JP5635445B2 - Method for producing hydrogenated ring-opening metathesis polymer - Google Patents

Description

The present invention relates to a method for producing a hydrogenated ring-opening metathesis polymer.

In recent years, integration of semiconductor integrated circuits has progressed, and large-scale integrated circuits and ultra-large-scale integrated circuits have been put into practical use. In addition to this, the minimum pattern of integrated circuits tends to be sub-micron and further miniaturized. It is in. To form a fine pattern, the substrate to be processed on which a thin film is formed is coated with a resist, and after selective exposure is performed to form a latent image of a desired pattern, development is performed to form a resist pattern, which is then used as a mask for dry etching After that, it is essential to use a lithography technique that obtains a desired pattern by removing the resist.
As the exposure light source used in this lithography technology, ultraviolet rays of g-line (wavelength 436 nm) and i-line (wavelength 365 nm) are used. Light, electron beam (EB), X-rays, and the like are used as light sources. Recently, excimer lasers (ArF lasers with a wavelength of 193 nm) have been used as exposure light sources for the most advanced fine pattern formation.

As a polymer used for a resist material that forms a submicron pattern using vacuum ultraviolet light, a resist composition comprising an aliphatic cyclic hydrocarbon as a main chain and a polymer compound having a cyclic skeleton having a functional group that is decomposed by an acid. It is known that a cyclic polymer as seen in a product is excellent in dry etching resistance and transparency to an exposure light source wavelength (for example, Patent Documents 1 and 2). Among them, the ring-opening metathesis polymer hydrogenated substance containing an ether bond (—O—) in the main chain has high polarity, excellent affinity for a developer, adhesion to a silicon substrate, etc., and a good resist composition. It is described that it becomes a raw material. (Patent Documents 3 and 4)
The excellent transparency of these cyclic polymers with respect to the exposure light source wavelength of 193 nm is a characteristic obtained by hydrogenating the double bond of the main chain of the aliphatic cyclic hydrocarbon, and in an unhydrogenated polymer, It is exemplified that the transmittance is greatly reduced, the resolution is deteriorated, and a good pattern shape cannot be obtained (Patent Documents 1 and 4), and the transmittance is high when the main chain double bond is hydrogenated. Obtaining a hydrogenated ring-opening metathesis polymer is an important issue.

Japanese Patent Laid-Open No. 9-230595 JP-A-9-244247 JP 2000-109545 A JP 2001-354756 A JP-A-4-202404 JP 2007-1967 A JP 2008-45118 A JP-A-11-193323

In the methods described in Patent Documents 5 to 7, metal complexes such as ruthenium, osmium, rhodium, and iridium are known as hydrogenation (hereinafter referred to as hydrogenation) catalysts for carbon-carbon double bonds. For example, RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ , RuH (OCOCH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ , RuH (OCOC ₆ H ₅ ) (CO) [P (C ₆ It is exemplified that metal hydride complexes represented by H ₅ ) ₃ ] ₂ are effective for hydrogenation of ring-opening metathesis polymers containing alkyl groups and ester groups. However, among the above ruthenium hydride complexes, RuHCl (CO) [P (C ₆ H ₅ ) ₃ ] ₃ which does not contain an ester group in the complex structure has a solubility in a hydrocarbon solvent such as toluene of 0.03%. When a concentrated catalyst solution is prepared, it becomes a slurry, and when it is put into the reactor, the hydrogenation catalyst adheres to the inner wall of the pipe etc. when it is put into the reactor, and it can not be put in short, resulting in a decrease in the hydrogenation rate. There are things to do. In addition, when a polar solvent such as tetrahydrofuran (THF) is used to improve solvent solubility, it is coordinated with the complex itself to reduce the hydrogenation efficiency. To use a metal hydride complex, RuH (OCOCH ₃ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ , RuH (OCOC ₆ H ₅ ) (CO) [P (C ₆ H ₅ ) ₃ ] ₂ It is necessary to modify the carboxylic acid to improve the solubility in a solvent.

Further, in the methods described in Patent Documents 3 to 4 and 8, as a hydrogenation method of a highly polar substituent such as a nitrile group, or a highly polar ring-opening metathesis polymer containing an ether bond in the main chain, Examples include methods in which a metal complex such as RuCl ₂ [P (C ₆ H ₅ ) ₃ ] ₃ , OsCl ₂ [P (C ₆ H ₅ ) ₃ ] ₃ and an amine compound are used in combination (Patent Documents 3, 4, and 8). ing. However, the amine compound used in the hydrogenation reaction may remain in the final product, reducing the product performance. For example, when this is used as a resist composition material, the residual amine compound generates photoacid. Since it acts as a base that suppresses the acid decomposition reaction by the agent, a good pattern shape in chemical amplification type lithography may not be obtained. Therefore, a hydrogenation method of a ring-opening metathesis polymer that does not remain in the final product and does not deteriorate the product performance has been desired.
The present invention has been made to solve the above problems, and provides a method for producing a highly polar ring-opening metathesis polymer hydrogenated product capable of overwhelmingly improving the efficiency of the catalyst. Objective.

The present invention is shown below.
[1] The repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2) have a molar ratio [A] / [B] = 10/90 to 90. Ring opening metathesis polymer solution composed of / 10 , dichlorotris (triphenylphosphine) ruthenium, dichlorotetrakis (triphenylphosphine) ruthenium, dibromotris (triphenylphosphine) ruthenium, dibromotetrakis (triphenylphosphine) ruthenium, Diiodotris (triphenylphosphine) ruthenium, diiodotetrakis (triphenylphosphine) ruthenium, dichlorotris (triphenylphosphine) osmium, dichlorotetrakis (triphenylphosphine) osmium, dibromotris (triphenylphosphine) osmium, dibu 2 mol times or more of carbon monoxide was brought into contact with an organometallic complex selected from the group consisting of lomotetrakis (triphenylphosphine) osmium, diiodotris (triphenylphosphine) osmium and diiodotetrakis (triphenylphosphine) osmium . A method for producing a hydrogenated ring-opening metathesis polymer in which a double bond of a main chain is hydrogenated with an organometallic complex .

(1)
^(Wherein at least one of R 1 to R ⁴ is an alkoxycarbonyl group having 2 to 20 carbon atoms, alkoxy alkyloxycarbonyl group having 3 to 20 carbon atoms or an alkoxycarbonyl alkyloxycarbonyl group having 4 to 20 carbon atoms, selected from, others are selected from hydrogen, alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms . Further, ^{X 1} is -O-, or ^-CR 5 ^{R 6} -. from ^(. R 5, ^{R 6} are representing hydrogen, an alkyl group having 1 to 20 carbon atoms) chosen, may be the same or different also , J is selected from 0 or 1.)

(2)
(Wherein R ^{7 to} R ¹⁰ are each independently selected from hydrogen or an alkyl group having 1 to 10 carbon atoms, and X ² represents —O— or —CR ¹¹ R ¹² — (R ¹¹ , R ¹² represents hydrogen, an alkyl group having 1 to 20 carbon atoms.) chosen.)

[2] In the above [1], any ^one of X ¹ and X ² of the ring-opening metathesis polymer composed of the repeating structural units [A] and [B] is —O—, and the other is —CH ₂ —. ] The manufacturing method of the ring-opening metathesis polymer hydrogenated substance of description .
[3] Dichlorotris (triphenylphosphine) ruthenium, dichlorotetrakis (triphenylphosphine) ruthenium, dibromotris (triphenylphosphine) ruthenium, dibromotetrakis (triphenylphosphine) ruthenium, diiodotris (triphenylphosphine) ruthenium, diiodotetrakis (Triphenylphosphine) ruthenium, dichlorotris (triphenylphosphine) osmium, dichlorotetrakis (triphenylphosphine) osmium, dibromotris (triphenylphosphine) osmium, dibromotetrakis (triphenylphosphine) osmium, diiodotris (triphenylphosphine) osmium , From the group consisting of diiodotetrakis (triphenylphosphine) osmium Wherein the organometallic complex, the molar ratio of carbon monoxide to be contacted, the manufacturing method of the hydrogenated ring-opening metathesis polymer according to the a 2-1000 [1] or [2] that barrel.
[4] The hydrogenated ring-opening metathesis polymer is, the a photoresist base polymer [1], prepared how hydrogenated ring-opening metathesis polymer according to [2] or [3].

ADVANTAGE OF THE INVENTION According to this invention, the purification method which can remove a metal component efficiently and can reduce a metal component reliably, and the polymer refine | purified by this purification method are provided.

The ^{1 H-NMR} spectrum of the resulting hydrogenated ring-opening metathesis polymer in Example 1.

The present invention is shown below.
In the present invention, the repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2) have a molar ratio [A] / [B] = 10/90 to A ring-opening metathesis polymer solution composed of 90/10 is an organometallic complex obtained by contacting a carbon monoxide with a molar ratio of 2 moles or more with respect to the organometallic complex represented by the general formula (3). It is a manufacturing method of the ring-opening metathesis polymer hydrogenation which hydrogenates a bond.

In the present invention, the repeating structural unit [A] represented by the general formula (1) is represented by the following formula.

(1)
^(Wherein at least one of R 1 to R ⁴ is an alkoxycarbonyl group having 2 to 20 carbon atoms, alkoxy alkyloxycarbonyl group having 3 to 20 carbon atoms or an alkoxycarbonyl alkyloxycarbonyl group having 4 to 20 carbon atoms, selected from, others are selected from hydrogen, alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms . Further, ^{X 1} is -O-, or ^-CR 5 ^{R 6} -. from ^(. R 5, ^{R 6} are representing hydrogen, an alkyl group having 1 to 20 carbon atoms) chosen, may be the same or different also , J is selected from 0 or 1.)

More specifically, in the general formula (1), at least one of R ^{1 to} R ⁴ and the alkoxycarbonyl group having 2 to 20 carbon atoms includes, for example, a methoxycarbonyl group , an ethoxycarbonyl group , and an n-propoxycarbonyl group. , Isopropoxycarbonyl group , n-butoxycarbonyl group , isobutoxycarbonyl group , tert-butoxycarbonyl group , cyclopentyloxycarbonyl group , cyclohexyloxycarbonyl group , cyclooctyloxycarbonyl group , norbornyloxycarbonyl group , 1-methylcyclopentyloxy carbonyl group, 1-ethyl cyclopentyloxy group, 1-methyl-norbornyl oxy group, 1-ethyl norbornyl oxy carbonyl group, tetrahydrofuran-2-yl-oxy group, and Tet Examples include a lahydropyran-2-yloxycarbonyl group , a 1-adamantyloxycarbonyl group , and a 2-adamantyloxycarbonyl group .

Examples of the alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms include methoxymethyloxycarbonyl group , ethoxymethyloxycarbonyl group , n-propoxymethyloxycarbonyl group , isopropoxymethyloxycarbonyl group , n-butoxymethyloxy group . Carbonyl group , isobutoxymethyloxycarbonyl group , tert-butoxymethyloxycarbonyl group , cyclopentyloxymethyloxycarbonyl group , cyclohexyloxymethyloxycarbonyl group , cyclooctyloxymethyloxycarbonyl group , norbornyloxymethyloxycarbonyl group , 1- Methylcyclopentyloxymethyloxycarbonyl group , 1-ethylcyclopentyloxymethyloxycarbonyl group , 1-methylnorbornyloxymethyloxy Sicarbonyl group , 1-ethylnorbornyloxymethyloxycarbonyl group , 1-ethoxypropyloxymethyloxycarbonyl group , 1-ethoxy-1-methylethyloxymethyloxycarbonyl group , tetrahydrofuran-2-yloxymethyloxycarbonyl group , And tetrahydropyran-2-yloxymethyloxycarbonyl group , 1-adamantyloxymethyloxycarbonyl group , 2-adamantyloxymethyloxycarbonyl group and the like.

