JP2005187804A - Ring-opening metathesis copolymer hydrogenated product and method for producing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a polymer having good film-forming properties and capable of being easily utilized as a semiconductor fine processing photoresist film. <P>SOLUTION: This ring-opening metathesis copolymer hydrogenated product comprises at least structural units expressed by general formula [3] [R<SP>8</SP>to R<SP>11</SP>are each H or a 1-10C alkyl; X<SP>2</SP>is -O- or -CR<SP>12</SP><SB>2</SB>- (R<SP>12</SP>is H or a 1-10C alkyl); and m is 0 or an integer of 1 to 3] and/or general formula [4] [R<SP>13</SP>to R<SP>16</SP>are each H or a 1-10C alkyl; X<SP>3</SP>is -O- or -CR<SP>12</SP><SB>2</SB>-; one of Y<SP>1</SP>and Y<SP>2</SP>is -(C=O)- and the other is -CR<SP>18</SP><SB>2</SB>- (R<SP>18</SP>is H or a 1-10C alkyl); and n is 0 or an integer of 1 to 3] and has a ratio (Mw/Mn) of a weight-average molecular weight (Mw) to a number-average molecular weight (Mn) of more than 2.0 and less than 5.0. <P>COPYRIGHT: (C)2005,JPO&NCIPI

Description

The present invention relates to a hydrogenated ring-opening metathesis polymer having a specific molecular weight distribution. Related to hydrogenated ring-opening metathesis polymers that have the properties of being easy to use as a resist film while having physical properties such as heat resistance, thermal decomposition resistance, and light transmission properties as compared to known polymers And a method for producing such a polymer hydrogenated product.

In recent years, integration of semiconductor integrated circuits has progressed, and large-scale integrated circuits (LSIs) and very large-scale integrated circuits (VLSIs) have been put into practical use. There is a tendency to further miniaturize in the future. 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 exposure light sources used in this lithography technique, ultraviolet light of g-line (wavelength 436 nm) and i-line (wavelength 365 nm) is used. Light, electron beams (EB), X-rays and the like have been used as light sources. Recently, excimer lasers (KrF laser with a wavelength of 248 nm, ArF laser with a wavelength of 193 nm) have attracted attention as an exposure light source, and are expected to be effective for forming fine patterns.

  As a polymer or copolymer used in a resist material that forms a submicron pattern using exposure light in the vacuum ultraviolet region, a cyclic skeleton having an aliphatic cyclic hydrocarbon as a main chain and a functional group that is decomposed by an acid is used. Cyclic polymers such as those found in photoresist compositions (see Patent Documents 1, 2, 3, and 4) comprising a polymer compound having excellent dry etching resistance and excellent transparency to deep ultraviolet light, There existed problems, such as the solubility with respect to the resist solvent in high concentration, the wettability with respect to a developing solution, and the adhesiveness to a silicon substrate.

In order to solve such problems, the present inventors previously proposed a polymer having a narrow molecular weight distribution obtained by living metathesis polymerization of a specific cyclic olefin and then hydrogenation (see Patent Document 5).
WO 97/33198 JP 09-230595 A JP 09-244247 A Japanese Patent Laid-Open No. 10-254139 WO 01/79324 publication

The polymers disclosed in the above publications are excellent in light transmittance, high sensitivity and high resolution for semiconductor microfabrication using ultraviolet rays or far ultraviolet rays (including excimer lasers) as a base polymer for resist materials. In addition, it has a high affinity for an alkali developer and is useful to satisfy all the performances required to be used as a base polymer for a positive photoresist composition resist material that provides a good pattern. There are problems such as a narrow range of practical use conditions, and further improvements are desired.

In order to solve the above problems, the present inventors have made various studies, found that the ring-opening metathesis polymer hydrogenated product of a specific cyclic olefin monomer has excellent characteristics, and completed the present invention. It came.
That is, the present invention provides the following general formula [1]

（式中、Ｒ¹〜Ｒ⁴のうち少なくとも一つが、下記一般式［２］

(In the formula, at least one of R ^{1 to} R ⁴ is represented by the following general formula [2]:

（式中、鎖線は結合手を示す。Ｒ⁵は水素原子、炭素数１〜１０の直鎖状、分岐状または環状のアルキル基、炭素数２〜１０の直鎖状、分岐状または環状のアルコキシアルキル基、または炭素数１〜１０の直鎖状、分岐状または環状のアシル基を示す。Ｒ⁶は炭素数１〜１０の直鎖状、分岐状または環状のアルキル基を示す。Ｗ¹は単結合または炭素数１〜１０のｋ＋２価の炭化水素基を示す。Ｚは炭素数２〜１５の２価の炭化水素基を示し、結合する炭素原子とともに単環または架橋環を形成する。ｋは０または１である。）で表される環状アルキルの三級エステル基を有する官能基であり、その他はそれぞれ独立に、水素原子、炭素数１〜２０の直鎖状、分岐状または環状のアルキル基、ハロゲン、炭素数１〜２０の直鎖状、分岐状または環状のハロゲン化アルキル基、炭素数１〜２０の直鎖状、分岐状または環状のアルコキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシアルキル基、炭素数２〜２０の直鎖状、分岐状または環状のアルキルカルボニルオキシ基、炭素数６〜２０のアリールカルボニルオキシ基、炭素数１〜２０の直鎖状、分岐状または環状のアルキルスルホニルオキシ基、炭素数６〜２０のアリールスルホニルオキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシカルボニル基、または炭素数３〜２０の直鎖状、分岐状または環状のアルコキシカルボニルアルキル基から選ばれ、Ｘ¹は−Ｏ−または−ＣＲ⁷ ₂−（Ｒ⁷は水素原子または炭素数１〜１０の直鎖状または分岐状のアルキル基を表す）であり、同一でも異なってもよい。ｊは０または１〜３の整数を表す。）で表される構造単位［Ａ］を所望により含み、かつ、下記一般式［３］

(In the formula, a chain line represents a bond. R ⁵ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, R ⁶ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, W ¹ Represents a single bond or a K + divalent hydrocarbon group having 1 to 10 carbon atoms, Z represents a divalent hydrocarbon group having 2 to 15 carbon atoms, and forms a single ring or a bridged ring together with the carbon atoms to be bonded. k is 0 or 1.) is a functional group having a cyclic alkyl tertiary ester group, and the others are each independently a hydrogen atom, a linear, branched or cyclic group having 1 to 20 carbon atoms. An alkyl group, halogen, linear, branched or 1 to 20 carbon atoms A halogenated alkyl group, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, and a carbon number 2 to 20 Linear, branched or cyclic alkylcarbonyloxy group, arylcarbonyloxy group having 6 to 20 carbon atoms, linear, branched or cyclic alkylsulfonyloxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms An arylsulfonyloxy group, a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a linear, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, ¹ is -O- or -CR ⁷ ₂ - (R ⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and may be the same or different j represents 0 or an integer of 1 to 3; A structural unit [A] represented by the following general formula [3]

（式中、Ｒ⁸〜Ｒ¹¹は、それぞれ独立に、水素原子または炭素数１〜１０の直鎖状、分岐状または環状のアルキル基であり、Ｘ²は−Ｏ−または−ＣＲ¹² ₂−（Ｒ¹²は水素原子または炭素数１〜１０の直鎖状または分岐状のアルキル基を表す）であり、同一でも異なってもよい。ｍは０または１〜３の整数を表す。）で表される構造単位［Ｂ］および／または下記一般式［４］

(Wherein R ^{8 to} R ¹¹ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and X ² is —O— or —CR ¹² ₂ —. (R ¹² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and may be the same or different. M represents an integer of 0 or 1 to 3). Structural unit [B] and / or the following general formula [4]

（式中、Ｒ¹³〜Ｒ¹⁶は、それぞれ独立に、水素原子または炭素数１〜１０の直鎖状、分岐状または環状のアルキル基であり、Ｘ³は−Ｏ−または−ＣＲ¹⁷ ₂−（Ｒ¹⁷は水素原子または炭素数１〜１０の直鎖状または分岐状のアルキル基を表す）であり、同一でも異なってもよい。Ｙ¹およびＹ²は、一方が−（Ｃ＝Ｏ）−であり、他方は、−ＣＲ¹⁸ ₂−（Ｒ¹⁸は水素原子または炭素数１〜１０の直鎖状または分岐状のアルキル基を表す）である。ｎは０または１〜３の整数を表す。）で表される構造単位［Ｃ］を少なくとも含み、かつ、一般式［１］で表される構造単位［Ａ］のＸ¹、一般式［３］で表される構造単位［Ｂ］のＸ²、および一般式［４］で表される構造単位［Ｃ］のＸ³のうち少なくとも１つが−Ｏ−であり、その構成モル比［Ａ］／（［Ｂ］および［Ｃ］）が０／１００〜９９／１であり、かつ重量平均分子量Ｍｗと数平均分子量Ｍｎとの比（Ｍｗ／Ｍｎ）が２．０より大きく５．０より小さいことを特徴とする開環メタセシス重合体水素添加物である。

(Wherein R ^{13 to} R ¹⁶ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and X ³ is —O— or —CR ¹⁷ ₂ —. (R ¹⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms) and may be the same or different, and ^one of Y ¹ and Y ² is — (C═O). And the other is —CR ¹⁸ ₂ — (R ¹⁸ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.) N is an integer of 0 or 1 to 3. X ¹ of the structural unit [A] represented by the general formula [1] and at least the structural unit [B] represented by the general formula [3]. X ^2, and at least one of X ³ of general formula [4] represented by the structural unit [C] is -O-, and its constituent molar ratio of A] / ([B] and [C]) is 0/100 to 99/1, and the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is greater than 2.0 and 5.0. A ring-opening metathesis polymer hydrogenated product characterized by being smaller.

  In addition to the structural units [A] and [B] and / or [C], the present invention can be represented by the general formula [5].

（式中、Ｒ^１９〜Ｒ^２２のうち少なくとも一つが、下記一般式［６］

(In the formula, at least one of R ^{19 to} R ²² is represented by the following general formula [6].

