent total light transmittance of 91%.

  Further, in the same manner as in Example 1, when the deashing treatment was performed, the Mo metal content derived from the polymerization catalyst in the dry polymer was 1 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 0 ppb and 0 ppb, respectively.

[Example 8]
In the same autoclave as in Example 1, 4,10-dioxa-tricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 122 g (0.8 mol), 8-methoxymethyl Oxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 199 g (0.8 mol), 8- (1-methyloxycarbonyl) tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene, was dissolved 524 g (2.4 mol) and 1,5-hexadiene, 2.9 g of (0.035 mol) in THF2.6kg, Mo (N-2,6- Pr i 2 C ₆ H ₃ ) (CHCMe ₂ Ph) (OCMe (CF ₃ ) ₂ ) ₂ , 306 mg (0.4 mmol) was added and reacted in the same manner as in Example 1 to obtain 3.4 kg of a ring-opening metathesis copolymer solution. It was. The polymerization rate was 100%, Mw = 48000, Mw / Mn = 1.96, and the content of Mo in the polymer precipitated with water was 40 ppm.

  To 0.5 kg separated from the obtained ring-opening metathesis copolymer solution, 7.27 g of 5 mass% Ru carbon used in Example 1 (dry mass 3.31 g, mass ratio 90%), 5 mass% Rh carbon. 0.75 g (dry mass 0.37 g, mass ratio 10%) was added, and a hydrogenation reaction was performed at a hydrogen pressure of 5 MPa and 100 ° C. for 12 hours.

  From the obtained hydrogenated solution of the ring-opening metathesis copolymer, a hydrogenated product of the ring-opening metathesis copolymer was precipitated in the same manner as in Example 1, and the white ring-opening metathesis copolymer having a hydrogenation rate of 100% was precipitated. A hydrogenated product of the polymer was obtained. The Mo metal content derived from the polymerization catalyst in the hydrogenated product of the obtained ring-opening metathesis copolymer was 280 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 180 ppb and 23 ppb, respectively. Mw = 69600, Mw / Mn = 2.02, [A] / [B] / [D] = 20/20/60, and the elimination of the 8-methoxymethyloxy group of the structural unit [A] is There wasn't. The test piece with a thickness of 100 μm produced by the hot melt press was not turbid, and the colorless and transparent total light transmittance was 90%.

  Further, in the same manner as in Example 1, when the deashing treatment was performed, the Mo metal content derived from the polymerization catalyst in the dry polymer was 2 ppb, and the Ru and Rh metal contents derived from the hydrogenation reaction catalyst were 0 ppb and 0 ppb, respectively.

[Example 9]
The hydrogenation product of the ring-opening metathesis copolymer synthesized in Example 8 (metal content: Mo = 280 ppb, Ru = 180 ppb, Rh = 23 ppb) was added with 0. 0 Sumilizer GP (manufactured by Sumitomo Chemical Co., Ltd.) as a heat-resistant antioxidant. After adding 5% by mass and pelletizing with a pelletizer, using a small injection molding machine Micro-1 manufactured by Meiho, the temperature of the heating and kneading part is set to 260 ° C., the temperature of the mold is set to 90 ° C., and the injection speed A plate-shaped test piece having a diameter of 20 mm and a thickness of 2 mm was produced under the conditions of 20 mm / sec and an injection pressure of 40 MPa. A part of the test piece was cut out and measured, and from the ¹³ C-NMR spectrum, there was no elimination of the 8-methoxymethyloxy group. The test piece having a diameter of 20 mm and a thickness of 2 mm had no turbidity and had a colorless and transparent total light transmittance of 90%.

[Comparative Example 1]
Ring-opening metathesis copolymer in the same manner as in Example 1 except that the hydrogenation reaction catalyst of Example 1 was changed to 19.34 g of 5 mass% Ru carbon (dry mass 8.82 g) having a water content of 54.4%. The hydrogenated product was synthesized. The hydrogenation rate of the hydrogenated product of the obtained ring-opening metathesis copolymer was 93%, the Mo metal content derived from the polymerization catalyst was 1200 ppb, and the Ru metal content derived from the hydrogenation reaction catalyst was 290 ppb. Mw = 10000, Mw / Mn = 2.05, [A] / [B] = 50/50, and there was no elimination of the 1-ethylcyclopentyl group of the structural unit [A].
A test piece having a thickness of 102 μm obtained by hot press molding the hydrogenated product of the obtained ring-opening metathesis copolymer at 200 ° C. was colored yellow, and the total light transmittance was 75%.