Furthermore, examples of the alkoxycarbonylalkyloxycarbonyl group having 4 to 20 carbon atoms include a methoxycarbonylmethyloxycarbonyl group , an ethoxycarbonylmethyloxycarbonyl group , an n-propoxycarbonylmethyloxycarbonyl group , an isopropoxycarbonylmethyloxycarbonyl group , n-butoxycarbonylmethyloxycarbonyl group , isobutoxycarbonylmethyloxycarbonyl group , tert-butoxycarbonylmethyloxycarbonyl group , cyclopentyloxycarbonylmethyloxycarbonyl group , cyclohexyloxycarbonylmethyloxycarbonyl group , cyclooctyloxycarbonylmethyloxycarbonyl group , Norbornyloxycarbonylmethyloxycarbonyl group , 1-methylcyclopentylo Alkoxycarbonylmethyl oxycarbonyl group, 1-ethyl Cyclopentyloxycarbonyl methyloxy carbonyl group, 1-methyl-norbornyl oxy carbonyl methyloxy carbonyl group, 1-ethyl norbornyl oxy carbonyl methyloxy carbonyl group, 1-ethoxypropyl oxycarbonyl methyloxy Carbonyl group , 1-ethoxy-1-methylethyloxycarbonylmethyloxycarbonyl group , tetrahydrofuran-2-yloxycarbonylmethyloxycarbonyl group , and tetrahydropyran-2-yloxycarbonylmethyloxycarbonyl group , 1-adamantyloxycarbonylmethyl Examples thereof include an oxycarbonyl group and a 2-adamantyloxycarbonylmethyloxycarbonyl group .
At least one of these R ^{1 to} R ⁴ contains a group that is decomposed by a photosensitizer, that is, an acid generated from an acid generator at the time of exposure. It is preferable to solubilize.

Specifically, among the above, tert-butoxycarbonyl group , cyclopentyloxycarbonyl group , norbornyloxycarbonyl group , 1-methylcyclopentyloxycarbonyl group , 1-ethylcyclopentyloxycarbonyl group , 1-methylnorbornyloxycarbonyl group , 1-ethyl-norbornyl oxy carbonyl group, tetrahydrofuran-2-yl-oxy group, and tetrahydropyran-2-yl-oxy group, 1-adamantyloxycarbonyl group, can be exemplified 2-adamantyloxycarbonyl group, also, methoxymethyl oxycarbonyl group, ethoxymethyl oxycarbonyl group, n- propoxymethyl oxycarbonyl group, isopropoxymethyl oxycarbonyl group, n- butoxymethyl oxycarbonyl group, Isobutoki Cymethyloxycarbonyl group , tert-butoxymethyloxycarbonyl group , cyclopentyloxymethyloxycarbonyl group , cyclohexyloxymethyloxycarbonyl group , cyclooctyloxymethyloxycarbonyl group , norbornyloxymethyloxycarbonyl group , 1-methylcyclopentyloxymethyl oxycarbonyl group, 1-ethyl-cyclopentyloxy-methyloxy carbonyl group, 1-methyl-norbornyl oxy methyloxy carbonyl group, 1-ethyl norbornyl oxy methyloxy carbonyl group, 1-ethoxypropyl oxymethyl oxycarbonyl group, 1-ethoxy - 1-methylethyloxymethyloxycarbonyl group , tetrahydrofuran-2-yloxymethyloxycarbonyl group , and tetrahydropyran-2- Ilylmethyloxycarbonyl group , 1-adamantyloxymethyloxycarbonyl group , and 2-adamantyloxymethyloxycarbonyl group can be exemplified.

Further, methoxycarbonylmethyloxycarbonyl group , ethoxycarbonylmethyloxycarbonyl group , n-propoxycarbonylmethyloxycarbonyl group , isopropoxycarbonylmethyloxycarbonyl group , n-butoxycarbonylmethyloxycarbonyl group , isobutoxycarbonylmethyloxycarbonyl group , tert-butoxycarbonylmethyloxycarbonyl group , cyclopentyloxycarbonylmethyloxycarbonyl group , cyclohexyloxycarbonylmethyloxycarbonyl group , cyclooctyloxycarbonylmethyloxycarbonyl group , norbornyloxycarbonylmethyloxycarbonyl group , 1-methylcyclopentyloxycarbonylmethyl Oxycarbonyl group , 1-ethylcyclopentyloxycarbonyl Methyloxy carbonyl group, 1-methyl-norbornyl oxy carbonyl methyloxy carbonyl group, 1-ethyl norbornyl oxy carbonyl methyloxy carbonyl group, 1-ethoxypropyl oxycarbonyl methyloxy carbonyl group, 1-ethoxy-1-methylethyl oxycarbonyl methyloxy carbonyl group, tetrahydrofuran-2-yl oxycarbonyl methyloxy carbonyl group, and tetrahydropyran-2-yl oxycarbonyl methyloxy carbonyl group, 1-adamantyloxycarbonyl methyloxy carbonyl group, 2-adamantyloxycarbonyl methyloxy carbonyl group Can be illustrated.

The the other ^R 1 to R ^4, a hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, aryloxycarbonyl of 6 to 20 carbon atoms are each independently selected from the group, the alkyl group having 1 to 20 carbon atoms, e.g., methyl group, ethyl group, propyl group, isopropyl group, n- butyl group, isobutyl group, tert- butyl group, cyclopentyl group, cyclohexyl group and the like, the alkoxy group having 1 to 20 carbon atoms, e.g., methoxy, ethoxy, n- propoxy, isopropoxy, n- butoxy group, etc. tert- butoxy or menthoxy group, and the like Examples of the alkoxyalkyl group having 2 to 20 carbon atoms include a methoxymethyl group , a methoxyethyl group , an ethoxymethyl group , and a tert-butyl group . Tokishimechiru group, such as tert- butoxyethyl group or a methoxy menthyl group. Furthermore, aryloxycarbonyl group having 6 to 20 carbon atoms, e.g., phenoxycarbonyl group or a naphthoxycarbonyl group and the like, and the like.