（式中、鎖線は結合手を示す。Ｒ^２３は水素原子、炭素数１〜１０の直鎖状、分岐状または環状のアルキル基、炭素数２〜１０の直鎖状、分岐状または環状のアルコキシアルキル基、または炭素数１〜１０の直鎖状、分岐状または環状のアシル基を示す。Ｗ^２は単結合または炭素数１〜１０のｑ＋２価の炭化水素基を示す。ｑは０または１である。）で表されるカルボン酸基を有する官能基であり、その他はそれぞれ独立に、水素原子、炭素数１〜２０の直鎖状、分岐状または環状のアルキル基、ハロゲン、炭素数１〜２０の直鎖状、分岐状または環状のハロゲン化アルキル基、炭素数１〜２０の直鎖状、分岐状または環状のアルコキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシアルキル基、炭素数２〜２０の直鎖状、分岐状または環状のアルキルカルボニルオキシ基、炭素数６〜２０のアリールカルボニルオキシ基、炭素数１〜２０の直鎖状、分岐状または環状のアルキルスルホニルオキシ基、炭素数６〜２０のアリールスルホニルオキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシカルボニル基、または炭素数３〜２０の直鎖状、分岐状または環状のアルコキシカルボニルアルキル基から選ばれ、Ｘ^４は−Ｏ−または−ＣＲ^２４ ₂−（Ｒ^２４は水素原子または炭素数１〜１０の直鎖状または分岐状のアルキル基を表す）であり、同一でも異なってもよい。ｐは０または１〜３の整数を表す。）で表される構造単位［Ｄ］を更に含む開環メタセシス重合体水素添加物である。

(In the formula, a chain line represents a bond. R ²³ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, W ² represents a single bond or a q + 2 valent hydrocarbon group having 1 to 10 carbon atoms, and q is 0 or 1 is a functional group having a carboxylic acid group, and the others are independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, halogen, and carbon number. 1-20 linear, branched or cyclic halogenated alkyl groups, 1-20 carbon linear, branched or cyclic alkoxy groups, 2-20 carbon linear, branched or cyclic An alkoxyalkyl group, a straight chain having 2 to 20 carbon atoms, Branched or cyclic alkylcarbonyloxy group, arylcarbonyloxy group having 6 to 20 carbon atoms, linear, branched or cyclic alkylsulfonyloxy group having 1 to 20 carbon atoms, arylsulfonyloxy having 6 to 20 carbon atoms A linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a linear, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and X ⁴ is —O — Or —CR ²⁴ ₂ — (R ²⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), which may be the same or different. p represents 0 or an integer of 1 to 3. A ring-opening metathesis polymer hydrogenated product further comprising a structural unit [D] represented by:

  In addition to the structural units [A] and [B] and / or [C], preferably in addition to [D], the present invention provides the general formula [7].

（式中、Ｒ^２５〜Ｒ^２８のうち少なくとも一つが、下記一般式［８］

(In the formula, at least one of R ^{25 to} R ²⁸ is represented by the following general formula [8]:

（式中、鎖線は結合手を示す。Ｒ^２９は水素原子、炭素数１〜１０の直鎖状、分岐状または環状のアルキル基、炭素数２〜１０の直鎖状、分岐状または環状のアルコキシアルキル基、または炭素数１〜１０の直鎖状、分岐状または環状のアシル基を示す。Ｒ^３０は炭素数１〜１０の直鎖状または分岐状のアルキル基、炭素数２〜１０の直鎖状、分岐状または環状のアルコキシアルキル基、炭素数１〜２０の直鎖状、分岐状または環状のハロゲン化アルキル基を示す。Ｗ^３は単結合または炭素数１〜１０のｓ＋２価の炭化水素基を示す。ｓは０または１である。）で表されるカルボン酸エステル基を有する官能基であり、その他はそれぞれ独立に、水素原子、炭素数１〜２０の直鎖状、分岐状または環状のアルキル基、ハロゲン、炭素数１〜２０の直鎖状、分岐状または環状のハロゲン化アルキル基、炭素数１〜２０の直鎖状、分岐状または環状のアルコキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシアルキル基、炭素数２〜２０の直鎖状、分岐状または環状のアルキルカルボニルオキシ基、炭素数６〜２０のアリールカルボニルオキシ基、炭素数１〜２０の直鎖状、分岐状または環状のアルキルスルホニルオキシ基、炭素数６〜２０のアリールスルホニルオキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシカルボニル基、または炭素数３〜２０の直鎖状、分岐状または環状のアルコキシカルボニルアルキル基から選ばれ、Ｘ^５は−Ｏ−または−ＣＲ^３１ ₂−（Ｒ^３１は水素原子または炭素数１〜１０の直鎖状または分岐状のアルキル基を表す）であり、同一でも異なってもよい。ｒは０または１〜３の整数を表す。）で表される構造単位［Ｅ］を更に含む開環メタセシス重合体水素添加物である。

(In the formula, a chain line represents a bond. R ²⁹ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, R ³⁰ is a linear or branched alkyl group having 1 to 10 carbon atoms, or a carbon number 2 to 10 A linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkyl halide group having 1 to 20 carbon atoms, W ³ is a single bond or an s + 2 valent group having 1 to 10 carbon atoms. Represents a hydrocarbon group. S is 0 or 1.) is a functional group having a carboxylic acid ester group, and the others are each independently a hydrogen atom, a straight chain having 1 to 20 carbon atoms, branched. Or cyclic alkyl group, halogen, 1 to carbon atoms A linear, branched or cyclic halogenated alkyl group of 0, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 2 to 20 carbon atoms An alkyl group, a linear, branched or cyclic alkylcarbonyloxy group having 2 to 20 carbon atoms, an arylcarbonyloxy group having 6 to 20 carbon atoms, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms A sulfonyloxy group, an arylsulfonyloxy group having 6 to 20 carbon atoms, a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a linear, branched or cyclic group having 3 to 20 carbon atoms selected from alkoxycarbonyl alkyl group, ^{X 5} is -O- or ^{-CR 31} ₂ - Table of ^{(R 31} is a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms ), And it may be the same or different. r represents 0 or an integer of 1 to 3. The ring-opening metathesis polymer hydrogenated product further comprising a structural unit [E] represented by:

  Furthermore, the present invention provides the following general formula [9]

（式中、Ｒ¹〜Ｒ⁴、Ｘ¹、およびｊは一般式［１］中の定義と同じ。）で表される環状オレフィン単量体を所望により用い、下記一般式［１０］

(Wherein R ^{1 to} R ⁴ , X ¹ and j are the same as defined in the general formula [1]), a cyclic olefin monomer represented by the following general formula [10] is optionally used.

（式中、Ｒ⁸〜Ｒ¹¹、 Ｘ²、およびｍは一般式［３］中の定義と同じ。）で表される環状オレフィン単量体および／または下記一般式［１１］

(Wherein R ^{8 to} R ¹¹ , X ² , and m are the same as defined in general formula [3]) and / or the following general formula [11]

（式中、Ｒ¹³〜Ｒ¹⁶、Ｘ³、Ｙ¹、Ｙ²およびｎは一般式［４］中の定義と同じ。）で表される環状オレフィン単量体を少なくとも用い、かつ一般式［９］のＸ¹、一般式［１０］のＸ²、および一般式［１１］のＸ³のうち少なくとも１つが−Ｏ−であり、これらを開環メタセシス触媒で重合し、そして水素添加触媒のもとに水素添加することを特徴とする開環メタセシス重合体水素添加物の製造方法であり、さらに、本発明は、水素添加後、一般式［２］における環状アルキルの三級エステル基の少なくとも一部をカルボン酸基に分解することを特徴とする開環メタセシス重合体水素添加物の製造方法である。

(Wherein R ^{13 to} R ¹⁶ , X ³ , Y ¹ , Y ² and n are the same as defined in the general formula [4]) and at least a cyclic olefin monomer represented by the general formula [ X ¹ 9], at least one of X ³ of X ^2, and of general formula [10] [11] Although -O-, and polymerizing them in ring-opening metathesis catalyst, and a hydrogenation catalyst A hydrogenated product of a ring-opening metathesis polymer characterized by hydrogenation, and the present invention further comprises at least a tertiary ester group of a cyclic alkyl in the general formula [2] after hydrogenation. A method for producing a hydrogenation product of a ring-opening metathesis polymer characterized in that a part thereof is decomposed into carboxylic acid groups.

  In addition to the general formulas [9] and [10] and / or [11], the present invention further includes the following general formula [12].

（式中、Ｒ²⁵〜Ｒ²⁸、Ｘ⁵、およびｒは一般式［７］中の定義と同じ。）で表される環状オレフィン単量体を用いることを特徴とする開環メタセシス重合体水素添加物の製造方法であり、さらに、水素添加後、そのエステル基の少なくとも一部をカルボン酸基に分解することを特徴とする開環メタセシス重合体水素添加物の製造方法である。

(Wherein R ^{25 to} R ²⁸ , X ⁵ , and r are the same as defined in the general formula [7]), a ring-opening metathesis polymer hydrogen characterized by using a cyclic olefin monomer This is a method for producing an additive, and further, after hydrogenation, at least a part of the ester group is decomposed into a carboxylic acid group, which is a method for producing a hydrogenated ring-opening metathesis polymer.

The polymer having a wide molecular weight distribution according to the present invention has excellent film forming properties and can easily form films having different thicknesses, which is extremely valuable industrially.

In the general formula [1] of the present invention, at least one of R ^{1 to} R ⁴ is the general formula [2].

（式中、鎖線は結合手を示す。Ｒ⁵は水素原子、炭素数１〜１０の直鎖状、分岐状または環状のアルキル基、炭素数２〜１０の直鎖状、分岐状または環状のアルコキシアルキル基、または炭素数１〜１０の直鎖状、分岐状または環状のアシル基を示す。Ｒ⁶は炭素数１〜１０の直鎖状、分岐状または環状のアルキル基を示す。Ｗ¹は単結合または炭素数１〜１０のｋ＋２価の炭化水素基を示す。Ｚは炭素数２〜１５の２価の炭化水素基を示し、結合する炭素原子とともに単環または架橋環を形成する。ｋは０または１である。）で表される環状アルキルの三級エステル基を有する官能基である。

(In the formula, a chain line represents a bond. R ⁵ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, R ⁶ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, W ¹ Represents a single bond or a K + divalent hydrocarbon group having 1 to 10 carbon atoms, Z represents a divalent hydrocarbon group having 2 to 15 carbon atoms, and forms a single ring or a bridged ring together with the carbon atoms to be bonded. k is 0 or 1.) is a functional group having a cyclic alkyl tertiary ester group represented by:

In R ⁵ , examples of the linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, and 1-ethyl. Examples thereof include cyclopentyl and 1-ethylcyclohexyl. Examples of the linear, branched or cyclic alkoxyalkyl group having 2 to 10 carbon atoms include methoxymethyl, 1-ethoxyethyl, 1-tert-butoxyethyl, 1 -Cyclohexyloxyethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl and the like. Examples of the cyclic acyl group include formyl, acetyl, and piva. Yl, and cyclohexylcarbonyl, and the like. Among these R ^5, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 7 carbon atoms, and a linear chain having 2 to 7 carbon atoms A branched or branched acyl group is preferable, and a hydrogen atom, methyl, ethyl, methoxymethyl, 1-ethoxyethyl, tetrahydrofuran-2-yl and acetyl are particularly preferable.

In R ⁶ , examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, cyclooctyl, Norbornyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methylnorbornyl, 1-ethylnorbornyl and the like, among these, methyl, ethyl, propyl, Isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl, norbornyl, 1-ethylcyclopentyl and 1-ethylcyclohexyl are preferred.

In W ¹ , the k + 1 divalent hydrocarbon group having 1 to 10 carbon atoms is a linear, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms when k is 0, for example, Methylene, dimethylmethylene, ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2,2 -Dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, tetramethylene, pentamethylene, 1,1-cyclopentylene, 1,2 -Cyclopentylene, 1,3-cyclopentylene, 1,1-cyclohexylene, 1,2-cyclohexylene, 1,3 Cyclohexylene, and 1,4-cyclohexylene. Of these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene, and 2-methyltrimethylene are preferred. When k is 1, for example, a bond formed by removing one hydrogen atom at an arbitrary position on the hydrocarbon group mentioned in the case where k is 0 is mentioned. Most preferred W ¹ is a single bond.