[Comparative Example 2]
Ring-opening metathesis copolymer in the same manner as in Example 1 except that the hydrogenation reaction catalyst of Example 1 was changed to 17.89 g of 5 wt% Rh carbon having a water content of 50.7% (dry mass of 8.82 g). The hydrogenated product was synthesized. The hydrogenation rate of the hydrogenated product of the obtained ring-opening metathesis copolymer is 100%, the Mo metal content derived from the polymerization catalyst in the hydrogenated product is 5.6 ppm, and the Rh metal content derived from the hydrogenation reaction catalyst The amount was 96 ppm. Mw = 8050, Mw / Mn = 2.54, and the structure of the obtained polymer is that the 1-ethylcyclopentyl group of the structural unit [A] is eliminated by 40 mol% to generate a carboxylic acid. Assuming that the structural unit is [C], [A] / [B] / [C] = 10/50/40.
The resulting hydrogenated product of the ring-opening metathesis copolymer having a constitutional molar ratio [A] / [B] / [C] = 10/50/40 is not dissolved in PGMEA, and a coating varnish is produced. I could not. Furthermore, the test piece having a thickness of 100 μm obtained by hot-melt pressing at 200 ° C. was colored yellow, haze was generated, and became white and cloudy. The haze value was 12% and the total light transmittance was 35%.

[Comparative Example 3]
The hydrogenation reaction catalyst of Example 1 was changed to 3.31 g of 10% by mass Ru alumina, and the hydrogenation reaction was performed in the same manner as in Example 1 except that the hydrogenation reaction was performed at 120 ° C. for 24 hours. A combined hydrogenated product was synthesized. The hydrogenation rate of the hydrogenated product of the obtained ring-opening metathesis copolymer is 100%, the Mo metal content in the hydrogenated product is 12 ppm, the Ru metal content is 18 ppm, and the Al metal content is 0.4 ppm. Met. Mw = 9800, Mw / Mn = 2.05, [A] / [B] = 50/50, and there was no elimination of the 1-ethylcyclopentyl group of the structural unit [A]. A test piece with a thickness of 100 μm produced by a hot melt press was colored yellow and the total light transmittance was 73%.
Further, in the same manner as in Example 1, when the deashing treatment was performed, the Mo metal content derived from the polymerization catalyst in the dry polymer was 500 ppb, and the Ru metal content derived from the hydrogenation reaction catalyst was 540 ppb.

[Comparative Example 4]
The hydrogenation reaction catalyst of Example 1 was changed to 3.14 g of 5 mass% Ru alumina (mass ratio 95%) and 0.17 g of 5 mass% Rh alumina (mass ratio 5%). A hydrogenated ring-opening metathesis copolymer was synthesized. The hydrogenation rate of the hydrogenated product of the obtained ring-opening metathesis copolymer was 97%, the Mo metal content derived from the polymerization catalyst in the hydrogenated product was 3 ppm, and the Ru, Rh, and Al metal contents were 7 respectively. 0.5 ppm, 0.3 ppm, and 0.1 ppm. Mw = 10000 and Mw / Mn = 2.05.
Here, 5 mass% Ru alumina means an alumina supported Ru catalyst in which the supported amount of Ru is 5 mass% with respect to 100 mass% of alumina. Moreover, 5 mass% Rh alumina means the alumina carrying | support Rh catalyst whose loading of Rh is 5 mass% with respect to 100 mass% of alumina.
A test piece with a thickness of 100 μm produced by a hot melt press was colored yellow and the total light transmittance was 73%.

[Comparative Example 5]
The hydrogenation reaction catalyst of Example 1 was changed to chlorohydridocarbonyltris (triphenylphosphine) ruthenium, 0.2 g (0.21 mmol), and the same as Example 1 except that triethylamine, 21 mg (0.2 mmol) was added. Thus, a hydrogenated product of a ring-opening metathesis copolymer was synthesized. The hydrogenation rate of the hydrogenated product of the obtained ring-opening metathesis copolymer was 100%, the Mo metal content derived from the polymerization catalyst was 7 ppm, and the Ru metal content derived from the hydrogenation reaction catalyst was 16 ppm. Mw = 28000, Mw / Mn = 2.05, [A] / [B] = 50/50, and there was no elimination of the 1-ethylcyclopentyl group of the structural unit [A]. The test piece with a thickness of 100 μm produced by the hot melt press was colored yellow and the total light transmittance was 69%.
Further, in the same manner as in Example 1, when the decalcification treatment was performed, the Mo metal content derived from the polymerization catalyst in the dry polymer was 3500 ppb, and the Ru metal content derived from the hydrogenation reaction catalyst was 5400 ppb.