X ¹ Is -O- or -CR ⁵ R ⁶ -From (R ⁵ , R ⁶ Represents hydrogen and alkyl having 1 to 20 carbon atoms), which may be the same or different. j represents 0 or 1;
Furthermore, in the present invention, among specific examples of the repeating structural unit represented by the general formula (1), X ¹ Is -CH ₂ As a specific example of −, j = 0,
Poly (1-methoxycarbonyl-2,4-cyclopentyleneethyne), poly (1-ethoxycarbonyl-2,4-cyclopentyleneethyne), poly (1-n-propoxycarbonyl-2,4-cyclopentylene) Ethyne), poly (1-isopropoxycarbonyl-2,4-cyclopentyleneethine), poly (1-n-butoxycarbonyl-2,4-cyclopentyleneethine), poly (1-isobutoxycarbonyl-2, 4-cyclopentyleneethine), poly (1-tert-butoxycarbonyl-2,4-cyclopentyleneethine), poly (1-cyclopentyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-cyclohexyl) Oxycarbonyl-2,4-cyclopentyleneethyne), poly (1-cyclooctyloxycarbonyl-) 2,4-cyclopentyleneethyne), poly (1-norbornyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-1′-methylcyclopentyloxycarbonyl-2,4-cyclopentyleneethine) , Poly (1-1′-ethylcyclopentyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-1′-methylnorbornyloxycarbonyl-2,4-cyclopentyleneethine), poly (1- 1'-ethylnorbornyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-tetrahydrofuran-2'-yloxycarbonyl-2,4-cyclopentyleneethine), poly (1-tetrahydropyran-2) '-Yloxycarbonyl-2,4-cyclopentyleneethyne), poly (1-1'-adamantyloxycarboni) Ru-2,4-cyclopentyleneethine), poly (1-2′-adamantyloxycarbonyl-2,4-cyclopentyleneethine),
Also, poly (1-methoxymethyloxycarbonyl-2,4-cyclopentylene ethyne), poly (1-ethoxymethyloxycarbonyl-2,4-cyclopentylene ethyne), poly (1-n-propoxymethyloxycarbonyl) -2,4-cyclopentyleneethine), poly (1-isopropoxymethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-n-butoxymethyloxycarbonyl-2,4-cyclopentyleneethine) ), Poly (1-isobutoxymethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-tert-butoxymethyloxycarbonyl-2,4-cyclopentyleneethyne), poly (1-cyclopentyloxymethyl) Oxycarbonyl-2,4-cyclopentyleneethyne), poly (1-cyclo Hexyloxymethyloxycarbonyl-2,4-cyclopentyleneethyne), poly (1-cyclooctyloxymethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-norbornyloxymethyloxycarbonyl-2, 4-cyclopentyleneethine), poly (1-1′-methylcyclopentyloxymethyloxycarbonyl-2,4-cyclopentyleneethyne), poly (1-1′-ethylcyclopentyloxymethyloxycarbonyl-2,4- Cyclopentyleneethine), poly (1-1′-methylnorbornyloxymethyloxycarbonyl-2,4-cyclopentyleneethyne), poly (1-1′-ethylnorbornyloxymethyloxycarbonyl-2,4- Cyclopentylene ethyne), poly (1-1'-ethoxypropyloxy) Methyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-1′-ethoxy-1′-methylethyloxymethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-tetrahydrofuran-2) '-Yloxymethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-tetrahydropyran-2'-yloxymethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-1') -Adamantyloxymethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-2'-adamantyloxymethyloxycarbonyl-2,4-cyclopentyleneethine),
Furthermore, poly (1-methoxycarbonylmethyloxycarbonyl-2,4-cyclopentylene ethyne), poly (1-ethoxycarbonylmethyloxycarbonyl-2,4-cyclopentylene ethyne), poly (1-n-propoxycarbonyl) Methyloxycarbonyl-2,4-cyclopentyleneethyne), poly (1-isopropoxycarbonylmethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-n-butoxycarbonylmethyloxycarbonyl-2,4) -Cyclopentyleneethine), poly (1-isobutoxycarbonylmethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-tert-butoxycarbonylmethyloxycarbonyl-2,4-cyclopentyleneethine), Poly (1-cyclopentyloxyca) Sulfonylmethyloxycarbonyl-2,4-cyclopentyleneethyne), poly (1-cyclohexyloxycarbonylmethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-cyclooctyloxycarbonylmethyloxycarbonyl-2, 4-cyclopentyleneethine), poly (1-norbornyloxycarbonylmethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-1′-methylcyclopentyloxycarbonylmethyloxycarbonyl-2,4-cyclo) Pentyleneethine), poly (1-1′-ethylcyclopentyloxycarbonylmethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-1′-methylnorbornyloxycarbonylmethyloxycarbonyl-2,4- Cyclopentile Ethyne), poly (1-1′-ethylnorbornyloxycarbonylmethyloxycarbonyl-2,4-cyclopentyleneethyne), poly (1-1′-ethoxypropyloxycarbonylmethyloxycarbonyl-2,4-cyclopentyl) Lenethine), poly (1-1′-ethoxy-1′-methylethyloxycarbonylmethyloxycarbonyl-2,4-cyclopentyleneethine), poly (1-tetrahydrofuran-2′-yloxycarbonylmethyloxycarbonyl-) 2,4-cyclopentyleneethyne), poly (1-tetrahydropyran-2′-yloxycarbonylmethyloxycarbonyl-2,4-cyclopentyleneethyne), poly (1-1′-adamantyloxycarbonylmethyloxycarbonyl) -2,4-cyclopentyleneethine), poly 1-2'- adamantyloxycarbonyl methyloxy carbonyl-2,4-cyclopentylene ethyne) and the like,
X ¹ Is -CH ₂ -, J = 1 is a specific example:
Poly (3-methoxycarbonyl-7,9-tricyclo [4.3.0.1 ^2,5 Decanylene ethyne), poly (3-ethoxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-n-propoxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-isopropoxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-n-butoxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-isobutoxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-tert-butoxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclopentyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclohexyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 ] Decanylene ethyne), poly (3-cyclooctyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-norbornyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-methylcyclopentyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-ethylcyclopentyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-methylnorbornyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-ethylnorbornyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-tetrahydrofuran-2′-yloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tetrahydropyran-2′-yloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-adamantyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-2′-adamantyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 ] Decanylene ethyne),
Also, poly (3-methoxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1 ^2,5 Decanylene ethyne), poly (3-ethoxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-n-propoxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-isopropoxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-n-butoxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-isobutoxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-tert-butoxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclopentyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclohexyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclooctyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-norbornyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-methylcyclopentyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-ethylcyclopentyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-methylnorbornyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-ethylnorbornyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-ethoxypropyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-ethoxy-1′-methylethyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tetrahydrofuran-2′-yloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-tetrahydropyran-2′-yloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Dedecanylene ethyne), poly (3-1′-adamantyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-2′-adamantyloxymethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 ] Decanylene ethyne),
Furthermore, poly (3-methoxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1 ^2,5 Decanylene ethyne), poly (3-ethoxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-n-propoxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-isopropoxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Dedecanylene ethyne), poly (3-n-butoxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-isobutoxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-tert-butoxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclopentyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-cyclohexyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclooctyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-norbornyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-methylcyclopentyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethylcyclopentyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-methylnorbornyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethylnorbornyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethoxypropyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethoxy-1′-methylethyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tetrahydrofuran-2′-yloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tetrahydropyran-2′-yloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-adamantyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-2′-adamantyloxycarbonylmethyloxycarbonyl-7,9-tricyclo [4.3.0.1] ^2,5 ] Decanylene ethyne)
X ¹ As a specific example in which -O- and j = 0,
Poly (1-methoxycarbonyl-3-oxa-2,4-cyclopentyleneethyne), poly (1-ethoxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-n-propoxycarbonyl) -3-oxa-2,4-cyclopentyleneethine), poly (1-isopropoxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-n-butoxycarbonyl-3-oxa-) 2,4-cyclopentyleneethine), poly (1-isobutoxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-tert-butoxycarbonyl-3-oxa-2,4-cyclo) Pentyleneethine), poly (1-cyclopentyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-cyclohexyl) Ruoxycarbonyl-3-oxa-2,4-cyclopentyleneethyne), poly (1-cyclooctyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-norbornyloxycarbonyl- 3-oxa-2,4-cyclopentyleneethyne), poly (1-1′-methylcyclopentyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1′-ethylcyclopentyloxy) Carbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1′-methylnorbornyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1′- Ethyl norbornyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-tetrahydrofuran-2′-ylo) Cycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-tetrahydropyran-2′-yloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1 '-Adamantyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-2'-adamantyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine),
Further, poly (1-methoxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-ethoxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly ( 1-n-propoxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-isopropoxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1 -N-butoxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-isobutoxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1- tert-butoxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethyne), poly (1-cyclopent Tiloxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-cyclohexyloxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-cyclooctyl) Oxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-norbornyloxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1 ′ -Methylcyclopentyloxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1'-ethylcyclopentyloxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), Poly (1-1'-methylnorbornyloxymethyloxycarbonyl-3-oxy -2,4-cyclopentyleneethine), poly (1-1'-ethylnorbornyloxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1'-ethoxypropyloxy) Methyloxycarbonyl-3-oxa-2,4-cyclopentyleneethyne), poly (1-1′-ethoxy-1′-methylethyloxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine) Poly (1-tetrahydrofuran-2′-yloxymethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethyne), poly (1-tetrahydropyran-2′-yloxymethyloxycarbonyl-3-oxa-) 2,4-cyclopentyleneethine), poly (1-1′-adamantyloxymethyloxycarbonyl-3-oxa-) , 4-cyclopentylene ethyne), poly (1-2'- adamantyloxymethyl oxycarbonyl-3-oxa-2,4-cyclopentylene ethyne),
Furthermore, poly (1-methoxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-ethoxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), Poly (1-n-propoxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-isopropoxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine) , Poly (1-n-butoxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-isobutoxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine) ), Poly (1-tert-butoxycarbonylmethyloxycarbo) Nyl-3-oxa-2,4-cyclopentyleneethyne), poly (1-cyclopentyloxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethyne), poly (1-cyclohexyloxycarbonylmethyloxy) Carbonyl-3-oxa-2,4-cyclopentyleneethyne), poly (1-cyclooctyloxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-norbornyloxycarbonyl) Methyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1′-methylcyclopentyloxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1 -1′-ethylcyclopentyloxycarbonylmethyl Xycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1′-methylnorbornyloxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1 -1′-ethylnorbornyloxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1′-ethoxypropyloxycarbonylmethyloxycarbonyl-3-oxa-2,4- Cyclopentyleneethine), poly (1-1′-ethoxy-1′-methylethyloxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-tetrahydrofuran-2′-yl) Oxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly Li (1-tetrahydropyran-2′-yloxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine), poly (1-1′-adamantyloxycarbonylmethyloxycarbonyl-3-oxa-2) , 4-cyclopentyleneethine), poly (1-2′-adamantyloxycarbonylmethyloxycarbonyl-3-oxa-2,4-cyclopentyleneethine) and the like,
X ¹ As a specific example where is -O- and j = 1,
Poly (3-methoxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1 ^2,5 Decanylene ethyne), poly (3-ethoxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Dedecanylene ethyne), poly (3-n-propoxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Dedecanylene ethyne), poly (3-isopropoxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-n-butoxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-isobutoxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-tert-butoxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclopentyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-cyclohexyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclooctyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-norbornyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-methylcyclopentyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethylcyclopentyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-methylnorbornyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethylnorbornyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tetrahydrofuran-2′-yloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tetrahydropyran-2′-yloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-adamantyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Dedecanylene ethyne), poly (3-2′-adamantyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-methoxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Dedecanylene ethyne), poly (3-ethoxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-n-propoxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-isopropoxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-n-butoxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-isobutoxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-tert-butoxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclopentyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-cyclohexyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-cyclooctyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-norbornyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-1′-methylcyclopentyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethylcyclopentyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-methylnorbornyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethylnorbornyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethoxypropyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethoxy-1′-methylethyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tetrahydrofuran-2′-yloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tetrahydropyran-2′-yloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-adamantyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1] ^2,5 Decanylene ethyne), poly (3-2′-adamantyloxymethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 ] Decanylene ethyne),
Furthermore, poly (3-methoxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-ethoxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-n-propoxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-isopropoxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-n-butoxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-isobutoxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tert-butoxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-cyclopentyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Dedecanylene ethyne), poly (3-cyclohexyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-cyclooctyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-norbornyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-methylcyclopentyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethylcyclopentyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-methylnorbornyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethylnorbornyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethoxypropyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-ethoxy-1′-methylethyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tetrahydrofuran-2′-yloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-tetrahydropyran-2′-yloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-1′-adamantyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 Decanylene ethyne), poly (3-2′-adamantyloxycarbonylmethyloxycarbonyl-8-oxa-7,9-tricyclo [4.3.0.1]. ^2,5 ] Decanylene ethyne) and the like.

In the present invention, the repeating structural unit [B] represented by the general formula (2) copolymerized with the repeating structural unit [A] represented by the general formula (1) is represented by the following formula:

(2)
(Wherein R ^{7 to} R ¹⁰ are each independently selected from hydrogen or an alkyl group having 1 to 10 carbon atoms, and X ² represents —O— or —CR ¹¹ R ¹² — (R ¹¹ , R ¹² represents hydrogen, an alkyl group having 1 to 20 carbon atoms.) chosen.)

More specifically, in the general formula (2), R ^{7 to} R ¹⁰ are each independently selected from hydrogen or an alkyl group having 1 to 10 carbon atoms, such as a methyl group , an ethyl group , a propyl group , an isopropyl group , Examples thereof include n-butyl group , isobutyl group , tert-butyl group , cyclopentyl group , cyclohexyl group and the like.
X ² is selected from —O— or —CR ¹¹ R ¹² — (R ¹¹ and R ¹² represent hydrogen and an alkyl group having 1 to 20 carbon atoms), and the alkyl group having 1 to 20 carbon atoms is selected . Examples thereof include a methyl group , an ethyl group , a propyl group , an isopropyl group , an n-butyl group , an isobutyl group , a tert-butyl group , a cyclopentyl group , and a cyclohexyl group .

Furthermore, in the present invention, among specific examples of the repeating structural unit represented by the general formula (2), as a specific example in which X ² is —CH ₂ —, poly (3-oxa-2- Oxo-6,8-bicyclo [3.3.0] octylene ethyne), poly (4,4-dimethyl-3-oxa-2-oxo-6,8-bicyclo [3.3.0] octylene ethyne), poly ( 1,5-dimethyl-3-oxa-2-oxo-6,8-bicyclo [3.3.0] octylene ethyne), poly (1,4,4,5-tetramethyl-3-oxa-2-oxo-) 6,8-bicyclo [3.3.0] octylene ethyne) and the like.

Specific examples of X ² being —O— include poly (3,7-dioxa-2-oxo-6,8-bicyclo [3.3.0] octylene ethyne), poly (4,4- Dimethyl-3,7-dioxa-2-oxo-6,8-bicyclo [3.3.0] octylene ethyne), poly (1,5-dimethyl-3,7-dioxa-2-oxo-6,8-bicyclo) [3.3.0] octylene ethyne), poly (1,4,4,5-tetramethyl-3,7-dioxa-2-oxo-6,8-bicyclo [3.3.0] octylene ethyne) and the like. It is done.

In the present invention, the organometallic complex represented by the general formula (3) is
MQ _k Z _m (3)
(In the formula, M represents a ruthenium atom or an osmium atom, Q represents a halogen atom, and is selected from fluorine, chlorine, bromine, or iodine. Z represents PR ′ ¹ R ′ ² R ′ ³ (P represents a phosphorus atom) R ′ ¹ R ′ ² R ′ ³ represents the same or different linear, branched or cyclic alkyl group, alkenyl group, aryl group, alkoxy group or aryloxy group . And k is an integer of 1 to 4, m is an integer of 2 to 4, and k + m is an integer of 4 to 6.

  Examples of the organic phosphorus compound represented by Z include trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-propylphosphine, tri-tert-butylphosphine, triisobutylphosphine, tri-n-butylphosphine, tri Cyclohexylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, tri-o-tolylphosphine, tri-m-tolylphosphine, tri-p-tolylphosphine, diethylphenylphosphine, dichloro (ethyl) phosphine, dichloro (phenyl) Examples include phosphine and chlorodiphenylphosphine.

In the present invention, the organometallic complex represented by the general formula (3) is, for example, dichlorotris (triphenylphosphine) ruthenium, dichlorotetrakis (triphenylphosphine) ruthenium, dichlorotris (trimethylphosphine) ruthenium, dichlorotris (triethyl). Phosphine) ruthenium, dichlorotris (tricyclohexylphosphine) ruthenium, dichlorotris (trimethyldiphenylphosphine) ruthenium, dichlorotris (tridimethylphenylphosphine) ruthenium, dichlorotris (tri-o-tolylphosphine) ruthenium, dichlorotris (dichloroethylphosphine) ) Ruthenium, dichlorotris (dichlorophenylphosphine) ruthenium,
Dibromotris (triphenylphosphine) ruthenium, dibromotetrakis (triphenylphosphine) ruthenium, dibromotris (trimethylphosphine) ruthenium, dibromotris (triethylphosphine) ruthenium, dibromotris (tricyclohexylphosphine) ruthenium, dibromotris (trimethyldiphenyl) Phosphine) ruthenium, dibromotris (tridimethylphenylphosphine) ruthenium, dibromotris (tri-o-tolylphosphine) ruthenium, diiodotris (triphenylphosphine) ruthenium, diiodotetrakis (triphenylphosphine) ruthenium, diiodotris (trimethylphosphine) ruthenium , Diiodotris (triethylphosphine) ruthenium, diiodo Scan (tricyclohexylphosphine) ruthenium, Jiyodotorisu (trimethyl diphenylphosphine) ruthenium, Jiyodotorisu (tri-dimethylphenyl phosphine) ruthenium, Jiyodotorisu (tri -o- tolyl phosphine) ruthenium and the like are exemplified,

  In addition, dichlorotris (triphenylphosphine) osmium, dichlorotetrakis (triphenylphosphine) osmium, dichlorotris (trimethylphosphine) osmium, dichlorotris (triethylphosphine) osmium, dichlorotris (tricyclohexylphosphine) osmium, dichlorotris (trimethyldiphenyl) Phosphine) osmium, dichlorotris (tridimethylphenylphosphine) osmium, dichlorotris (tri-o-tolylphosphine) osmium, dichlorotris (dichloroethylphosphine) osmium, dichlorotris (dichlorophenylphosphine) osmium, dibromotris (triphenylphosphine) Osmium, dibromotetrakis (triphenylphosphine) osmium Dibromotris (trimethylphosphine) osmium, dibromotris (triethylphosphine) ruthenium, dibromotris (tricyclohexylphosphine) osmium, dibromotris (trimethyldiphenylphosphine) osmium, dibromotris (tridimethylphenylphosphine) osmium, dibromotris (tri-o -Tolylphosphine) osmium, diiodotris (triphenylphosphine) osmium, diiodotetrakis (triphenylphosphine) osmium, diiodotris (trimethylphosphine) osmium, diiodotris (triethylphosphine) osmium, diiodotris (tricyclohexylphosphine) osmium, diiodotris (trimethyldiphenyl) Phosphine) Osmium, Jiyo Dotorisu (tri-dimethylphenyl phosphine) osmium, Jiyodotorisu (tri -o- tolyl phosphine) osmium, and the like.