  Z is a divalent hydrocarbon group having 2 to 15 carbon atoms, and is a hydrocarbon group that forms a single ring or a bridged ring with the carbon atoms to be bonded. For example, the following general formula [13]

（式中、鎖線は結合手を示す。Ｒ⁶は前記定義どおり。Ｒ³²〜Ｒ³⁷はそれぞれ独立に水素原子または炭素数１〜１０の直鎖状、分岐状または環状のアルキル基である。ｂは０または１〜６の整数であり、ｂが２〜６の場合、複数のＲ³⁴およびＲ³⁵はそれぞれ同一であっても異なっていてもよい。）で表される１−アルキルシクロアルキル基、下記一般式［１４］

(In the formula, a chain line represents a bond. R ⁶ is as defined above. R ^{32 to} R ³⁷ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. b is an integer of 0 or 1 to 6, and when b is 2 to 6, a plurality of R ³⁴ and R ³⁵ may be the same or different, respectively. Group represented by the following general formula [14]

（式中、鎖線は結合手を示す。Ｒ⁶は前記定義どおり。Ｒ³⁸〜Ｒ⁴⁷はそれぞれ独立に水素原子または炭素数１〜１０の直鎖状、分岐状または環状のアルキル基である。）で表される２−アルキルノルボルニル基、および２−メチル−２−アダマンチルおよび２−エチル−２−アダマンチル等の２−アルキル−２−アダマンチル基が挙げられる。一般式［１３］の具体例としては、１−メチルシクロプロピル、１−メチルシクロブチル、１−エチルシクロブチル、１−メチルシクロペンチル、１−エチルシクロペンチル、１−ｎ−プロピルシクロペンチル、１−ｉｓｏ−プロピルシクロペンチル、１−ｔｅｒｔ−ブチルシクロペンチル、１−シクロペンチルシクロペンチル、１−シクロヘキシルシクロペンチル、１−ノルボルニルシクロペンチル、１−メチルシクロヘキシル、１−エチルシクロヘキシル、１−メチルシクロヘプチル、１−エチルシクロヘプチル、１−メチルシクロオクチル、および１−メチルシクロノニル等が挙げられ、これらのうち、１−メチルシクロペンチル、１−エチルシクロペンチル、１−ｎ−プロピルシクロペンチル、１−ｉｓｏ−プロピルシクロペンチル、１−ｔｅｒｔ−ブチルシクロペンチル、１−シクロペンチルシクロペンチル、１−シクロヘキシルシクロペンチル、および１−ノルボルニルシクロペンチル等の化学式［１３−１］〜［１３−８］

(In the formula, a chain line represents a bond. R ⁶ is as defined above. R ^{38 to} R ⁴⁷ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms. ) And 2-alkyl-2-adamantyl groups such as 2-methyl-2-adamantyl and 2-ethyl-2-adamantyl. Specific examples of the general formula [13] include 1-methylcyclopropyl, 1-methylcyclobutyl, 1-ethylcyclobutyl, 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-iso- Propylcyclopentyl, 1-tert-butylcyclopentyl, 1-cyclopentylcyclopentyl, 1-cyclohexylcyclopentyl, 1-norbornylcyclopentyl, 1-methylcyclohexyl, 1-ethylcyclohexyl, 1-methylcycloheptyl, 1-ethylcycloheptyl, 1 -Methylcyclooctyl, 1-methylcyclononyl, etc., among which 1-methylcyclopentyl, 1-ethylcyclopentyl, 1-n-propylcyclopentyl, 1-iso-propylcyclopentyl 1-tert-butyl-cyclopentyl, 1-cyclopentyl cyclopentyl, 1-cyclohexyl-cyclopentyl, and 1-norbornyl cyclopentyl formula such as Le [13-1] - [13-8]

で表される１−アルキルシクロペンチルが好ましく、より好ましくは１−メチルシクロペンチル［１３−１］および１−エチルシクロペンチル［１３−２］である。一般式［１４］の具体例としては、化学式［１４−１］〜［１４−１１］

Are preferable, 1-methylcyclopentyl [13-1] and 1-ethylcyclopentyl [13-2] are more preferable. Specific examples of the general formula [14] include chemical formulas [14-1] to [14-11].

等の２−アルキルノルボルニル基が挙げられ、これらのうち、［１４−１］、［１４−２］、［１４−３］および［１４−４］が好ましい。

2-alkylnorbornyl groups such as [14-1], [14-2], [14-3] and [14-4] are preferable.

Others among R ^{1 to} R ⁴ are each independently a hydrogen atom, a linear or branched chain such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl having 1 to 20 carbon atoms. Or cyclic alkyl group, halogen such as chlorine atom, bromine atom, iodine atom or fluorine atom, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloro having 1 to 20 carbon atoms Linear, branched or cyclic halogenated alkyl groups such as methyl or tribromomethyl, linear or branched such as methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy or mentoxy having 1 to 12 carbon atoms Or cyclic alkoxy group, methoxymethyl having 2 to 20 carbon atoms, Linear, branched or cyclic alkoxyalkyl groups containing alkoxysaccharides such as toxiethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymenthol, or methyl glucose, linear chains such as acetoxy having 2 to 20 carbon atoms , Branched or cyclic alkylcarbonyloxy groups, arylcarbonyloxy groups such as naphthoyloxy having 6 to 20 carbon atoms, and linear, branched or cyclic alkylsulfonyloxy groups such as mesyloxy having 1 to 20 carbon atoms Arylsulfonyloxy groups such as tosyloxy having 6 to 20 carbon atoms, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, or cyclohexylo having 2 to 20 carbon atoms Linear, branched or cyclic alkoxycarbonyl groups such as xyloxycarbonyl, methoxycarbonylmethyl having 3 to 20 carbon atoms, 2- (methoxycarbonyl) ethyl, 1- (methoxycarbonyl) ethyl, ethoxycarbonylmethyl, 2- ( Specific examples include linear, branched or cyclic alkoxycarbonylalkyl groups such as ethoxycarbonyl) ethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, tert-butoxycarbonylmethyl, or cyclohexyloxycarbonylmethyl. Take as an example. Among these, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, and a straight chain having 2 to 20 carbon atoms. A linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, and a linear, branched or cyclic alkoxycarbonylalkyl having 3 to 20 carbon atoms Group, more preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxycarbonyl group having 2 to 10 carbon atoms, and 3 to 10 carbon atoms. A linear or branched alkoxycarbonylalkyl group.

X ¹ is —O— or —CR ⁷ ₂ — (R ⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and when j is 1 to 3, X ¹ May be the same or different. Specific examples of R ⁷ include a hydrogen atom or a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl having 1 to 10 carbon atoms. X ¹ is preferably —O— or —CH ₂ —, and more preferably all X ¹ are either —O— or —CH ₂ —. j is preferably 0 or 1.

  That is, specific examples of the general formula [1] include chemical formulas [1-1] to [1-64].

等で表される構造単位［Ａ］が挙げられる。

The structural unit [A] represented by etc. is mentioned.

In the general formula [3], R ^{8 to} R ¹¹ are each independently a hydrogen atom or methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl having 1 to 10 carbon atoms. Specific examples thereof include linear, branched or cyclic alkyl groups such as X ² is —O— or —CR ¹² ₂ — (R ¹² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and when m is 1 to 3, X ² May be the same or different. Specific examples of R ¹² include a hydrogen atom or a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl having 1 to 10 carbon atoms. X ² is preferably —O— or —CH ₂ —, and more preferably all X ² are either —O— or —CH ₂ —. m is preferably 0 or 1.

  That is, specific examples of the general formula [3] include chemical formulas [3-1] to [3-16].

等で表される構造単位［Ｂ］が挙げられる。
また、一般式［４］において、Ｒ¹³〜Ｒ¹⁶は、それぞれ独立に、水素原子、または炭素数１〜１０のメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチル、ｔｅｒｔ−ブチル、シクロヘキシルまたはメンチル等の直鎖状、分岐状または環状のアルキル基が具体例として挙げられる。Ｘ³は−Ｏ−または−ＣＲ¹⁷ ₂−（Ｒ¹⁷は水素原子または炭素数１〜１０の直鎖状または分岐状のアルキル基を表す）であり、 ｎが１〜３の場合、Ｘ³は同一でも異なってもよい。Ｒ¹⁷としては水素原子、または炭素数１〜１０のメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチルまたはｔｅｒｔ−ブチル等の直鎖状または分岐状のアルキル基が具体例として挙げられる。Ｘ³として、好ましくは−Ｏ−または−ＣＨ₂−であり、より好ましくはすべてのＸ³が−Ｏ−または−ＣＨ₂−の何れかである。Ｙ¹およびＹ²は、一方が−（Ｃ＝Ｏ）−であり、他方は、−ＣＲ¹⁸ ₂−（Ｒ¹⁸は水素原子または炭素数１〜１０の直鎖状または分岐状のアルキル基を表す）である。Ｒ¹⁸としては水素原子、または炭素数１〜１０のメチル、エチル、ｎ−プロピル、イソプロピル、ｎ−ブチルまたはｔｅｒｔ−ブチル等の直鎖状または分岐状のアルキル基が具体例として挙げられる。Ｙ¹およびＹ²として、好ましくは一方が−（Ｃ＝Ｏ）−であり、他方が−ＣＨ₂−である。ｎとして好ましくは、０または１である。

The structural unit [B] represented by etc. is mentioned.
Moreover, in General formula [4], R < ¹³ > -R < ¹⁶ > is respectively independently a hydrogen atom or a C1-C10 methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or Specific examples include linear, branched or cyclic alkyl groups such as menthyl. X ³ is —O— or —CR ¹⁷ ₂ — (R ¹⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and when n is 1 to ^3, May be the same or different. Specific examples of R ¹⁷ include a hydrogen atom or a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl having 1 to 10 carbon atoms. X ³ is preferably —O— or —CH ₂ —, and more preferably all X ³ are either —O— or —CH ₂ —. One of Y ¹ and Y ² is — (C═O) —, and the other is —CR ¹⁸ ₂ — (R ¹⁸ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms. Express). Specific examples of R ¹⁸ include a hydrogen atom or a linear or branched alkyl group such as methyl, ethyl, n-propyl, isopropyl, n-butyl or tert-butyl having 1 to 10 carbon atoms. As Y ¹ and Y ² , one is preferably — (C═O) — and the other is —CH ₂ —. n is preferably 0 or 1.

  That is, specific examples of the general formula [4] include chemical formulas [4-1] to [4-16].