  The hydrogenated product of a highly polar ring-opening metathesis copolymer containing heteroatoms obtained by the production method of the present invention has a small amount of residual production catalyst metal component, and is used particularly in a semiconductor production process by ArF exposure. It can be used for semiconductor materials such as resist compositions. In addition, the hydrogenated ring-opening metathesis copolymer obtained by the production method of the present invention is used for optical parts that are not yellowed and require high transparency, and for organic EL, liquid crystal plastic substrate, or electronic materials. It can also be used.

Claims (7)

A production method for producing a hydrogenated product of a ring-opening metathesis copolymer comprising:
Hydrogenating a carbon-carbon double bond of a ring-opening metathesis copolymer using a carbon-supported hydrogenation reaction catalyst of ruthenium (Ru) metal and rhodium (Rh) metal in the presence of hydrogen,
The ring-opening metathesis copolymer includes a repeating structural unit [A] represented by the following general formula (1) and a repeating structural unit [B] represented by the following general formula (2), and the structural unit [A ] And the molar ratio ([A] / [B]) of the structural unit [B] is 5/95 or more and 90/10 or less,
A mass ratio (Ru / Rh) of the ruthenium and the rhodium in the carbon-supported hydrogenation reaction catalyst is 80/20 or more and 99/1 or less,
The hydrogenation rate of the double bond of the hydrogenated product of the obtained ring-opening metathesis copolymer is 99.5 mol% or more,
The elimination rate of the acid labile group in the structural unit [A] in the hydrogenated product of the obtained ring-opening metathesis copolymer is 1 mol% or less,
A method for producing a hydrogenated product of a ring-opening metathesis copolymer, wherein the total content of the polymerization catalyst and the metal derived from the hydrogenation reaction catalyst in the hydrogenated product of the obtained ring-opening metathesis copolymer is 1000 ppb or less.

Wherein R ¹ is selected from an acid labile alkoxy group having 4 to 20 carbon atoms, an alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms, or an alkoxycarbonylalkyloxycarbonyl group having 4 to 20 carbon atoms, j is 0 or 1.)

(In the formula, R ^{2 to} R ³ are each independently selected from hydrogen or an alkyl group having 1 to 10 carbon atoms, and X ¹ is —O— or —CR ⁴ R ⁵ — (R ⁴ and R ⁵ are Each represents hydrogen or an alkyl group having 1 to 20 carbon atoms). In the manufacturing method of the hydrogenated product of the ring-opening metathesis copolymer according to claim 1,
A method for producing a hydrogenated product of a ring-opening metathesis copolymer, wherein the metal derived from the polymerization catalyst and the hydrogenation reaction catalyst includes one or more selected from molybdenum, tungsten, ruthenium, and rhodium. In the method for producing a hydrogenated product of the ring-opening metathesis copolymer according to claim 1 or 2,
Hydrogenation of a ring-opening metathesis copolymer in which the total mass of ruthenium and rhodium in the carbon-supported hydrogenation reaction catalyst is 0.05% by mass or more and 1.0% by mass or less with respect to the ring-opening metathesis copolymer. Manufacturing method. In the manufacturing method of the hydrogenated product of the ring-opening metathesis copolymer as described in any one of Claims 1 thru | or 3,
A method for producing a hydrogenated product of a ring-opening metathesis copolymer, wherein the obtained hydrogenated product of the ring-opening metathesis copolymer is a resist material used in a semiconductor production lithography process. The repeating structural unit [A] represented by the general formula (1), the repeating structural unit [B] represented by the general formula (2), and the repeating structural unit [D] represented by the following general formula (3) And the total of the repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2), and represented by the following general formula (3) A hydrogenated product of a ring-opening metathesis copolymer having a structural molar ratio with the repeating structural unit [D] of ([A] + [B]) / [D] = 99/1 to 1/99. A hydrogenated product of a ring-opening metathesis copolymer produced by the method according to any one of claims 1 to 3.

(Wherein R ^{6 to} R ⁹ are hydrogen, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, X ² is selected from an alkoxycarbonyl group having 2 to 20 carbon atoms or an aryloxycarbonyl group having 7 to 20 carbon atoms, and X ² is —O— and —CR ¹⁰ R ¹¹ — (R ¹⁰ and R ¹¹ are each a hydrogen atom or a carbon atom. (Represents an alkyl group of 1 to 20), which may be the same or different, and R ^{6 to} R ⁹ may be bonded to each other, and k is 0 or 1.)   The hydrogenated product of a ring-opening metathesis copolymer according to claim 5, which is a raw material for optical components.   7. The ring-opening metathesis characterized in that the total content of all metal components derived from each catalyst is 10 ppb or less by demetallizing the hydrogenated ring-opening metathesis copolymer according to claim 5 or 6. Copolymer hydrogenated product.