  Particularly effective organometallic complexes include dichlorotris (triphenylphosphine) ruthenium, dichlorotetrakis (triphenylphosphine) ruthenium, dibromotris (triphenylphosphine) ruthenium, dibromotetrakis (triphenyl) containing triphenylphosphine. Phosphine) ruthenium, diiodotris (triphenylphosphine) ruthenium, diiodotetrakis (triphenylphosphine) ruthenium, dichlorotris (triphenylphosphine) osmium, dichlorotetrakis (triphenylphosphine) osmium, dibromotris (triphenylphosphine) osmium, dibromo Tetrakis (triphenylphosphine) osmium, diiodotris (triphenylphosphine) osmium, Iodotetrakis (triphenylphosphine) osmium is preferably used, more preferably dichlorotris (triphenylphosphine) ruthenium, dichlorotetrakis (triphenylphosphine) ruthenium, dichlorotris (triphenylphosphine) osmium, dichlorotetrakis (triphenylphosphine). It is preferred to use osmium as a hydrogenation catalyst.

  In the present invention, the repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2) have a molar ratio [A] / [B] = 10/90 to A ring-opening metathesis polymer solution composed of 90/10 is an organometallic complex obtained by contacting a carbon monoxide with a molar ratio of 2 moles or more with respect to the organometallic complex represented by the general formula (3). This is a method for producing a hydrogenated ring-opening metathesis polymer in which a bond is hydrogenated. In particular, the hydrogenated ring-opening metathesis polymer produced by the present invention is useful as a method for producing a base polymer for a photoresist.

  For example, a photoresist base polymer is used as a positive resist composition together with an acid generator and a solvent. Here, the acid generator is a substance that generates Bronsted acid or Lewis acid when exposed to activating radiation such as excimer laser. Furthermore, a dissolution rate modifier, a surfactant, a storage stabilizer, a sensitizer, a striation inhibitor, or the like can be added to the resist composition. This resist composition can be formed into a resist film by applying the composition to a substrate surface such as a silicon wafer by a conventional method such as spin coating and then removing the solvent by drying. The exposure for is performed by irradiating the resist film with far ultraviolet rays, a KrF excimer laser, an ArF excimer laser, or an electron beam, and further heat treatment (post-exposure baking) can increase the sensitivity. Next, a relief pattern is obtained by washing out the exposed portion with a developing solution such as an alkaline aqueous solution. The relief pattern formed by using the hydrogenated ring-opening metathesis polymer of the present invention has extremely good resolution and contrast. Furthermore, the substrate can be etched using the pattern formed as described above as a mask.

  Furthermore, in the ring-opening metathesis polymer hydrogenated product of the present invention, the cyclic ring-opening metathesis polymer of the precursor is generally 10 to 90 mol% of the repeating structural unit [A] represented by the general formula (1). The repeating structural unit [B] represented by the formula (2) is 90 to 10 mol%, and the molar ratio [A] / [B] = 10/90 to 90/10. The molar ratio is preferably a molar ratio [A] / [B] = 20/80 to 80/20, and more preferably 30/70 to 70/30.

At least one of R ^{1 to} R ⁴ of the structural unit [A] is an alkoxycarbonyl having 2 to 20 carbon atoms, an alkoxyalkyloxycarbonyl having 3 to 20 carbon atoms, or an alkoxycarbonylalkyloxycarbonyl having 4 to 20 carbon atoms. And preferably contains a group that is decomposed by an acid generated from the photosensitizer during exposure. However, after exposure, they change to carboxylic acids, so that the aqueous solution is solubilized and developed to form a resist pattern by developing, if the molar ratio is less than 10 mol%, the development becomes insufficient. Further, when the structural unit [B] is less than 10 mol%, the polarity is remarkably lowered, and being in this range improves the wetting tension at the time of development with an alkaline aqueous solution after exposure and solves uneven development. Is important to. When these structural units are in this range, it is suitable for preparing a resist composition, and is dissolved in a polar solvent such as 2-heptanone together with a highly polar photosensitizer so as to be processed like a silicon substrate. This is extremely important as a resist material applied to the substrate. That is, the hydrogenated product of the ring-opening metathesis polymer can form a uniform smooth coating film by increasing the solubility in the polar solvent or the dissolution rate when preparing the resist composition.

The ring-opening metathesis polymer hydrogenated product in the production method of the present invention is preferably X ^{1 of} the repeating structural unit [A] represented by the general formula (1), and the repeating structural unit represented by the general formula (2). Aliphatic cyclic compound in which at least one of X ^{2 in} [B] is —O— and the other is —CH ₂ —, which is a hydrogenated ring-opening metathesis polymer, and in which the oxygen atom is the main chain. By being present in the substrate, adhesion to a substrate to be processed such as a silicon substrate, improvement in wet tension at the time of development with an alkaline aqueous solution, ketones, alcohols, etc. used in the process of applying a resist agent to a silicon wafer There is an effect of further improving the solubility in a polar organic solvent, the affinity for water is also improved, and the developability for a release agent (or developer) such as an alkaline aqueous solution after exposure is also improved.

In addition, the hydrogenated ring-opening metathesis polymer in the production method of the present invention has a general formula after the hydrogenation reaction in order to appropriately adjust the adhesion to a substrate to be treated such as a silicon substrate and the developability with an alkaline aqueous solution. At least one of the repeating structural units [A] represented by (1) is an alkoxycarbonyl having 2 to 20 carbon atoms, an alkoxyalkyloxycarbonyl having 3 to 20 carbon atoms, or an alkoxycarbonylalkyloxycarbonyl having 4 to 20 carbon atoms. The selected alkoxy or alkoxyalkyl of R ^{1 to} R ⁴ may be partially eliminated at an arbitrary ratio to form a carboxylic acid. When forming this carboxylic acid, Preferably it is 1 to 40% of range with respect to the repeating structural unit [A] represented by the general formula (1), more preferably 5 to 20%. It is a range.

  A ring-opening metathesis polymer solution composed of the repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2) is represented by the general formula (3). A method for producing a hydrogenated ring-opening metathesis polymer in which a double bond of a main chain is hydrogenated with an organometallic complex brought into contact with carbon monoxide at least 2 mole times the organometallic complex represented by By contacting or coexisting with carbon monoxide of 2 mole times or more as a donor in the formula (3), sufficient hydrogenation reaction catalyst efficiency is shown. If it is less than 2 mol times, the efficiency of the catalyst is insufficient, and the effect of contact with carbon monoxide does not appear. Furthermore, there is no particular upper limit on the amount ratio of carbon monoxide to be brought into contact, but even if it exists in excess, it does not show an effect of improving the catalyst efficiency, and it is 2 to 1000 mol with respect to the complex of the general formula (3). Double is preferable, More preferably, it is 2-500 mol times, Most preferably, it is 2-200 mol times.

  On the other hand, when carbon monoxide is used in the presence of carbon monoxide in the coexistence of a carbonyl complex such as dichlorocarbonyltris (triphenylphosphine) ruthenium hydride having carbon monoxide as an organometallic complex, the hydrogenation reaction The catalytic efficiency is significantly reduced. Therefore, it can be estimated that the donor effect of carbon monoxide is effective only in the electronic state of the organometallic complex represented by the general formula (3).

  In the present invention, when carbon monoxide is contacted as a donor, particularly when the ring-opening metathesis polymer hydrogenated product produced according to the present invention is used as a base polymer for photoresist, the performance of chemically amplified resist is greatly increased. Bring quality improvement. That is, when organic compounds such as amines of basic compounds remain in the product as catalyst donors, in the case of chemically amplified photoresists, the acid generated by light irradiation disappears by these compounds and is optimal. May interfere with chemical amplification of the acid. On the other hand, by using carbon monoxide as a donor as in the present invention, the residue of the donor in the product is completely eliminated, and the chemically amplified resist performance is improved without being affected by impurities. be able to.

In the present invention, the double bond of the main chain is hydrogenated with an organometallic complex in which the ring-opening metathesis polymer solution is brought into contact with carbon monoxide at 2 mol times or more with respect to the organometallic complex represented by the general formula (3). In the method for producing a ring-opening metathesis polymer hydrogenated product, a method of contacting or dissolving carbon monoxide and an organometallic complex and further contacting with hydrogen is not particularly limited. For example, 1) an organic solvent and an organic solvent A method of dissolving and contacting two or more moles of carbon monoxide in a mixed solution of a metal complex, and then adding the mixed solution to a ring-opening metathesis polymer solution and then contacting with hydrogen;
Or
2) A method in which carbon monoxide is contacted or dissolved in a mixed solution of a ring-opening metathesis polymer solution and an organometallic complex at 2 mole times or more and then contacted with hydrogen. The contact method may mix a liquid mixture or a solution by well-known stirring.

  Furthermore, in the method 1), the concentration of the organometallic complex in which the organic solvent, the organometallic complex, and 2 mol times or more of carbon monoxide are contacted is usually 0.01 to 10% by mass, preferably 0.1%. ˜5 mass%. If it is 0.01% by mass or less, the contact efficiency between the organometallic complex and carbon monoxide may be deteriorated and a sufficient effect may not be obtained. If it is 10% by mass or more, the organometallic complex is dissolved in an organic solvent. From the viewpoint of safety, the efficiency of mixing by stirring may decrease, and sufficient contact with carbon monoxide may not be obtained.

  Furthermore, the temperature at which the organometallic complex is brought into contact with carbon monoxide at 2 mole times or more is not particularly limited, but is usually in the range of -40 to 200 ° C, preferably -20 to 100 ° C, and more preferably. Is 0-50 ° C. In addition, the mixed state is not particularly limited as long as the contact between the organic metal complex in the organic solvent or the solution and carbon monoxide is successful, but a laminar flow state is usually preferable.

  In the present invention, the hydrogen pressure brought into contact with hydrogen is usually in the range of normal pressure to 30 MPa, preferably 0.5 MPa to 20 MPa, particularly preferably 2 MPa to 15 MPa. The hydrogenation reaction temperature is usually from 0 ° C to 300 ° C, preferably from room temperature to 250 ° C, particularly preferably from 50 ° C to 200 ° C. Furthermore, the reaction time is usually 15 minutes to 50 hours, preferably 0.5 hours to 30 hours, and particularly preferably 1 hour to 20 hours.

  In the present invention, the amount of the organometallic complex represented by the general formula (3) is not particularly limited, but the metal weight relative to the weight of the ring-opening metathesis polymer is usually 5 ppm to 5000 ppm, preferably 10 ppm to 1000 ppm, particularly preferably. 20 ppm to 500 ppm, and used for the hydrogenation reaction in contact with or coexistence with carbon monoxide. Two or more kinds of organometallic complexes may be mixed at an arbitrary ratio and used in the presence of carbon monoxide.

  In the present invention, the organic solvent used when contacting the organic metal complex represented by the general formula (3) with carbon monoxide is not particularly limited, but a solvent in which the solvent itself is not hydrogenated by a hydrogenation reaction is preferable. For example, ethers such as tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane or dioxane, aliphatic hydrocarbons such as pentane, hexane or heptane, aliphatic cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane or decalin And esters such as methyl acetate or ethyl acetate.