等で表される構造単位［Ｃ］が挙げられる。
本発明における開環メタセシス重合体水素添加物は、一般式［１］で表される構造単位［Ａ］のＸ¹、一般式［３］で表される構造単位［Ｂ］のＸ²、および一般式［４］で表される構造単位［Ｃ］のＸ³のうち少なくとも１つが−Ｏ−である開環メタセシス重合体水素添加物であり、このように酸素原子が主鎖に存在することにより、シリコン基板のような被処理基板への密着性、アルカリ水溶液による現像時に濡れ張力の改善、レジスト剤のシリコンウエハに塗布する工程で使用されるケトン類、アルコール類等の極性有機溶媒に対する溶解性をさらに向上させる効果があり、また、水に対する親和性も向上し、露光後のアルカリ水溶液等の剥離剤（または現像剤）に対する現像性も向上する。好ましくは、一般式［１］で表される構造単位［Ａ］のＸ¹、一般式［３］で表される構造単位［Ｂ］のＸ²、および一般式［４］で表される構造単位［Ｃ］のＸ³のうち少なくとも１つが−Ｏ−であり、その他が−ＣＨ₂−である開環メタセシス重合体水素添加物である。Ｘ¹、Ｘ²およびＸ³の全合計単位モル量に対する−Ｏ−単位のモル量は、０．０１〜０．９９であり、好ましくは０．０２〜０．９５であり、より好ましくは０．０５〜０．８０であり、最も好ましくは０．１０〜０．７０である。

The structural unit [C] represented by etc. is mentioned.
The hydrogenated ring-opening metathesis polymer in the present invention includes X ¹ of the structural unit [A] represented by the general formula [1], X ^{2 of the} structural unit [B] represented by the general formula [3], and It is a ring-opening metathesis polymer hydrogenated product in which at least one of X ³ of the structural unit [C] represented by the general formula [4] is —O—, and oxygen atoms are present in the main chain in this way. Adhesion to a substrate to be processed such as a silicon substrate, improvement of wetting tension at the time of development with an alkaline aqueous solution, dissolution in polar organic solvents such as ketones and alcohols used in the process of applying a resist agent to a silicon wafer In addition, the affinity for water is improved, and the developability for a release agent (or developer) such as an aqueous alkali solution after exposure is also improved. Preferably, X ¹ of the structural unit [A] represented by the general formula [1], X ² of the structural unit [B] represented by the general formula [3], and a structure represented by the general formula [4] It is a ring-opening metathesis polymer hydrogenated product in which at least one of X ³ of the unit [C] is —O— and the other is —CH ₂ —. The molar amount of —O— units with respect to the total total unit molar amount of X ¹ , X ² and X ³ is 0.01 to 0.99, preferably 0.02 to 0.95, more preferably 0. 0.05 to 0.80, and most preferably 0.10 to 0.70.

  In the present invention, the structural unit [A] represented by the general formula [1], the structural unit [B] represented by the general formula [3] and / or the structural unit [C] represented by the general formula [4]. The molar ratio [A] / ([B] and [C]) is 0/100 to 99/1, preferably 20/80 to 99/1. It is essential that at least a certain amount of the structural unit [B] and / or [C] is present. Here, the structural unit [A] includes a cyclic alkyl tertiary ester group represented by the general formula [2], that is, a group that decomposes with an acid generated from a photosensitizer during exposure to generate a carboxylic acid. After exposure, it is necessary for developing with an alkaline aqueous solution to form a resist pattern. Further, the structural units [B] and / or [C] are necessary for developing adhesion to a substrate to be processed such as a silicon substrate. When the molar ratio [A] / ([B] and [C]) is less than 20/80, development may be insufficient. Moreover, when it exceeds 99/1, adhesiveness with a to-be-processed substrate will not express. More preferably, the molar ratio [A] / ([B] and [C]) is 20/80 to 95/5, particularly preferably 25/75 to 90/10, and most preferably 30/70 to 85. / 15. The fact that these structural units are within this range 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 ring-opening metathesis polymer hydrogenated product can form a uniform smooth coating film by increasing the solubility or dissolution rate in a polar solvent when preparing a resist composition.

  In the hydrogenated ring-opening metathesis polymer of the present invention, at least one of the structural unit [B] or [C] is essential, and the structural unit is composed of the structural units [B] and [C] in addition to the structural unit [A]. The terpolymer may be a terpolymer that is composed of only one of the structural units [B] or [C].

  The present invention relates to a hydrogenated ring-opening metathesis polymer having a ratio (Mw / Mn) of weight average molecular weight Mw to number average molecular weight Mn of more than 2.0 and less than 5.0, and a resist film on a silicon wafer substrate. The coating solution having a uniform film thickness can be formed without changing the film formation conditions by reducing the dependency of the resist coating film on the thickness unevenness when the film is applied by spin coating. In addition, this makes it possible to widen the range of operating conditions such as solution concentration and spin coating conditions for forming a uniform and smooth coating film. On the other hand, when the molecular weight distribution is 2.0 or less, when the coating film becomes thick at a high solution concentration, uneven thickness is likely to be formed, resulting in non-uniform film, and uneven resist resolution between thick and thin films. May occur. Furthermore, if the molecular weight distribution exceeds 5.0, a difference occurs in the dissolution rate in the developer during alkali development, so that uneven development occurs and resolution performance may be degraded. By making the molecular weight distribution within the range of the present invention, it becomes possible to form a uniform and smooth resist coating film regardless of the solution concentration, and good coating under wide film forming operating conditions while maintaining resolution performance. A film can be formed.

    As for the molecular weight of the ring-opening metathesis polymer hydrogenated product of the present invention, the weight average molecular weight Mw is usually 500 to 1,000,000. Preferably, it is 1,000-100,000, Especially preferably, it is 3,000-50,000. In addition, the number average molecular weight and weight average molecular weight described in this specification were measured by gel permeation chromatography (GPC) in terms of polystyrene.

  These ring-opening metathesis polymer hydrogenated products may be composed of one type of structural unit for each of the structural units [A], [B] and / or [C]. Alternatively, all may be composed of two or more structural units. For example, the structural unit [A] is represented by the following general formulas [A-1] and [A-2].

（式中、Ｒ⁴⁸〜Ｒ⁵¹のうち少なくとも一つが、一般式［２］で表される環状アルキルの三級エステル基を有する官能基であり、その他はそれぞれ独立に、水素原子、炭素数１〜２０の直鎖状、分岐状または環状のアルキル基、ハロゲン、炭素数１〜２０の直鎖状、分岐状または環状のハロゲン化アルキル基、炭素数１〜２０の直鎖状、分岐状または環状のアルコキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシアルキル基、炭素数２〜２０の直鎖状、分岐状または環状のアルキルカルボニルオキシ基、炭素数６〜２０のアリールカルボニルオキシ基、炭素数１〜２０の直鎖状、分岐状または環状のアルキルスルホニルオキシ基、炭素数６〜２０のアリールスルホニルオキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシカルボニル基、または炭素数３〜２０の直鎖状、分岐状または環状のアルコキシカルボニルアルキル基から選ばれ、ｊ¹は０または１〜３の整数を表す。）

(In the formula, at least one of R ^{48 to} R ⁵¹ is a functional group having a tertiary ester group of cyclic alkyl represented by the general formula [2], and the others are each independently a hydrogen atom, carbon number 1 -20 linear, branched or cyclic alkyl group, halogen, 1-20 carbon linear, branched or cyclic alkyl halide, 1-20 carbon linear, branched or A cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkylcarbonyloxy group having 2 to 20 carbon atoms, a carbon number 6 to 20 Arylcarbonyloxy group, linear, branched or cyclic alkylsulfonyloxy group having 1 to 20 carbon atoms, arylsulfonyloxy group having 6 to 20 carbon atoms, linear chain, branched or cyclic having 2 to 20 carbon atoms of (It is selected from an alkoxycarbonyl group or a linear, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and j ¹ represents 0 or an integer of 1 to 3).

（式中、Ｒ⁵²〜Ｒ⁵⁵のうち少なくとも一つが、一般式［２］で表される環状アルキルの三級エステル基を有する官能基であり、その他はそれぞれ独立に、水素原子、炭素数１〜２０の直鎖状、分岐状または環状のアルキル基、ハロゲン、炭素数１〜２０の直鎖状、分岐状または環状のハロゲン化アルキル基、炭素数１〜２０の直鎖状、分岐状または環状のアルコキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシアルキル基、炭素数２〜２０の直鎖状、分岐状または環状のアルキルカルボニルオキシ基、炭素数６〜２０のアリールカルボニルオキシ基、炭素数１〜２０の直鎖状、分岐状または環状のアルキルスルホニルオキシ基、炭素数６〜２０のアリールスルホニルオキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシカルボニル基、または炭素数３〜２０の直鎖状、分岐状または環状のアルコキシカルボニルアルキル基から選ばれ、ｊ²は０または１〜３の整数を表す。）と、構造単位［Ｂ］が下記一般式［Ｂ−１］および［Ｂ−２］で表される

(In the formula, at least one of R ^{52 to} R ⁵⁵ is a functional group having a tertiary ester group of a cyclic alkyl represented by the general formula [2], and the others are independently a hydrogen atom, a carbon number of 1 -20 linear, branched or cyclic alkyl group, halogen, 1-20 carbon linear, branched or cyclic alkyl halide, 1-20 carbon linear, branched or A cyclic alkoxy group, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkylcarbonyloxy group having 2 to 20 carbon atoms, a carbon number 6 to 20 Arylcarbonyloxy group, linear, branched or cyclic alkylsulfonyloxy group having 1 to 20 carbon atoms, arylsulfonyloxy group having 6 to 20 carbon atoms, linear chain, branched or cyclic having 2 to 20 carbon atoms of Selected from an alkoxycarbonyl group or a linear, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, j ² represents an integer of 0 or 1 to 3) and the structural unit [B] is Represented by the following general formulas [B-1] and [B-2]

（式中、Ｒ⁵⁶〜Ｒ⁵⁹は、それぞれ独立に、水素原子または炭素数１〜１０の直鎖状、分岐状または環状のアルキル基であり、ｍ¹は０または１〜３の整数を表す。）

Wherein R ^{56 to} R ⁵⁹ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and m ¹ represents an integer of 0 or 1 to 3. .)

（式中、Ｒ⁶⁰〜Ｒ⁶³は、それぞれ独立に、水素原子または炭素数１〜１０の直鎖状、分岐状または環状のアルキル基であり、ｍ²は０または１〜３の整数を表す。）
および／または構造単位［Ｃ］が下記一般式［Ｃ−１］および［Ｃ−２］で表される

Wherein R ^{60 to} R ⁶³ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and m ² represents an integer of 0 or 1 to 3. .)
And / or the structural unit [C] is represented by the following general formulas [C-1] and [C-2].

（式中、Ｒ⁶⁴〜Ｒ⁶⁷は、それぞれ独立に、水素原子または炭素数１〜１０の直鎖状、分岐状または環状のアルキル基であり、Ｙ³およびＹ⁴は一方が−（Ｃ＝Ｏ）−であり他方は−ＣＨ₂−であり、ｎ¹は０または１〜３の整数を表す。）

(Wherein R ^{64 to} R ⁶⁷ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and one of Y ³ and Y ⁴ is — (C═ O) —, the other is —CH ₂ —, and n ¹ represents 0 or an integer of ^{1 to} _3. )

（式中、Ｒ⁶⁸〜Ｒ⁷¹は、それぞれ独立に、水素原子または炭素数１〜１０の直鎖状、分岐状または環状のアルキル基であり、Ｙ⁵およびＹ⁶は一方が−（Ｃ＝Ｏ）−であり他方は−ＣＨ₂−であり、ｎ²は０または１〜３の整数を表す。）から成る開環メタセシス重合体水素添加物である。
本発明の開環メタセシス共重合体水素添加物は、構造単位［Ａ］と［Ｂ］および／または［Ｃ］に加えて、一般式［５］で表される構造単位［Ｄ］を更に構造単位として有していることが、基板密着性および現像液への親和性が更に向上するために好ましい。

(Wherein R ^{68 to} R ⁷¹ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and one of Y ⁵ and Y ⁶ is — (C═ O) - and is the other is -CH ₂ -, n ² is a hydrogenated ring-opening metathesis polymer comprising a representative) 0 or an integer of 1 to 3..
The hydrogenated ring-opening metathesis copolymer of the present invention further comprises a structural unit [D] represented by the general formula [5] in addition to the structural units [A] and [B] and / or [C]. It is preferable to have it as a unit in order to further improve the adhesion to the substrate and the affinity for the developer.