  In the present invention, the hydrogenation concentration of the ring-opening metathesis polymer to be hydrogenated varies depending on the polymer, the type of the organic solvent, etc., but the concentration of the ring-opening metathesis polymer with respect to 1 kg of the organic solvent is usually 0.01 mass ratio to It is 3 mass ratio, Preferably it is 0.05 mass ratio-2 mass ratio, Most preferably, it is the range of 0.1 mass ratio-1 mass ratio. Further, in the present invention, the ring-opening metathesis polymer can be dissolved in a solvent again after isolating the ring-opening metathesis polymer from the ring-opening metathesis polymer solution. It can also be used for the reaction.

  In the present invention, the hydrogenated ring-opening metathesis polymer is composed of the repeating structural unit [A] represented by the general formula (1) and the main chain of the repeating structural unit [B] represented by the general formula (2). The double bond portion is composed of a hydrogenated repeating structure, and the weight average molecular weight (Mw) based on polystyrene standards is 1,000 to 200,000, preferably 2,000 to 100,000, especially Preferably it is 3,000-20,000.

  The hydrogenation rate of the ring-opening metathesis polymer according to the present invention is usually 80% or more, preferably 90% or more, particularly preferably 95% or more. If the hydrogenation rate is less than 80%, light absorption due to residual double bonds occurs, and the light transmittance at the wavelength of the exposure light source deteriorates, so that it is not preferable as a base polymer for photoresist applied to lithography.

  In the present invention, the method for recovering the ring-opening metathesis polymer hydrogenated product from the solution after the hydrogenation reaction is not particularly limited, and the hydrogenated reaction solution is discharged into a poor solvent under stirring to coagulate the polymer hydride. A known method such as a filtration method, a centrifugal separation method, a decantation method or the like, a steam stripping method in which steam is blown into the reaction solution to precipitate, a method of directly removing the solvent from the reaction solution by heating or the like. Can be used.

  In the present invention, the ring-opening metathesis polymer to be hydrogenated is produced by the cyclic olefin 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). It can be obtained by copolymerizing the corresponding cyclic olefin with a ring-opening metathesis catalyst.

As a specific example of the cyclic olefin in which X ¹ is —CH ₂ — and j = 0 corresponding to the repeating structural unit [A] represented by the general formula (1), 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-isopropoxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- (n-butoxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5-isobutoxycarbonyl- Bicyclo [2.2.1] hept-2-ene, 5- (tert-butoxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5-cyclopentyloxycarbonyl-bicyclo [2.2.1 ] Hepta 2-ene, 5-cyclohexyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyclooctyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-norbornyl Oxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- (1-methylcyclopentyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1′-ethylcyclopentyl) Oxycarbonyl) -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- (tetrahydrofuran-2'-yloxycarbonyl) -bicyclo [2.2. 1] Hept-2-ene, 5- (tetrahydropyran-2′-yloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1′-adamantyloxycarbonyl) -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] hepta-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-butoxymethyloxycarbonyl) -bicyclo [2.2 .1] Hept-2-ene, 5-cyclopentyloxymethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxymethyloxycarbonyl-bicyclo [2.2.1] hepta-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′-eth Cyclopentyloxymethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1′-methylnorbornyloxymethyloxycarbonyl) -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'-adamantyloxy) Methyloxycarbonyl) -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-isopropoxycarbonylmethyloxycarbonyl-bicyclo [ 2.2.1] hept-2-ene, 5- (n-butoxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] Hept-2-ene, 5-isobutoxycarbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5- (tert-butoxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hepta 2-ene, 5-cyclopentyloxycarbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene 5-cyclooctyloxycarbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5-norbornyloxycarbonylmethyloxycarbonyl-bicyclo [2.2.1] hept-2-ene, 5, -(1'-methylcyclopentyloxycarbonylmethyloxycarbonyl) -bi Chlo [2.2.1] hept-2-ene, 5- (1′-ethylcyclopentyloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1′-methyl) Norbornyloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1′-ethylnorbornyloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hepta 2-ene, 5- (1′-ethoxypropyloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (1′-ethoxy-1′-methylethyloxycarbonylmethyl) Oxycarbonyl) -bicyclo [2.2.1] hept-2-ene, 5- (tetrahydrofuran-2-yloxycarbonylmethyloxycal) Nyl) -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'-adamantyloxycarbonylmethyloxycarbonyl) -bicyclo [2.2.1] hepta 2-ene and the like.

As a specific example of the cyclic olefin in which X ¹ is —CH ₂ — and j = 1, 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-isopropoxycarbonyl-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, 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- (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-isobutoxymethyloxycarbonyl-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-isobutoxycarbonylmethyloxycarbonyl-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 . ^{17, 10} ] -3-dodecene and the like.

Further, specific examples of the cyclic olefin in which X ¹ is —O— and j = 0 include 5-methoxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonyl -7-oxabicyclo [2.2.1] hept-2-ene, 5- (n-propoxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5-isopropoxycarbonyl- 7-oxabicyclo [2.2.1] hept-2-ene, 5- (n-butoxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5-isobutoxycarbonyl-7 -Oxabicyclo [2.2.1] hept-2-ene, 5- (tert-butoxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5-cyclopentyloxycarbonyl-7- Xabicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5-cyclooctyloxycarbonyl-7-oxabicyclo [2 2.1] hept-2-ene, 5-norbornyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5- (1'-methylcyclopentyloxycarbonyl) -7- Oxabicyclo [2.2.1] hept-2-ene, 5- (1′-ethylcyclopentyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1′- Methylnorbornyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1′-ethylnorbornyloxycarbonyl) -7-oxabicycle [2.2.1] hept-2-ene, 5- (1′-ethoxypropyloxyoxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1′-ethoxy -1′-methylethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (tetrahydrofuran-2′-yloxycarbonyl) -7-oxabicyclo [2.2.1] ] Hept-2-ene, 5- (tetrahydropyran-2′-yloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1′-adamantyloxycarbonyl) -7 -Oxabicyclo [2.2.1] hept-2-ene, 5- (2'-adamantyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5-methoxymethyloxycal Nyl-7-oxabicyclo [2.2.1] hept-2-ene, 5-ethoxymethyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5- (n-propoxymethyl) Oxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5-isopropoxymethyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5- (n -Butoxymethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (2'-methyl-propoxymethyloxycarbonyl) -7-oxabicyclo [2.2.1] hepta 2-ene, 5- (tert-butoxymethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5-cyclopentyloxymethyloxycarbo 7-oxabicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxymethyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5-cyclooctyloxymethyl Oxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5-norbornyloxymethyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5- ( 1'-methylcyclopentyloxymethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1'-ethylcyclopentyloxymethyloxycarbonyl) -7-oxabicyclo [2.2 .1] Hept-2-ene, 5- (1′-methylnorbornyloxymethyloxycarbonyl) -7-oxabicyclo [2.2.1] But-2-ene, 5- (1′-ethylnorbornyloxymethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1′-ethoxypropyloxymethyloxy) Carbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1′-ethoxy-1′-methylethyloxymethyloxycarbonyl) -7-oxabicyclo [2.2.1] Hept-2-ene, 5- (tetrahydrofuran-2′-yloxymethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (tetrahydropyran-2′-yloxymethyl) Oxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1'-adamantyloxymethyloxycarbonyl) -7-oxabicyclo [2 2.1] Hept-2-ene, 5- (2′-adamantyloxymethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5-methoxycarbonylmethyloxycarbonyl-7- Oxabicyclo [2.2.1] hept-2-ene, 5-ethoxycarbonylmethyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5- (n-propoxycarbonylmethyloxycarbonyl) ) -7-oxabicyclo [2.2.1] hept-2-ene, 5-isopropoxycarbonylmethyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5- (n- Butoxycarbonylmethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5-isobutoxycarbonylmethyl Xoxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5- (tert-butoxycarbonylmethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5 -Cyclopentyloxycarbonylmethyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5-cyclohexyloxycarbonylmethyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene 5-cyclooctyloxycarbonylmethyloxycarbonyl-7-oxabicyclo [2.2.1] hept-2-ene, 5-norbornyloxycarbonylmethyloxycarbonyl-7-oxabicyclo [2.2.1] hepta 2-ene, 5- (1′-methylcyclopentyloxycarbonylmethyloxycarboni) ) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1′-ethylcyclopentyloxycarbonylmethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2- Ene, 5- (1′-methylnorbornyloxycarbonylmethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1′-ethylnorbornyloxycarbonylmethyloxy) Carbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (1′-ethoxypropyloxycarbonylmethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2- Ene, 5- (1′-ethoxy-1′-methylethyloxycarbonylmethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene 5- (Tetrahydrofuran-2'-yloxycarbonylmethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (tetrahydropyran-2'-yloxycarbonylmethyloxycarbonyl)- 7-oxabicyclo [2.2.1] hept-2-ene, 5- (1′-adamantyloxycarbonylmethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene, 5- (2′-adamantyloxycarbonylmethyloxycarbonyl) -7-oxabicyclo [2.2.1] hept-2-ene and the like.

As a specific example of the cyclic olefin in which X ¹ is —O— and j = 1, 8-methoxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-propoxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropoxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-butoxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isobutoxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tert-butoxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclopentyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclohexyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclooctyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-norbornyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-methylcyclopentyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethylcyclopentyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-methylnorbornyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethylnorbornyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethoxypropyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethoxy-1′-methylethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydrofuran-2′-yloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydropyran-2′-yloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-adamantyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (2′-adamantyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methoxymethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxymethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-propoxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropoxymethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-butoxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isobutoxymethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tert-butoxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclopentyloxymethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclohexyloxymethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclooctyloxymethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-norbornyloxymethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-methylcyclopentyloxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethylcyclopentyloxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-methylnorbornyloxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethylnorbornyloxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethoxypropyloxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethoxy-1′-methylethyloxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydrofuran-2′-yloxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydropyran-2′-yloxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-adamantyloxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (2′-adamantyloxymethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-methoxycarbonylmethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-ethoxycarbonylmethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-propoxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isopropoxycarbonylmethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (n-butoxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-isobutoxycarbonylmethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tert-butoxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclopentyloxycarbonylmethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclohexyloxycarbonylmethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-cyclooctyloxycarbonylmethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8-norbornyloxycarbonylmethyloxycarbonyl-11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-methylcyclopentyloxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1-ethylcyclopentyloxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-methylnorbornyloxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethylnorbornyloxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethoxypropyloxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-ethoxy-1′-methylethyloxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydrofuran-2′-yloxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (tetrahydropyran-2′-yloxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (1′-adamantyloxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene, 8- (2′-adamantyloxycarbonylmethyloxycarbonyl) -11-oxatetracyclo [4.4.0.1 ^2,5 . ^{17, 10} ] -3-dodecene and the like.

On the other hand, specific examples of the cyclic olefin in which X ² corresponding to the repeating structural unit [B] represented by the general formula (2) is —CH ₂ — include 4-oxatricyclo [5.2.1]. .0 ^2,6] dec-8-en-3-one, 4-oxa-5,5-dimethyl - tricyclo [5.2.1.0 ^2,6] dec-8-en-3-one, 4 -Oxa- ^2,6 -dimethyl-tricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 4-oxa-2,5,5,6-tetramethyl-tricyclo [5 .2.1.0 ^2,6 ] dec-8-en-3-one and the like, and specific examples of the cyclic olefin in which X ² is —O— include 4,10-dioxa -Tricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 4,10-dioxa-5,5-dimethyl-tri Cyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one, 4,10-dioxa-2,6-dimethyl-tricyclo [5.2.1.0 ^2,6 ] deca- 8-en-3-one, 4,10-dioxa-2,5,5,6-tetramethyl-tricyclo [5.2.1.0 ^2,6 ] dec-8-en-3-one and the like. It is done.

As the ring-opening metathesis polymerization catalyst used in the present invention is not particularly limited as long as ring-opening metathesis polymerization can be catalyzed, for ^{_{example, 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) (CHBu t) (OC (CF 3) 3) 2, W (N-2 _{, 6- (Me) 2 C 6} H 3) (CHBu t) (OC (CF 3) 3) 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) ( ^{_{CMe 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 or, W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OBu ^t ) ₂ (PR ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OBu ^t ) ₂ (PR ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCPh ₂ ) (OBu ^t ) ₂ (PR ₃ ), W (N-2,6-Me ₂ C ₆ H _{3 ) (CHCHCMePh) (OCMe 2 (} CF 3)) 2 (PR 3), W (N _{2,6-Me 2 C 6 H 3} ) (CHCHCMe 2) (OCMe 2 (CF 3)) 2 (PR 3), W (N-2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OCMe ₂ (CF ₃ )) ₂ (PR ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OCMe (CF ₃ ) ₂ ) ₂ (PR ₃ ), W (N-2, 6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OCMe (CF ₃ ) ₂ ) ₂ (PR ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCPh ₂ ) (OCMe (CF ₃ ) ₂ ) ₂ (PR ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OC (CF ₃ ) ₃ ) ₂ (PR ₃ ), W (N-2,6- Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OC (CF _{3 3} ) ₂ (PR ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCPh ₂ ) (OC (CF ₃ ) ₃ ) ₂ (PR ₃ ), W (N-2,6- ^{_{Pr i 2 C 6 H 3)}} (CHCHCMePh) (OCMe 2 (CF 3)) 2 (PR 3), W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OCMe (CF 3) ^{_{2) 2 (PR 3),}} W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OC (CF 3) 3) 2 (PR 3), W (N-2,6-Pr ⁱ ₂ C ₆ H ₃ ) (CHCHCMePh) (OPh) ₂ (PR ₃ ), or W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OBu ^t ) ₂ (Py), W (N _{-2,6-Me 2 C 6 H 3} ) (CHCHCMe 2) ( OBu ^t ) ₂ (Py), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCPh ₂ ) (OBu ^t ) ₂ (Py), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OCMe ₂ (CF ₃ )) ₂ (Py), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OCMe ₂ (CF ₃ )) ₂ (Py), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCPh ₂ ) (OCMe ₂ (CF ₃ )) ₂ (Py), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) ( OCMe (CF ₃ ) ₂ ) ₂ (Py), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMe ₂ ) (OCMe (CF ₃ ) ₂ ) ₂ (Py), W (N-2, _{6-Me 2 C 6 H 3} ) (CHCHCPh 2) (OCMe ( _{F 3) 2) 2 (Py} ), W (N-2,6-Me 2 C 6 H 3) (CHCHCMePh) (OC (CF 3) 3) 2 (Py), W (N-2,6-Me _{2 C 6 H 3) (CHCHCMe} 2) (OC (CF 3) 3) 2 (Py), W (N-2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OC (CF 3) 3) ^{_{2 (Py), W (N}} -2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OCMe 2 (CF 3)) 2 (Py), W (N-2,6-Pr i 2 C 6 _{H 3) (CHCHCMePh) (OCMe} (CF 3) 2) 2 (Py), W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OC (CF 3) 3) 2 (Py) ^{_{, W (N-2,6-Pr}} i 2 C 6 H 3) (CHCHCMePh) _(OPh) 2 (Py) 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-Me 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) (OCMe 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) _{(CHCMe 2 Ph) (OCMe 2} (CF 3)) 2, Mo (N-2,6-P ^{_{i 2 C 6 H 3) (}} CHCMe 2 Ph) (OCMe (CF 3) 2) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OC (CF 3) 3 _{) 2, Mo (N-2,6} -Me 2 C 6 H 3) (CHCMe 2 Ph) (OC (CF 3) 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) ( ^{_{CHCMe 2 Ph) (OBu t)}} 2 (PR 3), Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2 (PR 3), Mo (N ^{_{-2,6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 (PR 3), Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe ₂ Ph) (OC (CF ₃ ) ₃ ) ₂ (PR ₃ ), Mo (N-2,6 _{-Me 2 C 6 H 3) (} CHCMe 2 Ph) (OC (CF 3) 3) 2 (PR 3), Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu ^{_{t) 2 (Py), Mo}} (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2 (Py), Mo (N-2,6-Pr i 2 _{C 6 H 3) (CHCMe 2} Ph) (OCMe (CF 3) 2) 2 (Py), Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OC (CF 3) ₃ ) ₂ (Py), Mo (N-2,6-Me ₂ C ₆ H ₃ ) (CHCMe
_{2 Ph) (OC (CF 3} ) 3) 2 (Py) ( where, Pr ⁱ in the formula represents an iso- propyl group, R represents an alkyl group or a methoxy group such as a methyl group, an ethyl group, such as an ethoxy group an alkoxy group, Bu ^t represents a tert- butyl group, Me represents methyl group, Ph represents a phenyl group, Py represents a pyridine group.) molybdenum-based alkylidene catalyst such as, Ru (CHCHCPh ₂₎ ( Examples include a ruthenium alkylidene catalyst such as PPh ₃ ) ₂ Cl ₂ (wherein Ph represents a phenyl group). These ring-opening metathesis polymerization catalysts may be used alone or in combination of two or more.

  In addition to the above alkylidene catalyst, a ring-opening metathesis polymerization catalyst comprising a combination of an organic transition metal complex, a transition metal halide or a transition metal oxide and a Lewis acid as a cocatalyst can be used. As the metathesis polymerization catalyst, the above tungsten-based alkylidene catalyst, molybdenum-based alkylidene catalyst, and ruthenium-based alkylidene catalyst are preferably used, and more preferably, the tungsten-based alkylidene catalyst and the molybdenum-based alkylidene catalyst are used.

  In the polymerization reaction, the cyclic olefin is 100 to 30,000 mol, preferably 1,000 to 20,000 mol, per 1 mol of the ring-opening metathesis polymerization catalyst. Furthermore, examples of the polymerization reaction solvent include ethers such as tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane, and dioxane, aliphatic hydrocarbons such as pentane, hexane, and heptane, cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane or Examples thereof include aliphatic cyclic hydrocarbons such as decalin, halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, and tetrachloroethane, and esters such as methyl acetate and ethyl acetate. Further, two or more of these ethers, aliphatic hydrocarbons, aliphatic cyclic hydrocarbons, halogenated hydrocarbons or esters may be used in combination.

Furthermore, olefins or dienes can be used as chain transfer agents to control the molecular weight and its distribution. Examples of olefins include α-olefins such as ethylene, propylene, 1-butene, 1-pentene, 1-hexene, 1-octene, and further, vinyltrimethylsilane, allyltrimethylsilane, allyltriethylsilane, allyltriethyl. Examples include silicon-containing olefins such as isopropylsilane. Examples of the diene include non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, and 1,6-heptadiene. Furthermore, each may be used alone or in combination of two or more.
The amount of the olefin or diene used is usually in the range of 0.001 to 1,000 mol, preferably 0.01 to 100 mol, per mol of cyclic olefin.

  The ring-opening metathesis polymer in the present invention comprises a repeating structural unit [A] represented by the general formula (1) and a repeating structural unit [B] represented by the general formula (2). The weight average molecular weight (Mw) is 1,000 to 200,000, preferably 2,000 to 100,000, and particularly preferably 3,000 to 20,000.

  The monomer concentration of the polymerization reaction for producing the ring-opening metathesis polymer is not particularly limited because it varies depending on the reactivity of the cyclic olefin and the solubility in the polymerization solvent, but the concentration of the cyclic olefin relative to 1 kg of the solvent is usually 0. 0.01 mass ratio to 3 mass ratio, preferably 0.05 mass ratio to 2 mass ratio, more preferably 0.1 mass ratio to 1 mass ratio. The reaction temperature varies depending on the type and amount of the cyclic olefin 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 15 minutes to 10 hours, preferably 15 minutes to 8 hours, and more preferably 15 minutes to 6 hours. Furthermore, after the polymerization reaction, although not particularly limited, a ring-opening metathesis polymer solution can be obtained by stopping the reaction with aldehydes such as butyraldehyde, alcohols such as methanol, or water.

  EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not restrict | limited by these.

Moreover, the analysis and evaluation regarding the polymer obtained in the Example were implemented with the following method.
The weight average molecular weight (Mw) and molecular weight distribution (Mw / Mn) were determined by the polystyrene standard using the gel permeation chromatography (GPC) under the following conditions, and the Mw and Mn of the polymer dissolved in THF under the following conditions. The molecular weight was calibrated and measured. Detector: RI-2031 and 875-UV manufactured by JASCO Corporation, serial connection column: Shodex K-806M, 804, 803, 802.5, column temperature: 40 ° C., flow rate: 1.0 ml / min, sample concentration: 3. 0 mg / ml

The hydrogenation rate was determined by dissolving a powder of hydrogenated ring-opening metathesis polymer in deuterated chloroform, measuring a 1H-NMR spectrum using a nuclear magnetic resonance apparatus EX270 manufactured by JEOL, and a chemical shift δ = 4.0. The magnitude by which the peak integrated value derived from hydrogen bonded to the double-bonded carbon of the main chain in the range of ˜6.5 ppm decreases due to the hydrogenation reaction was calculated.
The molar ratio of repeating structural units ([A] / [B]) was determined by dissolving a ring-opening metathesis polymer and a hydrogenated ring-opening metathesis polymer hydrogenated powder in deuterated tetrahydrofuran, and making it a JEOL nuclear magnetic resonance apparatus ECX400P Was used to measure the ¹³ C-NMR spectrum, and the percent molar ratio of the structural unit [A] / [B] was calculated from the integrated value of the peaks attributable to each carbonyl at δ = 170 to 190 ppm.

The photoresist was evaluated by developing to form 1: 1 and 1:10 line and space patterns. The developed wafer is cleaved and observed with a cross-sectional SEM (scanning electron microscope), and at an exposure amount (optimum exposure amount = Eop, mJ / cm ² ) for resolving a 0.13 μm line and space in 1: 1. The minimum line width (μm) of the separated lines and spaces is defined as the resolution of the evaluation resist, and the smaller the value, the better. In addition, the value obtained by subtracting the line width of the 0.13 μm 1:10 line and space pattern from the line width of the 0.13 μm 1: 1 line and space pattern at that time was defined as a sparse / dense dimensional difference (the smaller the value, the better ). For resist materials that do not resolve the 0.13 μm line and space pattern, the optimal exposure amount is the exposure amount at which a 1: 1 line and space pattern with a larger line width of 0.14 μm or 0.15 μm is obtained. The density difference was measured. The optimum SB (post-treatment heat treatment) / PEB (post-exposure heat treatment) temperature for each resist is also shown.

Synthesis example 1
In a 5 L autoclave equipped with a magnetic stirrer under a nitrogen atmosphere, add 8- (1′-ethylcyclopentyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene and 602g (2.0mol), 4,10- dioxatricyclo [5.2.1.0 ^{2, 6]} dec-8-en-3-one 305 g (2 0.0 mol), 35 g (0.4 mol) of 1,5-hexadiene and 3 kg of THF were added and stirred.
Mo a _{^{(N-2,6- Pr i 2 C}} 6 H 3) (CHCMe 2 Ph) THF solution of _{(OCMe (CF 3) 2)} 2 and 310 mg (0.4 mmol), was added to the monomer solution under stirring And heated at 60 ° C. for 2 hours. The solution was extracted into a container to obtain 3.9 kg of a ring-opening metathesis polymer solution.
The molar ratio of the repeating structural units [A] and [B] of the obtained ring-opening metathesis polymer was [A] / [B] = 50/50, Mw was 6720, and Mw / Mn was 1.85. It was.