本発明の一般式［５］において、Ｒ¹⁹〜Ｒ²²のうち少なくとも一つは、一般式［６］

In the general formula [5] of the present invention, at least one of R ^{19 to} R ²² is represented by the general formula [6].

（式中、鎖線は結合手を示す。Ｒ²³は水素原子、炭素数１〜１０の直鎖状、分岐状または環状のアルキル基、炭素数２〜１０の直鎖状、分岐状または環状のアルコキシアルキル基、または炭素数１〜１０の直鎖状、分岐状または環状のアシル基を示す。Ｗ²は単結合または炭素数１〜１０のｑ＋２価の炭化水素基を示す。ｑは０または１である。）で表されるカルボン酸基を有する官能基である。Ｒ²³において、炭素数１〜１０の直鎖状、分岐状または環状のアルキル基としては、例えばメチル、エチル、プロピル、イソプロピル、ｎ−ブチル、イソブチル、ｔｅｒｔ−ブチル、シクロペンチル、シクロヘキシル、１−エチルシクロペンチル、および１−エチルシクロヘキシル等が挙げられ、炭素数２〜１０の直鎖状、分岐状または環状のアルコキシアルキル基としては、例えばメトキシメチル、１−エトキシエチル、１−ｔｅｒｔ−ブトキシエチル、１−シクロヘキシルオキシエチル、１−エトキシプロピル、１−エトキシ−１−メチルエチル、テトラヒドロフラン−２−イル、およびテトラヒドロピラン−２−イル等が挙げられ、炭素数１〜１０の直鎖状、分岐状または環状のアシル基としては、例えばフォルミル、アセチル、ピバロイル、およびシクロヘキシルカルボニル等が挙げられる。これらＲ²³のうち、炭素数１〜６の直鎖状または分岐状のアルキル基、炭素数２〜７の直鎖状、分岐状または環状のアルコキシアルキル基、および炭素数２〜７の直鎖状または分岐状のアシル基が好ましく、特に水素原子、メチル、エチル、メトキシメチル、１−エトキシエチル、テトラヒドロフラン−２−イルおよびアセチルが好ましい。

(In the formula, a chain line represents a bond. R ²³ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, W ² represents a single bond or a q + 2 valent hydrocarbon group having 1 to 10 carbon atoms, and q is 0 or 1 is a functional group having a carboxylic acid group. In R ²³ , examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl and 1-ethyl. Examples thereof include cyclopentyl and 1-ethylcyclohexyl, and examples of the linear, branched or cyclic alkoxyalkyl group having 2 to 10 carbon atoms include methoxymethyl, 1-ethoxyethyl, 1-tert-butoxyethyl, 1 -Cyclohexyloxyethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl and the like. Examples of the cyclic acyl group include formyl, acetyl, and piva. Yl, and cyclohexylcarbonyl, and the like. Among these R ^23, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 7 carbon atoms, and a linear chain having 2 to 7 carbon atoms A branched or branched acyl group is preferable, and a hydrogen atom, methyl, ethyl, methoxymethyl, 1-ethoxyethyl, tetrahydrofuran-2-yl and acetyl are particularly preferable.

In W ² , the q + 1 divalent hydrocarbon group having 1 to 10 carbon atoms is a linear, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms when q is 0, for example, Methylene, dimethylmethylene, ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2,2 -Dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, tetramethylene, pentamethylene, 1,1-cyclopentylene, 1,2 -Cyclopentylene, 1,3-cyclopentylene, 1,1-cyclohexylene, 1,2-cyclohexylene, 1,3 Cyclohexylene, and 1,4-cyclohexylene. Of these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene, and 2-methyltrimethylene are preferred. When q is 1, for example, a bond formed by removing one hydrogen atom at an arbitrary position on the hydrocarbon group mentioned in the case where q is 0 is mentioned. Most preferred W ² is a single bond.

The other of R ^{19 to} R ²² are each independently a hydrogen atom, a linear or branched chain such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl having 1 to 20 carbon atoms. Or cyclic alkyl group, halogen such as chlorine atom, bromine atom, iodine atom or fluorine atom, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloro having 1 to 20 carbon atoms Linear, branched or cyclic halogenated alkyl groups such as methyl or tribromomethyl, linear or branched such as methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy or mentoxy having 1 to 12 carbon atoms Or a cyclic alkoxy group, methoxymethyl having 2 to 20 carbon atoms, Linear, branched or cyclic alkoxyalkyl groups containing alkoxysaccharides such as methoxyethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymenthol, or methylglucose, and straight chain such as acetoxy having 2 to 20 carbon atoms. Linear, branched or cyclic alkylsulfonyloxy groups such as chain, branched or cyclic alkylcarbonyloxy groups, arylcarbonyloxy groups such as naphthoyloxy having 6 to 20 carbon atoms, and mesyloxy having 1 to 20 carbon atoms Group, arylsulfonyloxy group such as tosyloxy having 6 to 20 carbon atoms, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, or cyclohexyl having 2 to 20 carbon atoms Linear, branched or cyclic alkoxycarbonyl groups such as xycarbonyl, methoxycarbonylmethyl having 3 to 20 carbon atoms, 2- (methoxycarbonyl) ethyl, 1- (methoxycarbonyl) ethyl, ethoxycarbonylmethyl, 2- ( Specific examples include linear, branched, or cyclic alkoxycarbonylalkyl groups such as ethoxycarbonyl) ethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, tert-butoxycarbonylmethyl, or cyclohexyloxycarbonylmethyl. Take an example. Among these, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, and a straight chain having 2 to 20 carbon atoms. A linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, and a linear, branched or cyclic alkoxycarbonylalkyl having 3 to 20 carbon atoms Group, more preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxycarbonyl group having 2 to 10 carbon atoms, and 3 to 10 carbon atoms. A linear or branched alkoxycarbonylalkyl group.

X ⁴ is —O— or —CR ²⁴ ₂ — (R ²⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and when p is 1 to 3, X ⁴ May be the same or different. Specific examples of R ²⁴ include a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl. X ⁴ is preferably —O— or —CH ₂ —, and more preferably all X ⁴ are either —O— or —CH ₂ —. p is preferably 0 or 1.

  That is, specific examples of the general formula [5] include chemical formulas [5-1] to [5-64].

等で表される構造単位［Ｄ］が挙げられる。

The structural unit [D] represented by etc. is mentioned.

  In a preferred embodiment of the present invention, the structural unit [A] represented by the general formula [1], the structural unit [B] represented by the general formula [3], and the structural unit represented by the general formula [4] [ The molar ratio ([A] + [B] + [C]) / [D] of the structural unit [D] represented by the general formula [5] to C] is 100/0 to 20/80, and the structural unit It is preferable that a certain amount of the structural unit [D] is present in addition to [A], [B] and [C]. Here, the structural unit [D] extremely enhances the adhesion with a substrate to be processed such as a silicon substrate, and further improves the affinity with the developer. The molar ratio ([A] + [B] + [C]) / [D] is preferably 98/2 to 50/50, more preferably 97/3 to 60/40, most preferably 95/5 to 5. 70/30.

  The hydrogenated ring-opening metathesis copolymer of the present invention has a structure represented by the general formula [7] in addition to the structural units [A] and [B] and / or [C], preferably [D]. Unit [E] may be further included as a structural unit.

一般式［７］において、Ｒ²⁵〜Ｒ²⁸のうち少なくとも一つは、一般式［８］

In the general formula [7], at least one of R ^{25 to} R ²⁸ is represented by the general formula [8].

（式中、鎖線は結合手を示す。Ｒ²⁹は水素原子、炭素数１〜１０の直鎖状、分岐状または環状のアルキル基、炭素数２〜１０の直鎖状、分岐状または環状のアルコキシアルキル基、または炭素数１〜１０の直鎖状、分岐状または環状のアシル基を示す。Ｒ³⁰は炭素数１〜１０の直鎖状または分岐状のアルキル基、炭素数２〜１０の直鎖状、分岐状または環状のアルコキシアルキル基、または炭素数１〜２０の直鎖状、分岐状または環状のハロゲン化アルキル基を示す。Ｗ³は単結合または炭素数１〜１０のｓ＋２価の炭化水素基を示す。ｓは０または１である。）で表されるカルボン酸エステル基を有する官能基である。

(In the formula, a chain line represents a bond. R ²⁹ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkoxyalkyl group, or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, R ³⁰ is a linear or branched alkyl group having 1 to 10 carbon atoms, or a carbon number having 2 to 10 carbon atoms; A linear, branched or cyclic alkoxyalkyl group, or a linear, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms, W ³ is a single bond or s + 2 valence having 1 to 10 carbon atoms. And s is 0 or 1.) is a functional group having a carboxylic acid ester group.

In R ²⁹ , examples of the linear, branched or cyclic alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, cyclopentyl, cyclohexyl and 1-ethyl. Examples thereof include cyclopentyl and 1-ethylcyclohexyl, and examples of the linear, branched or cyclic alkoxyalkyl group having 2 to 10 carbon atoms include methoxymethyl, 1-ethoxyethyl, 1-tert-butoxyethyl, 1 -Cyclohexyloxyethyl, 1-ethoxypropyl, 1-ethoxy-1-methylethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl and the like. Examples of the cyclic acyl group include formyl, acetyl, and piva. Yl, and cyclohexylcarbonyl, and the like. Among these R ^29, a linear or branched alkyl group having 1 to 6 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 7 carbon atoms, and a linear chain having 2 to 7 carbon atoms Or a branched acyl group is preferable, and a hydrogen atom, methyl, ethyl, methoxymethyl, 1-ethoxyethyl, tetrahydrofuran-2-yl and acetyl are particularly preferable.

In R ³⁰ , examples of the linear or branched alkyl group having 1 to 10 carbon atoms include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, tert-butyl, and the like. -10 linear, branched or cyclic alkoxyalkyl groups include, for example, methoxymethyl, 1-ethoxyethyl, 1-tert-butoxyethyl, 1-cyclohexyloxyethyl, 1-ethoxypropyl, 1-ethoxy-1 -Methylethyl, tetrahydrofuran-2-yl, tetrahydropyran-2-yl and the like. Examples of the linear, branched or cyclic halogenated alkyl group having 1 to 20 carbon atoms include, for example, fluoromethyl, chloromethyl , Bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, triflu Romechiru, trichloromethyl and tribromomethyl and the like. Of these R ^30, a linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and tert-butyl are particularly preferable.