Synthesis example 2
In a 2 L autoclave equipped with a magnetic stirrer under a nitrogen atmosphere, 8- (1′-ethylcyclopentyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene and 265g (0.9mol), 4,10- dioxatricyclo [5.2.1.0 ^{2, 6]} dec-8-en-3-one 15 g (0 0.1 mol), 12 g (0.1 mol) of 1,5-hexadiene and 0.9 kg of THF were added and stirred.
Mo (N-2,6-Me ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) (OC (CF ₃ ) ₃ ) ₂ in 160 mg (0.2 mmol) in THF was added to the monomer solution under stirring, Heated at 60 ° C. for 2 hours. The solution was extracted into a container to obtain 1.2 kg of a ring-opening metathesis polymer solution.
The molar ratio of the repeating structural units [A] and [B] of the obtained ring-opening metathesis polymer was [A] / [B] = 90/10, Mw was 5150, and Mw / Mn was 1.42. It was.

Synthesis example 3
8- (1′-ethylcyclopentyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene and 106g (0.4mol), 4,10- dioxatricyclo [5.2.1.0 ^{2, 6]} dec-8-en-3-one 159 g (1 0.0 mol), 15 g (0.2 mol) of 1,5-hexadiene, 0.9 kg of THF, Mo (N-2,6-Me ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) (OC (CF ₃ ) ₃ ) ₂ except for using 230 mg (0.3 mmol), and in the same manner as in synthesis example 2 performed to obtain a ring-opening metathesis polymer solution 1.1 kg.
The molar ratio of the repeating structural units [A] and [B] of the obtained ring-opening metathesis polymer was [A] / [B] = 25/75, Mw was 5870, and Mw / Mn was 1.43. It was.

Synthesis example 4
8- (1′-methylcyclopentyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene and 168g (0.6mol), 4,10- dioxatricyclo [5.2.1.0 ^{2, 6]} dec-8-en-3-one 90 g (0 .6mol), 1- hexene 16g (0.2mol), 0.9kg of ^{THF, Mo (N-2,6- Pr} i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) except _{that 2} using 180 mg (0.2 mmol), in the same manner as in synthesis example 2 performed to obtain 1.1kg of the ring-opening metathesis polymer solution.
The molar ratio of the repeating structural units [A] and [B] of the obtained ring-opening metathesis polymer was [A] / [B] = 50/50, Mw was 7050, and Mw / Mn was 1.90. It was.

Synthesis example 5
8-methoxymethyloxycarbonyl-tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene and 496g (2.0mol), 4,10- dioxatricyclo [5.2.1.0 ^{2, 6]} dec-8-en-3-one 304g (2 1.0 mol), 71 g (0.8 mol) of 1-hexene, 3.2 kg of THF, Mo (N-2,6-Me ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) (OC (CF ₃ ) ₃ ) ₂ Was performed in the same manner as in Synthesis Example 1 except that 410 mg (0.5 mmol) was used, and 4.0 kg of a ring-opening metathesis polymer solution was obtained.
The molar ratio of the repeating structural units [A] and [B] of the obtained ring-opening metathesis polymer was [A] / [B] = 50/50, Mw was 5600, and Mw / Mn was 1.43. It was.

Synthesis Example 6
8- (tert-Butoxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene and 127g (0.5mol), 4,10- dioxatricyclo [5.2.1.0 ^{2, 6]} dec-8-en-3-one 74 g (0 .5mol), 1,5-hexadiene 7g (0.09mol), 0.8kg of ^{THF, Mo (N-2,6- Pr} i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2 ₂ ) Except having used 170 mg (0.2 mmol), it carried out similarly to the synthesis example 2, and obtained 1.0kg of ring-opening metathesis polymer solutions.
The molar ratio of the repeating structural units [A] and [B] of the obtained ring-opening metathesis polymer was [A] / [B] = 50/50, Mw was 7680, and Mw / Mn was 1.91. It was.

Synthesis example 7
8- (1′-ethylcyclopentyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene and 141g (0.5mol), 4,10- dioxa-5,5-dimethyl tricyclo [5.2.1.0 ^{2, 6]} dec-8-en-3 on the 85 g (0.5 mol), 1,5-hexadiene 6.5g (0.08mol), 0.9kg of ^{THF, Mo (N-2,6- Pr} i 2 C 6 H 3) (CHBu t) Except that 170 mg (0.2 mmol) of (OCMe (CF ₃ ) ₂ ) ₂ was used, the same procedure as in Synthesis Example 2 was performed to obtain 1.1 kg of a ring-opening metathesis polymer solution.
The obtained ring-opening metathesis polymer solution was precipitated with water and dried under reduced pressure to obtain 219 g of a ring-opening metathesis polymer. The molar ratio of the repeating structural units [A] and [B] was [A] / [B] = 50/50, Mw was 8000, and Mw / Mn was 1.92.

Synthesis Example 8
8- (1′-ethylcyclopentyloxycarbonyl) -tetracyclo [4.4.0.1 ^2,5 . 1 ^7,10] -3-dodecene and 42g (0.14mol), 4,10- dioxatricyclo [5.2.1.0 ^{2, 6]} dec-8-en-3-one 193 g (1 .27 mol), 26 g (0.3 mol) of 1,5-hexadiene, 0.8 kg of THF, Mo (N-2,6-Me ₂ C ₆ H ₃ ) (CHCMe ₂ Ph) (OC (CF ₃ ) ₃ ) Except for using 230 mg (0.3 mmol) of ₂ in the same manner as in Synthesis Example 3, 1.0 kg of a ring-opening metathesis polymer solution was obtained.
The obtained ring-opening metathesis polymer solution was precipitated with water and dried under reduced pressure to obtain 228 g of a ring-opening metathesis polymer. The molar ratio of the repeating structural units [A] and [B] was [A] / [B] = 10/90, Mw was 4000, and Mw / Mn was 1.40.

Example 1
In a nitrogen glove box, 27.6 mg (0.029 mmol) of dichlorotris (triphenylphosphine) ruthenium and 20 g of THF were placed in a 50 ml container, and 7 ml of carbon monoxide in an amount of 10 mol times the ruthenium complex was weighed. After pouring into the solution, it was stirred for 5 minutes.

  A THF solution of 92 g of the ring-opening metathesis polymer of Synthesis Example 1 was put in a 1 L autoclave, and further a solution of a ruthenium complex brought into contact with carbon monoxide was added. Then, the inside was replaced with hydrogen, a reaction temperature of 125 ° C., a pressure Heated at 8 MPa for 5 hours. The reaction solution was precipitated with water and dried under reduced pressure to obtain a hydrogenated ring-opening metathesis polymer.

¹ H-NMR spectrum is shown in FIG. There was no peak derived from double bonds in the spectrum, and the hydrogenation rate of the polymer was 100%. The molar ratio of the repeating structural units [A] and [B] was [A] / [B] = 50/50, Mw was 9670, and Mw / Mn was 2.10.

Example 2
Except for using 20.8 mg (0.017 mmol) of dichlorotetrakis (triphenylphosphine) ruthenium, 12.8 ml of 31 mol-fold amount of carbon monoxide and 99 g of the ring-opening metathesis polymer of Synthesis Example 1 in THF. In the same manner as in Example 1, a hydrogenated ring-opening metathesis polymer having a hydrogenation rate of 100% was obtained.

Example 3
In a nitrogen glove box, 41.4 mg (0.034 mmol) of dichlorotetrakis (triphenylphosphine) ruthenium and 30 g of THF were placed in a 50 ml container and stirred for 5 minutes.
A THF solution of 104 g of the ring-opening metathesis polymer of Synthesis Example 1 and the entire solution in the container are placed in a 1 L autoclave, and 370.5 ml of carbon monoxide in an amount of 450 moles with respect to the ruthenium complex is injected into the inside, and stirred for 10 minutes. did. Thereafter, the inside was replaced with hydrogen, and the same procedure as in Example 1 was performed to obtain a hydrogenated ring-opening metathesis polymer having a hydrogenation rate of 100%.

Example 4
Using a THF solution of 41.4 mg (0.043 mmol) of dichlorotris (triphenylphosphine) ruthenium and 104 g of the ring-opening metathesis polymer of Synthesis Example 2, 472 ml of carbon monoxide in an amount of 450 mol times the ruthenium complex was added. Except that it was used, the same procedure as in Example 3 was carried out to obtain a hydrogenated ring-opening metathesis polymer having a hydrogenation rate of 100%. The molar ratio of the repeating structural units [A] and [B] was [A] / [B] = 90/10, Mw was 7350, and Mw / Mn was 1.53.

Example 5
Dichlorotris (triphenylphosphine) ruthenium 31.1 mg (0.032 mmol) and 5 mol times carbon monoxide 4 ml with respect to the ruthenium complex were subjected to contact treatment in the same manner as in Example 1, and the ring-opening metathesis of Synthesis Example 3 was performed. Hydrogenation was performed in the same manner as in Example 1 using a THF solution of 104 g of the polymer. The molar ratio of the repeating structural units [A] and [B] of the hydrogenated ring-opening metathesis polymer having a hydrogenation rate of 100% was [A] / [B] = 25/75, and Mw was 8420. , Mw / Mn was 1.52.

Example 6
In a nitrogen glove box, put 27.6 mg (0.023 mmol) of dichlorotetrakis (triphenylphosphine) ruthenium and 30 g of THF in a 50 ml container, and weigh 2.8 ml of carbon monoxide in a 5-fold volume with respect to the ruthenium complex. The mixture was poured into the solution and stirred for 5 minutes.
A THF solution of 92 g of the ring-opening metathesis polymer of Synthesis Example 4 was put in a 1 L autoclave, and further a solution of a ruthenium complex brought into contact with carbon monoxide was added. Then, the inside was replaced with hydrogen, a reaction temperature of 100 ° C., a pressure Heated at 7 MPa for 12 hours. The reaction solution was precipitated with water and dried under reduced pressure to obtain a hydrogenated ring-opening metathesis polymer. The hydrogenation rate of the polymer is 100%, the molar ratio of the repeating structural units [A] and [B] is [A] / [B] = 50/50, Mw is 10520, and Mw / Mn is 2.11. Met.

Example 7
Using 24.0 mg (0.020 mmol) of dichlorotetrakis (triphenylphosphine) ruthenium and 80 g of the ring-opening metathesis polymer of Synthesis Example 5 in THF solution, 86 ml of carbon monoxide in an amount of 180 moles with respect to the ruthenium complex was added. Except that it was used, the same procedure as in Example 3 was carried out to obtain a hydrogenated ring-opening metathesis polymer having a hydrogenation rate of 100%. The molar ratio of the repeating structural units [A] and [B] was [A] / [B] = 50/50, Mw was 8050, and Mw / Mn was 1.54.

Example 8
The contact treatment was carried out in the same manner as in Example 6 except that 33.0 mg (0.034 mmol) of dichlorotris (triphenylphosphine) ruthenium and 2 ml of carbon monoxide in an amount of 2.4 mol times the ruthenium complex were used.

A solution prepared by dissolving 110 g of the ring-opening metathesis polymer of Synthesis Example 6 in 300 g of THF was put in a 1 L autoclave, and further a solution of a ruthenium complex brought into contact with carbon monoxide was added. C. and a pressure of 8 MPa were heated for 5 hours.
The reaction solution was precipitated with water and dried under reduced pressure to obtain a hydrogenated ring-opening metathesis polymer. The hydrogenation rate of the polymer is 100%, the molar ratio of the repeating structural units [A] and [B] is [A] / [B] = 50/50, Mw is 11400, and Mw / Mn is 2.11. Met.

Example 9
Contact treatment was carried out in the same manner as in Example 6 except that 36.0 mg (0.029 mmol) of dichlorotetrakis (triphenylphosphine) ruthenium and 22.2 ml of carbon monoxide in an amount of 31 mol times the ruthenium complex were used.
A solution prepared by dissolving 120 g of the ring-opening metathesis polymer of Synthesis Example 7 in 300 g of THF was put in a 1 L autoclave, and further a solution of a ruthenium complex brought into contact with carbon monoxide was added. C. and a pressure of 7 MPa for 10 hours. The reaction solution was precipitated with water and dried under reduced pressure to obtain a hydrogenated ring-opening metathesis polymer. The hydrogenation rate of the polymer is 100%, the molar ratio of the repeating structural units [A] and [B] is [A] / [B] = 50/50, Mw is 11580, and Mw / Mn is 2.13. Met.

Example 10
Contact treatment was carried out in the same manner as in Example 6 except that 36.0 mg (0.038 mmol) of dichlorotris (triphenylphosphine) ruthenium and 27.4 ml of carbon monoxide in an amount of 30 moles relative to the ruthenium complex were used.
A solution obtained by dissolving 120 g of the ring-opening metathesis polymer of Synthesis Example 8 in 300 g of THF was hydrogenated in the same manner as in Example 9 to obtain a hydrogenated ring-opening metathesis polymer having a hydrogenation rate of 100%. The molar ratio of the repeating structural units [A] and [B] was [A] / [B] = 10/90, Mw was 5800, and Mw / Mn was 1.51.

Example 11
In a nitrogen glove box, 24.0 mg (0.023 mmol) of dichlorotris (triphenylphosphine) osmium and 30 g of THF were placed in a 50 ml container and stirred for 5 minutes.

A solution obtained by dissolving 80 g of the ring-opening metathesis polymer of Synthesis Example 6 in 460 g of THF and the entire solution in the container were placed in a 1 L autoclave, and 556 ml of carbon monoxide in an amount of 1000 moles with respect to the osmium complex was injected therein. Stir for minutes. Thereafter, the inside was replaced with hydrogen, and heated at a reaction temperature of 100 ° C. and a pressure of 8 MPa for 15 hours to obtain a hydrogenated ring-opening metathesis polymer. The hydrogenation rate of this polymer was 95.4%.
The molar ratio of the repeating structural units [A] and [B] was [A] / [B] = 50/50, Mw was 10850, and Mw / Mn was 2.10.

Example 12
1 part by weight of triphenylsulfonium nonafluorobutanesulfonate, 1 part by weight of trismethoxymethoxyethylamine and 640 parts by weight of cyclohexanone with respect to 80 parts by weight of the hydrogenated ring-opening metathesis polymer obtained in Example 1 After mixing and dissolution, a solution of a photoresist composition was prepared by filtering through a membrane filter having a pore size of 0.2 μm.

The photoresist composition in the solution is spin-coated on a silicon wafer coated with an antireflection film (ARC29A, manufactured by Nissan Chemical Industries, Ltd., 78 nm), and subjected to a heat treatment at 120 ° C. for 60 seconds to form a resist having a thickness of 250 nm. A film was formed. This was exposed using an ArF excimer laser stepper (manufactured by Nikon Corporation, NA = 0.68), heat-treated at 130 ° C. for 60 seconds, and then used with a 2.38% tetramethylammonium hydroxide aqueous solution Paddle development was performed for 60 seconds to form 1: 1 and 1:10 line and space patterns.

The developed wafer was cut and observed with a scanning electron microscope, and separated at an exposure amount (optimum exposure amount = Eop, mJ / cm ² ) for resolving a 0.13 μm line and space with 1: 1. The minimum line width (μm) of the existing line and space was defined as the resolution of the evaluation resist. As a result, the SB temperature was 100 ° C., the PEB temperature was 110 ° C., the optimum exposure was 25.0 mJ / cm ² , the resolution was 0.11 μm, and the density difference was 14 nm.

Comparative Example 1
Ring-opening metathesis polymer water having a hydrogenation rate of 62% was obtained in the same manner as in Example 1 except that the THF solution of dichlorotris (triphenylphosphine) ruthenium of Example 1 was used without contact treatment with carbon monoxide. An accessory was obtained.

Comparative Example 2
As in Example 6, a THF solution of a ring-opening metathesis polymer and a solution of 30 g of dichlorotetrakis (triphenylphosphine) ruthenium in THF were placed in a 1 L autoclave and stirred for 10 minutes without injecting carbon monoxide into the interior. Thereafter, the inside was replaced with hydrogen and heated at a reaction temperature of 100 ° C. and a pressure of 8 MPa for 12 hours to obtain a hydrogenated ring-opening metathesis polymer having a hydrogenation rate of 61%.

Comparative Example 3
In a nitrogen glove box, 24.2 mg (0.025 mmol) of chlorohydridocarbonyltris (triphenylphosphine) ruthenium and 30 g of THF were placed in a 50 ml container and stirred for 5 minutes.

  A solution of 110 g of the ring-opening metathesis polymer of Synthesis Example 1 in 110 g of THF and the entire solution in the container were placed in a 1 L autoclave, and 617 ml of carbon monoxide in an amount of 1000 moles with respect to the ruthenium complex was injected into the interior, and stirred for 10 minutes. . Thereafter, the inside was replaced with hydrogen and the same procedure as in Example 3 was carried out, but no hydrogenation reaction occurred.

Comparative Example 4
A solution of 36.2 mg (0.038 mmol) of chlorohydridocarbonyltris (triphenylphosphine), 104 g of the ring-opening metathesis polymer of Synthesis Example 2, and 415.4 ml of carbon monoxide in an amount of 450 moles with respect to the ruthenium complex. A hydrogenation reaction was carried out in the same manner as in Example 4 except that the hydrogenation rate of the ring-opening metathesis polymer was 20%.

Comparative Example 5
A hydrogenation reaction was carried out in the same manner as in Example 1 except that instead of carbon monoxide, 15 mol (0.15 mmol) of triethylamine and a catalyst solution of 5 mol times with respect to the ruthenium complex were used. A hydrogenated ring-opening metathesis polymer having a rate of 100% was obtained. This polymer was prepared in a solution of a photoresist composition in the same manner as in Example 12, and the resist was evaluated in the same manner. The SB temperature was 100 ° C., the PEB temperature was 110 ° C., the optimum exposure was 23.0 mJ / cm ² , the resolution was 0.14 μm, and the density difference was 19 nm.

According to the present invention, by using an organometallic complex in contact with carbon monoxide at 2 mole times or more of the organometallic complex as a hydrogenation catalyst, a double chain of a highly polar ring-opening metathesis polymer can be obtained. The efficiency of the hydrogenation catalyst for bonding can be improved, and an industrially valuable ring-opening metathesis polymer hydrogenated product can be obtained.
Hereinafter, examples of the reference form will be added.
<1>
The repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2) are in a molar ratio [A] / [B] = 10/90 to 90/10. Hydrogenate the double bond of the main chain with an organometallic complex in which the configured ring-opening metathesis polymer solution is contacted with carbon monoxide at least 2 mole times the organometallic complex represented by the general formula (3) A method for producing a hydrogenated ring-opening metathesis polymer.
(1)
(In the formula, at least one of R ^{1 to} R ⁴ is an alkoxycarbonyl group having 2 to 20 carbon atoms, an alkoxyalkyloxycarbonyl group having 3 to 20 carbon atoms, or an alkoxycarbonylalkyloxycarbonyl group having 4 to 20 carbon atoms. The others are selected from hydrogen, an alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, and an aryloxycarbonyl group having 6 to 20 carbon atoms. X ¹ is selected from —O— or —CR ⁵ R ⁶ — (R ⁵ and R ⁶ represent hydrogen, alkyl having 1 to 20 carbon atoms), and may be the same or different. Is selected from 0 or 1.)
(2)
(Wherein R ^{7 to} R ¹⁰ are each independently selected from hydrogen or an alkyl group having 1 to 10 carbon atoms, and X ² represents —O— or —CR ¹¹ R ¹² — (R ¹¹ , R ¹² represents hydrogen and an alkyl group having 1 to 20 carbon atoms.)
MQ _k Z _m (3)
(In the formula, M represents a ruthenium atom or an osmium atom, Q represents a halogen atom, and is selected from fluorine, chlorine, bromine, or iodine. Z represents PR ′ ¹ R ′ ² R ′ ³ (P represents a phosphorus atom) R ′ ¹ R ′ ² R ′ ³ represents the same or different linear, branched or cyclic alkyl group, alkenyl group, aryl group, alkoxy group or aryloxy group. And k is an integer of 1 to 4, m is an integer of 2 to 4, and k + m is an integer of 4 to 6.)
<2>
<1> according to <1>, wherein any ^one of X ¹ and X ² of the ring-opening metathesis polymer composed of the repeating structural units [A] and [B] is —O— and the other is —CH ₂ —. A method for producing a hydrogenated product of a ring-opening metathesis polymer.
<3>
The method for producing a hydrogenated ring-opening metathesis polymer according to <1> or <2>, wherein the molar ratio of the organic metal complex represented by the general formula (3) to carbon monoxide to be contacted is 2 to 1000 .
<4>
The method for producing a hydrogenated ring-opening metathesis polymer according to any one of <1> to <3>, wherein the hydrogenated ring-opening metathesis polymer is a base polymer for photoresist.

Claims (4)

The repeating structural unit [A] represented by the general formula (1) and the repeating structural unit [B] represented by the general formula (2) are in a molar ratio [A] / [B] = 10/90 to 90/10. The constituted ring-opening metathesis polymer solution is mixed with dichlorotris (triphenylphosphine) ruthenium, dichlorotetrakis (triphenylphosphine) ruthenium, dibromotris (triphenylphosphine) ruthenium, dibromotetrakis (triphenylphosphine) ruthenium, diiodotris (tri Phenylphosphine) ruthenium, diiodotetrakis (triphenylphosphine) ruthenium, dichlorotris (triphenylphosphine) osmium, dichlorotetrakis (triphenylphosphine) osmium, dibromotris (triphenylphosphine) osmium, dibromote Rakisu (triphenylphosphine) osmium, Jiyodotorisu (triphenylphosphine) osmium, organic contacted with di-iodo-tetrakis (triphenylphosphine) 2 mol times of carbon monoxide to the organic metal complex selected from the group consisting of osmium A method for producing a hydrogenated ring-opening metathesis polymer in which a double bond in a main chain is hydrogenated with a metal complex.
(1)
^(Wherein at least one of R 1 to R ⁴ is an alkoxycarbonyl group having 2 to 20 carbon atoms, alkoxy alkyloxycarbonyl group having 3 to 20 carbon atoms or an alkoxycarbonyl alkyloxycarbonyl group having 4 to 20 carbon atoms, selected from, others are selected from hydrogen, alkyl group having 1 to 20 carbon atoms, an alkoxy group having 1 to 20 carbon atoms, an alkoxyalkyl group having 2 to 20 carbon atoms, aryloxycarbonyl group having 6 to 20 carbon atoms . Further, ^{X 1} is -O-, or ^-CR 5 ^{R 6} -. from ^(. R 5, ^{R 6} are representing hydrogen, an alkyl group having 1 to 20 carbon atoms) chosen, may be the same or different also , J is selected from 0 or 1.)
(2)
(Wherein R ^{7 to} R ¹⁰ are each independently selected from hydrogen or an alkyl group having 1 to 10 carbon atoms, and X ² represents —O— or —CR ¹¹ R ¹² — (R ¹¹ , R ¹² represents hydrogen, an alkyl group having 1 to 20 carbon atoms.) chosen.) 2. The ring-opening metathesis polymer composed of repeating structural units [A] and [B], wherein ^one of X ¹ and X ² is —O—, and the other is —CH ₂ —. A method for producing a hydrogenated product of a ring-opening metathesis polymer. Dichlorotris (triphenylphosphine) ruthenium, dichlorotetrakis (triphenylphosphine) ruthenium, dibromotris (triphenylphosphine) ruthenium, dibromotetrakis (triphenylphosphine) ruthenium, diiodotris (triphenylphosphine) ruthenium, diiodotetrakis (triphenyl) Phosphine) ruthenium, dichlorotris (triphenylphosphine) osmium, dichlorotetrakis (triphenylphosphine) osmium, dibromotris (triphenylphosphine) osmium, dibromotetrakis (triphenylphosphine) osmium, diiodotris (triphenylphosphine) osmium, diiodo Selected from the group consisting of tetrakis (triphenylphosphine) osmium Wherein the organometallic complex, the molar ratio of carbon monoxide to be contacted, the manufacturing method of the hydrogenated ring-opening metathesis polymer according a to claim 1 or claim 2 2-1000.   The method for producing a hydrogenated ring-opening metathesis polymer according to any one of claims 1 to 3, wherein the hydrogenated ring-opening metathesis polymer is a base polymer for photoresist.