In W ³ , the s + 2 valent hydrocarbon group having 1 to 10 carbon atoms is a linear, branched or cyclic divalent hydrocarbon group having 1 to 10 carbon atoms when s is 0. Methylene, dimethylmethylene, ethylidene, propylidene, butylidene, ethylene, 1-methylethylene, 2-methylethylene, 1-ethylethylene, 2-ethylethylene, 1,1-dimethylethylene, 1,2-dimethylethylene, 2,2 -Dimethylethylene, 1-ethyl-2-methylethylene, trimethylene, 1-methyltrimethylene, 2-methyltrimethylene, 3-methyltrimethylene, tetramethylene, pentamethylene, 1,1-cyclopentylene, 1,2 -Cyclopentylene, 1,3-cyclopentylene, 1,1-cyclohexylene, 1,2-cyclohexylene, 1,3 Cyclohexylene, and 1,4-cyclohexylene. Of these, methylene, ethylidene, ethylene, 1-methylethylene, 2-methylethylene, trimethylene, and 2-methyltrimethylene are preferred. When s is 1, for example, a bond formed by removing one hydrogen atom at an arbitrary position on the hydrocarbon group mentioned in the case where s is 0 is mentioned. Most preferred W ³ is a single bond.

The other of R ^{25 to} R ²⁸ are each independently a hydrogen atom, a linear or branched chain such as methyl, ethyl, propyl, isopropyl, n-butyl, tert-butyl, cyclohexyl or menthyl having 1 to 20 carbon atoms. Or cyclic alkyl group, halogen such as chlorine atom, bromine atom, iodine atom or fluorine atom, fluoromethyl, chloromethyl, bromomethyl, difluoromethyl, dichloromethyl, dibromomethyl, trifluoromethyl, trichloro having 1 to 20 carbon atoms Linear, branched or cyclic halogenated alkyl groups such as methyl or tribromomethyl, linear or branched such as methoxy, ethoxy, isopropoxy, n-butoxy, tert-butoxy or mentoxy having 1 to 12 carbon atoms Or cyclic alkoxy group, methoxymethyl having 2 to 20 carbon atoms, Linear, branched or cyclic alkoxyalkyl groups containing alkoxysaccharides such as methoxyethyl, tert-butoxymethyl, tert-butoxyethyl or methoxymenthol, or methylglucose, and straight chain such as acetoxy having 2 to 20 carbon atoms. Linear, branched or cyclic alkylsulfonyloxy groups such as chain, branched or cyclic alkylcarbonyloxy groups, arylcarbonyloxy groups such as naphthoyloxy having 6 to 20 carbon atoms, and mesyloxy having 1 to 20 carbon atoms Group, arylsulfonyloxy group such as tosyloxy having 6 to 20 carbon atoms, methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, isopropoxycarbonyl, n-butoxycarbonyl, tert-butoxycarbonyl, or cyclohexyl having 2 to 20 carbon atoms Linear, branched or cyclic alkoxycarbonyl groups such as xycarbonyl, methoxycarbonylmethyl having 3 to 20 carbon atoms, 2- (methoxycarbonyl) ethyl, 1- (methoxycarbonyl) ethyl, ethoxycarbonylmethyl, 2- ( Specific examples include linear, branched, or cyclic alkoxycarbonylalkyl groups such as ethoxycarbonyl) ethyl, n-propoxycarbonylmethyl, isopropoxycarbonylmethyl, n-butoxycarbonylmethyl, tert-butoxycarbonylmethyl, or cyclohexyloxycarbonylmethyl. Take an example. Among these, a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, and a straight chain having 2 to 20 carbon atoms. A linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, and a linear, branched or cyclic alkoxycarbonylalkyl having 3 to 20 carbon atoms Group, more preferably a hydrogen atom, a linear or branched alkyl group having 1 to 10 carbon atoms, a linear or branched alkoxycarbonyl group having 2 to 10 carbon atoms, and 3 to 10 carbon atoms. A linear or branched alkoxycarbonylalkyl group.

X ⁵ is —O— or —CR ³¹ ₂ — (R ³¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and when r is 1 to 3, X ⁵ May be the same or different. Specific examples of R ³¹ include a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms such as methyl, ethyl, n-propyl, isopropyl, n-butyl, or tert-butyl. X ⁵ is preferably —O— or —CH ₂ —, and more preferably all X ⁵ are either —O— or —CH ₂ —. r is preferably 0 or 1.

  That is, specific examples of the general formula [7] include chemical formulas [7-1] to [7-64].

等で表される構造単位［Ｅ］が挙げられる。

The structural unit [E] represented by etc. is mentioned.

  In addition to the structural units [A] and [B] and / or [C], preferably [D], and in some cases [E], the ring-opening metathesis copolymer hydrogenated product of the present invention contains Formula [15]

（式中、Ｒ⁷²〜Ｒ⁷⁵は、それぞれ独立に、水素原子、炭素数１〜２０の直鎖状、分岐状または環状のアルキル基、ハロゲン、炭素数１〜２０の直鎖状、分岐状または環状のハロゲン化アルキル基、炭素数１〜２０の直鎖状、分岐状または環状のアルコキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルコキシアルキル基、ヒドロキシ基、炭素数１〜２０の直鎖状、分岐状または環状のヒドロキシアルキル基、シアノ基、炭素数２〜２０の直鎖状、分岐状または環状のシアノアルキル基、炭素数２〜２０の直鎖状、分岐状または環状のアルキルカルボニルオキシ基、炭素数３〜２０の直鎖状、分岐状または環状のアルキルカルボニルオキシアルキル基、炭素数６〜２０のアリールカルボニルオキシ基、炭素数１〜２０の直鎖状、分岐状または環状のアルキルスルホニルオキシ基、炭素数２〜２０の直鎖状、分岐状または環状のアルキルスルホニルオキシアルキル基、または炭素数６〜２０のアリールスルホニルオキシ基から選ばれ、Ｘ⁶は−Ｏ−または−ＣＲ⁷⁶ ₂−（Ｒ⁷⁶は水素原子または炭素数１〜１０の直鎖状または分岐状のアルキル基を表す）であり、同一でも異なってもよい。ｔは０または１〜３の整数を表す。）で表される構造単位［Ｆ］を更に構造単位として有してもよい。

(In the formula, R ^{72 to} R ⁷⁵ are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, halogen, a linear or branched chain having 1 to 20 carbon atoms. Or a cyclic halogenated alkyl group, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, a hydroxy group, a carbon number 1-20 linear, branched or cyclic hydroxyalkyl group, cyano group, C2-C20 linear, branched or cyclic cyanoalkyl group, C2-C20 linear, branched Or cyclic alkylcarbonyloxy group, straight chain having 3 to 20 carbon atoms, branched or cyclic alkylcarbonyloxyalkyl group, arylcarbonyloxy group having 6 to 20 carbon atoms, straight chain having 1 to 20 carbon atoms , Branched Or a cyclic alkylsulfonyloxy group, a linear, branched or cyclic alkylsulfonyloxyalkyl group having 2 to 20 carbon atoms, or an arylsulfonyloxy group having 6 to 20 carbon atoms, and X ⁶ is —O—. Or —CR ⁷⁶ ₂ — (R ⁷⁶ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and may be the same or different, and t is an integer of 0 or 1 to 3 The structural unit [F] represented by the formula (1) may be further included as a structural unit.

  The hydrogenated ring-opening metathesis copolymer of the present invention has a structural unit [A] represented by the general formula [1], a structural unit [B] represented by the general formula [3] and / or the general formula [4]. ], A structural unit [E] represented by the general formula [7] as necessary, and a structural unit [F] represented by the general formula [15] as necessary. It is obtained by polymerizing a cyclic olefin monomer corresponding to each of the above with a ring-opening metathesis catalyst and hydrogenating under a hydrogenation catalyst.

  The cyclic olefin monomer corresponding to the structural unit [A] represented by the general formula [1] is a cyclic olefin monomer having the structure of the general formula [9] and represented by the general formula [3]. The cyclic olefin monomer corresponding to the structural unit [B] is a cyclic olefin monomer having the structure of the general formula [10] and corresponds to the structural unit [C] represented by the general formula [4]. And the cyclic olefin monomer corresponding to the structural unit [E] represented by the general formula [7] is a cyclic olefin monomer having the structure of the general formula [11]. And general formula [12]

（式中R²⁵〜R²⁸、X^５、およびｒは一般式［７］中の定義と同じ）
の構造を有する環状オレフィン単量体であり、一般式［１５］で表される構造単位［Ｆ］に対応する環状オレフィン単量体とは、下記一般式［１６］

(Wherein R ^{25 to} R ²⁸ , X ⁵ , and r are the same as defined in general formula [7])
And the cyclic olefin monomer corresponding to the structural unit [F] represented by the general formula [15] is the following general formula [16]

（式中Ｒ⁷²〜Ｒ⁷⁵、Ｘ⁶およびｔは前記一般式［１５］と同じ。）の構造を有する環状オレフィン単量体である。

(Wherein R ^{72 to} R ⁷⁵ , X ⁶ and t are the same as those in the general formula [15]).

In these formulas, specific examples of R ^{48 to} R ⁷⁵ are the substituents already described as the corresponding substituents, and include the same substituents including preferred ranges.

That is, the hydrogenated ring-opening metathesis copolymer of the present invention includes at least a cyclic olefin monomer represented by the general formula [9], a cyclic olefin monomer represented by the general formula [10], and / or The cyclic olefin monomer represented by the general formula [11], and if necessary, the cyclic olefin monomer represented by the general formula [12], and if necessary, the cyclic olefin monomer represented by the general formula [16] X ¹ of an olefin monomer, and having the general formula [9], these cyclic olefin monomers at least one of which is -O- of X ³ of X ^2, and of general formula [10] [11] The product is obtained by polymerizing with a ring-opening metathesis catalyst and hydrogenating under a hydrogenation catalyst. Preferably, the cyclic olefin monomer represented by the general formula [9], the cyclic olefin monomer represented by the general formula [10], and the cyclic olefin monomer represented by the general formula [11] The charge molar ratio is 0/100 to 99/1, preferably 20/80 to 99/1, more preferably 20/80 to 95/5, particularly preferably 25/75 to 90/10, and most preferably 30. / 70 to 85/15. When the cyclic olefin monomer represented by the general formula [12] is used, it is usually used in an amount of 50 mol% or less, preferably 30 mol% or less, based on the total molar amount of the olefin monomer used. Preferably it is 20 mol% or less. When the cyclic olefin monomer represented by the general formula [16] is used, it is usually used in an amount of 50 mol% or less, preferably 30 mol% or less, based on the total molar amount of the olefin monomer used. More preferably, it is 20 mol% or less.

Further, X ¹ of the cyclic olefin monomer represented by the general formula [9], X ² of the cyclic olefin monomer represented by the general formula [10], and a cyclic olefin represented by the general formula [11] It is preferable that at least one of the monomers X ³ is —O— and the other is —CH ₂ —, and the moles of —O— units with respect to the total total unit molar amount of X ¹ , X ² and X ^3. The amount is from 0.01 to 0.99, preferably from 0.02 to 0.95, more preferably from 0.05 to 0.80, most preferably from 0.10 to 0.70. . Even when the cyclic olefin monomer represented by the general formula [12] and / or the general formula [16] is used, the amount of X ¹ , X ² , X ³ , X ⁵ and X ⁶ with respect to the total unit molar amount is − The molar amount of O-unit is 0.01 to 0.99, preferably 0.02 to 0.95, more preferably 0.05 to 0.80, most preferably 0.10 to 0.10. 0.70.

  Further, the hydrogenated ring-opening metathesis copolymer of the present invention is a chain transfer agent such as olefin or diene, more preferably using the above cyclic olefin monomer as a ring-opening metathesis catalyst, preferably a living ring-opening metathesis catalyst. In the presence of, it is obtained by polymerizing in a solvent or without solvent and then hydrogenating in a solvent using a hydrogenation catalyst under hydrogen pressure.

As the polymerization catalyst used in the present invention, it may be mentioned any catalyst for ring-opening metathesis polymerization, specific examples of the living ring-opening metathesis catalyst, W (N-2,6-Pr i 2 ^{_{C 6 H 3) (CHBu t}} ) (OBu t) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe 2 CF 3) 2, W (N-2,6 _{^{-Pr i 2 C 6 H 3)}} (CHBu t) (OCMe (CF 3) 2) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OBu t) 2, ^{W (N-2,6-Pr i} 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, W (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) _{(OCMe (CF 3) 2)} 2, (Pr i is iso- propyl group in the formula, Bu ^t is tert- butyl group, Me represents a methyl group, Ph refers to a Fe A tungsten-based alkylidene catalyst such as W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCMePh) (OBu ^t ) ₂ (PMe ₃ ), W (N-2,6-Me). _{2 C 6 H 3) (CHCHCMe} 2) (OBu t) 2 (PMe 3), W (N-2,6-Me 2 C 6 H 3) (CHCHCPh 2) (OBu t) 2 (PMe 3), W _{(N-2,6-Me 2 C} 6 H 3) (CHCHCMePh) (OCMe 2 (CF 3)) 2 (PMe 3), W (N-2,6-Me 2 C 6 H 3) (CHCHCMe 2) (OCMe ₂ (CF ₃ )) ₂ (PMe ₃ ), W (N-2,6-Me ₂ C ₆ H ₃ ) (CHCHCPh ₂ ) (OCMe ₂ (CF ₃ )) ₂ (PMe ₃ ), W (N _{-2,6-Me 2 C 6 H 3} ) (CHCHCMe 2) (OCMe (CF 3) 2) 2 (PMe 3), W _{N-2,6-Me 2 C 6} H 3) (CHCHCPh 2) (OCMe (CF 3) 2) 2 (PMe 3), W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh) _{(OCMe 2 (CF 3))} 2 (PMe 3), W (N-2,6-Pr i 2 C 6 H 3) (CHCHCMePh) (OCMe (CF 3) 2) 2 (PMe 3), W (N _{^{-2,6-Pr i 2 C 6 H}} 3) (CHCHCMePh) (OPh) 2 (PMe 3), (Pr i is iso- propyl group in the formula, Bu ^t is tert - butyl group, Me represents a methyl group, Ph represents a phenyl group. ) Tungsten-based, such as alkylidene catalyst, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H 3) _{^{(CHBu t) (OCMe 2 CF}} 3) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHBu t) (OCMe (CF 3) 2) 2, Mo (N-2,6- _{^{Pr i 2 C 6 H 3)}} (CHCMe 2 Ph) (OBu t) 2, Mo (N-2,6-Pr i 2 C 6 H 3) (CHCMe 2 Ph) (OCMe 2 CF 3) 2, Mo ( _{^{N-2,6-Pr i 2 C}} 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2, (Pr i is iso- propyl group in the formula, Bu ^t is tert - butyl group, Me represents a methyl group, Ph refers to a phenyl group.) molybdenum-based alkylidene catalyst such ^{as, Re (CBu t) (CHBu} t) (O-2 _{^{6-Pr i 2 C 6 H}} 3) 2, Re (CBu t) (CHBu t) (O-2-Bu t C 6 H 4) 2, Re (CBu t) (CHBu t) (OCMe 2 CF 3) ^{_{2, Re (CBu t) (}} CHBu t) (OCMe (CF 3) 2) 2, Re (CBu t) (CHBu t) (O-2,6-Me 2 C 6 H 3) 2, in (formula Bu ^t is tert -. represents a butyl group) rhenium-based alkylidene catalyst such as, Ta [C (Me) C (Me) CHCMe 3] (O-2,6-Pr i 2 C 6 H 3) 3 Py, Ta [C (Ph) C (Ph ) CHCMe 3] (O-2,6-Pr i 2 C 6 H 3) 3 Py, (Me in the formula is methyl, Ph is phenyl, Py represents a pyridine group ) Tantalum alkylidene catalyst, Ru (CHCHCPh ₂ ) (PPh ₃ ) ₂ Cl ₂ , Ru (CHCHCPh ₂ ) Examples thereof include ruthenium-based alkylidene catalysts and titanacyclobutane catalysts such as (P (C ₆ H ₁₁ ) ₃ ) ₂ Cl ₂ (Ph represents a phenyl group).

  In addition to the above, a living ring-opening metathesis catalyst system based on a combination of an organic transition metal complex and a Lewis acid as a cocatalyst, for example, a transition metal halogen complex such as molybdenum or tungsten, and an organoaluminum compound or organotin as a cocatalyst A ring-opening metathesis catalyst comprising a compound or an organometallic compound such as lithium, sodium, magnesium, zinc, cadmium and boron can also be used. A ring-opening metathesis catalyst comprising a combination of a known transition metal halide and a similar Lewis acid as a cocatalyst can also be used.

Specific examples of the organic transition metal halogen complex, W (N-2,6-Pr i 2 C 6 H 3) (thf) (OBu t) 2 Cl 2, W (N-2,6- Pr i 2 C _{6 H 3) (thf) (} OCMe 2 CF 3) 2 Cl 2, W (N-2,6-Pr i 2 C 6 H 3) (thf) (OCMe (CF 3) 2) 2 Cl 2, W ( _{N-2,6-Me 2 C 6} H 3) (thf) (OBu t) 2 Cl 2, W (N-2,6-Me 2 C 6 H 3) (thf) (OCMe 2 CF 3) 2 Cl _{2, W (N-2,6-} Me 2 C 6 H 3) (thf) (OCMe (CF 3) 2) 2 Cl 2, (Pr i is iso- propyl group in the formula, Bu ^t is tert- butyl Group, Me is a methyl group, Ph is a phenyl group, and thf is tetrahydrofuran)) or a combination of the following organometallic compounds Ranaru catalyst or ^{Mo (N-2,6-Pr i} 2 C 6 H 3) (thf) (OBu t) 2 Cl 2, Mo (N-2,6-Pr i 2 C 6 H 3) (thf, _{) (OCMe 2 CF 3) 2} Cl 2, Mo (N-2,6-Pr i 2 C 6 H 3) (thf) (OCMe (CF 3) 2) 2 Cl 2, Mo (N-2,6- _{Me 2 C 6 H 3) (} thf) (OBu t) 2 Cl 2, Mo (N-2,6-Me 2 C 6 H 3) (thf) (OCMe 2 CF 3) 2 Cl 2, Mo (N- _{2,6-Me 2 C 6 H 3} ) (thf) (OCMe (CF 3) 2) 2 Cl 2, (Pr i is iso- propyl group in the formula, Bu ^t is tert- butyl group, Me represents a methyl group , Ph represents a phenyl group, thf represents a tetrahydrofuran.) molybdenum-based halogen complex such _{or,, WCl 6, WOCl 4,} ReCl 5, T Cl _4, RuCl _3, the catalyst can be mentioned a combination of IrCl ₃ or the like and the following organometallic compounds.

  Specific examples of the organometallic compound as a promoter include trimethylaluminum, triethylaluminum, triisobutylaluminum, trihexylaluminum, trioctylaluminum, triphenylaluminum, tribenzylaluminum, diethylaluminum monochloride, di-n- Organoaluminum compounds such as butylaluminum, diethylaluminum monobromide, diethylaluminum monoiodide, diethylaluminum monohydride, ethylaluminum sesquichloride, ethylaluminum dichloride, tetramethyltin, diethyldimethyltin, tetraethyltin, dibutyldiethyltin, tetrabutyltin , Tetraoctyl tin, trioctyl tin fluoride, trioctyl tin chloride, trioctyl tin bromide, Lioctyltin iodide, dibutyltin difluoride, dibutyltin dichloride, dibutyltin dibromide, dibutyltin diiodide, butyltin trifluoride, butyltin trichloride, butyltin tribromide, organotin compounds such as butyltin triiodide, organolithium such as n-butyllithium Compounds, organic sodium compounds such as n-pentyl sodium, methylmagnesium iodide, ethylmagnesium bromide, methylmagnesium bromide, n-propylmagnesium bromide, t-butylmagnesium chloride, allylmagnesium chloride and other organomagnesium compounds, diethyl zinc and the like Organic zinc compounds, organic cadmium compounds such as diethyl cadmium, organic boron compounds such as trimethylboron, triethylboron, tri-n-butylboron Etc. The.

  In the living ring-opening metathesis polymerization of the present invention, the molar ratio of the cyclic olefin monomer and the ring-opening metathesis catalyst is a transition metal alkylidene catalyst such as tungsten, molybdenum, rhenium, tantalum, or ruthenium or a titanacyclobutane catalyst. The cyclic olefin monomer is 2 to 50000 in molar ratio with respect to the transition metal alkylidene complex, and preferably 10 to 10000. In the case of a ring-opening metathesis catalyst composed of an organic transition metal halogen complex and an organic metal compound, the cyclic olefin monomer is 2 to 50000, preferably 10 to 10,000 in terms of molar ratio to the organic transition metal halogen complex. The organometallic compound as a co-catalyst is in a range of 0.1 to 100, preferably 1 to 50 in molar ratio to the organic transition metal halogen complex.

  In the present invention, when polymerizing using a ring-opening metathesis catalyst, it is preferable to polymerize in the presence of a chain transfer agent such as olefin or diene in order to increase the catalyst efficiency. These chain transfer agents are used for controlling the molecular weight in order to obtain a polymer having a desired molecular weight. Examples of the olefin used as the chain transfer agent include α-olefins such as ethylene, propylene, butene, pentene, hexene, octene, and vinyltrimethylsilane, allyltrimethylsilane, allyltriethylsilane, allyltriisopropylsilane. Examples of the diene include non-conjugated dienes such as 1,4-pentadiene, 1,5-hexadiene, and 1,6-heptadiene. Furthermore, these olefins or dienes may be used alone or in combination of two or more.

The amount of the olefin or diene used in the present invention is in the range of 0.001 to 1000 times mol, preferably 0.01 to 100 times mol of the olefin or diene with respect to the cyclic olefin monomer. The olefin or diene is in the range of 0.1 to 1000 equivalents, preferably 1 to 500 equivalents, relative to 1 equivalent of the alkylidene of the transition metal alkylidene complex. The desired molecular weight can be set by arbitrarily setting these ratios.
In order to produce the hydrogenated ring-opening metathesis polymer in the range of the molecular weight distribution in which the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn in the present invention is greater than 2.0 and less than 5.0 The molecular weight distribution needs to be widened at the polymerization stage, and in particular, it cannot be produced by a usual method using a complex catalyst of a living polymerization catalyst system. In addition, even if batch polymerization is carried out in the presence of the above chain transfer agent in one kind of living polymerization catalyst, it is a polymer having a molecular weight distribution within the probability distribution range of the chain transfer reaction, and only a polymer having a relatively narrow distribution. Was only obtained.

In the present invention, (1) a cyclic olefin monomer is polymerized in at least two stages, a polymer component having a high molecular weight and a polymer component having a low molecular weight are polymerized with a ring-opening metathesis polymerization catalyst, and then under a hydrogenation catalyst. Hydrogenation of a ring-opening metathesis polymer with a broad molecular weight distribution is produced by hydrogenation. Or (2) polymerizing a polymer component having a high molecular weight and a polymer component having a low molecular weight in the presence of at least two kinds of polymerization catalysts in the presence of a cyclic olefin monomer, and then hydrogenating under a hydrogenation catalyst Thus, a hydrogenated ring-opening metathesis polymer having a wide molecular weight distribution can be produced.
In the present invention, the ratio of the weight average molecular weight (HMw) of the polymer component having a high molecular weight to the weight average molecular weight (LMw) of the polymer component having a low molecular weight is HMw / LMw ≧ 2. The ratio of the polymer component having a high molecular weight and a low molecular weight to the weight average molecular weight is at least 10 to 90% by mass, preferably 20 to 80% by mass.

The method of polymerizing the cyclic olefin monomer (1) in at least two stages is a method in which the chain transfer agent is divided into at least two stages and sequentially introduced into the polymerization reaction system, and the living polymerization catalyst is at least 2 stages. A method of charging the polymerization reaction system in stages or more, a method of charging the cyclic olefin monomer in at least two stages, a method of changing the polymerization temperature in at least two stages, or these This is done by combining the methods. The molecular weight produced by these methods depends on the reactivity of the living polymerization catalyst, the cyclic olefin monomer, and the chain transfer agent, and the quantitative ratio of the cyclic olefin monomer to the polymerization catalyst or the chain transfer. The molecular weight of the polymer is determined by the ratio between the amount of the agent and the amount of the cyclic olefin monomer and the chain transfer agent. The size of the weight average molecular weight of the polymer obtained by polymerization and the ratio of each polymer can be determined. When the cyclic olefin monomer is polymerized in two or more stages, the polymerization ratio in each stage is 10 to 90% by mass, preferably 20 to 80% by mass in at least one stage.

The method of polymerizing the cyclic olefin monomer (2) in the presence of at least two kinds of polymerization catalysts is a molecular weight generated by polymerization reactivity of the polymerization catalyst with respect to the cyclic olefin monomer or chain transferability with respect to the chain transfer agent. This is a method in which a catalyst for obtaining a polymer component having a high molecular weight is combined with a catalyst for obtaining a polymer having a low molecular weight. The combination of these polymerization catalysts includes a weight average molecular weight (HMw) of a polymer component obtained by a catalyst capable of polymerizing a high molecular weight polymer and a weight average molecular weight of a polymer component obtained from a catalyst capable of polymerizing a low molecular weight polymer ( The ratio of (LMw) is selected from the polymerization catalysts in which HMw / LMw ≧ 2. These polymerization reactivity and chain transfer properties, that is, controllability of the polymerization reaction rate and molecular weight depend on the insertion property of the cyclic olefin monomer into the polymerization catalyst and the stability after the insertion. Therefore, it depends on the kind of transition metal of the polymerization catalyst and the kind of various ligands giving or pulling electrons to metal atoms. For example, it is recognized that even when the catalysts have the same ligand species, the polymerization reactivity and the chain transfer properties differ as a result of the difference in the electron density of the outermost contour of the catalyst itself when the types of metals are different. By utilizing these properties, a combination of at least two types of catalysts in the living polymerization catalyst can be selected, so that a polymer having a high molecular weight and a polymer having a low molecular weight can be produced under the same polymerization conditions. For each polymerization catalyst selected, the molecular weight of the polymer is determined by the amount ratio of the cyclic olefin monomer or the chain transfer agent, and the amount ratio of the cyclic olefin monomer and the chain transfer agent. The ratio of the polymer component can be arbitrarily generated by changing the amount of each polymerization catalyst. The polymerization ratio in each catalyst selected is appropriately determined so that at least one of them is 10 to 90% by mass, preferably 20 to 80% by mass.

  In addition, the ring-opening metathesis polymerization of the present invention may be solventless or may use a solvent. Particularly, as a solvent to be used, ethers such as tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane or dioxane, benzene, toluene, Aromatic hydrocarbons such as xylene or ethylbenzene, aliphatic hydrocarbons such as pentane, hexane or heptane, aliphatic cyclic hydrocarbons such as cyclopentane, cyclohexane, methylcyclohexane, dimethylcyclohexane or decalin, or methylene dichloride, dichloroethane, dichloroethylene, Examples thereof include halogenated hydrocarbons such as tetrachloroethane, chlorobenzene, and trichlorobenzene, and two or more of these may be used in combination.

  The concentration of ring-opening metathesis polymerization in the present invention varies depending on the reactivity of the cyclic olefin monomer and the solubility in the polymerization solvent, etc., but the concentration of the cyclic olefin monomer relative to the solvent is usually the same. It is 0.001-500 mol / L, Preferably it is 0.01-100 mol / L, More preferably, it is the range of 0.05-50 mol / L. Although the reaction temperature also varies depending on the type and amount of the cyclic olefin monomer and ring-opening metathesis catalyst used, it is usually a reaction temperature of -30 to 150 ° C, preferably 0 to 120 ° C, more preferably 15 to 100. It is a temperature of ° C. The reaction time is usually 1 minute to 10 hours, preferably 5 minutes to 8 hours, and more preferably 10 minutes to 6 hours.

  After the polymerization reaction, the reaction is stopped with a deactivator such as aldehydes such as butyraldehyde, ketones such as acetone, alcohols such as methanol, etc., and a ring-opening metathesis polymer solution can be obtained.

  In the present invention, since the polymer obtained by living ring-opening metathesis polymerization is a living polymerization reaction, a polymer having a desired molecular weight is obtained by controlling the molar ratio of the monomer and the catalyst. be able to. In addition, by performing living ring-opening metathesis polymerization in the presence of olefin or diene as a chain transfer agent, while maintaining the living polymerization reaction, it is also possible to control the molar ratio of the monomer, the chain transfer agent, and the catalyst. A molecular weight polymer can be obtained. As for the molecular weight obtained by this living polymerization, the weight average molecular weight Mw in terms of polystyrene is 500 to 1,000,000. Preferably, it is 1,000-100,000, Especially preferably, it is 3,000-50,000.

  As described above, by polymerizing the cyclic olefin monomer of the present invention with a ring-opening metathesis catalyst, a ring-opening metathesis polymer having an olefinically unsaturated bond in the main chain portion having a wide molecular weight distribution can be obtained. In the present invention, in order to lower the ultraviolet (UV) maximum absorption wavelength region, in particular to maximize the UV transmittance in this region with respect to the ArF excimer laser region having a wavelength of 193 nm, the main feature of the ring-opening metathesis polymer is as follows. It is necessary to hydrogenate the olefin in the chain portion. A known hydrogenation catalyst can be used for this hydrogenation reaction. As a result, a resist material having a ring-opening metathesis polymer hydrogenated product having a wide molecular weight distribution has a wide range of conditions for obtaining a uniform film, and has a film-forming property that improves film-forming properties on a silicon wafer substrate as a resist film. it can.

  Specific examples of hydrogenation catalysts include heterogeneous catalysts in which supported metals such as palladium, platinum, nickel, rhodium, and ruthenium are supported on a carrier such as carbon, silica, alumina, titania, magnesia, diatomaceous earth, and synthetic zeolite. For catalysts or homogeneous catalysts, nickel naphthenate / triethylaluminum, nickel acetylacetonate / triisobutylaluminum, cobalt octenoate / n-butyllithium, titanocene dichloride / diethylaluminum chloride, rhodium acetate, dichlorobis (triphenylphosphine) palladium Chlorotris (triphenylphosphine) rhodium, dihydridotetrakis (triphenylphosphine) ruthenium, and the following general formula [17] in the presence of hydrogen as a homogeneous catalyst. It may be hydrogenated using an organic metal complex and a hydrogenation catalyst consisting of amine compounds represented.

（式中、Ｍはルテニウム、ロジウム、オスミウム、イリジウム、パラジウム、白金またはニッケルを表し、Ｈは水素原子を表し、Ｑはハロゲン原子を表し、ＴはＣＯ、ＮＯ、トルエン、アセトニトリルまたはテトラヒドロフランを表し、ＵはＰＲ'¹Ｒ'²Ｒ'³（Ｐはリンを示し、Ｒ'¹、Ｒ'²、Ｒ'³はそれぞれ同一または異なる直鎖、分岐または環状のアルキル、アルケニル、アリール、アルコキシまたはアリロキシを示す。）で表せる有機リン化合物を表し、ｗは０または１の整数、ｘは１〜３の整数、ｙは０または１の整数、ｚは２〜４の整数を表す。）
一般式［１７］におけるＱは、ハロゲン原子を表し具体例として、塩素、フッ素、臭素または沃素原子を例示できる。更に、ＴはＣＯ、ＮＯ、トルエン、アセトニトリルまたはテトラヒドロフランを表し、Ｕは有機リン化合物を表し具体例として、トリメチルホスフィン、トリエチルホスフィン、トリイソプロピルホスフィン、トリｎ−プロピルホスフィン、トリｔ−ブチルホスフィン、トリイソブチルホスフィン、トリｎ−ブチルホスフィン、トリシクロヘキシルホスフィン、トリフェニルホスフィン、メチルジフェニルホスフィン、ジメチルフェニルホスフィン、トリｏ−トリルホスフィン、トリｍ−トリルホスフィン、トリｐ−トリルホスフィン、ジエチルフェニルホスフィン、ジクロロ（エチル）ホスフィン、ジクロロ（フェニル）ホスフィン、クロロジフェニルホスフィン、トリメチルホスフィト、トリイソプロピルホスフィト、トリフェニルホスフィトを例示できる。

(Wherein M represents ruthenium, rhodium, osmium, iridium, palladium, platinum or nickel, H represents a hydrogen atom, Q represents a halogen atom, T represents CO, NO, toluene, acetonitrile or tetrahydrofuran; U represents PR ′ ¹ R ′ ² R ′ ³ (P represents phosphorus, and R ′ ¹ , R ′ ² and R ′ ³ are the same or different linear, branched or cyclic alkyl, alkenyl, aryl, alkoxy or allyloxy, respectively. And w is an integer of 0 or 1, x is an integer of 1 to 3, y is an integer of 0 or 1, and z is an integer of 2 to 4.)
Q in the general formula [17] represents a halogen atom, and specific examples thereof include a chlorine, fluorine, bromine or iodine atom. Further, T represents CO, NO, toluene, acetonitrile or tetrahydrofuran, U represents an organic phosphorus compound, and specific examples thereof include trimethylphosphine, triethylphosphine, triisopropylphosphine, tri-n-propylphosphine, tri-t-butylphosphine, tri Isobutylphosphine, tri-n-butylphosphine, tricyclohexylphosphine, triphenylphosphine, methyldiphenylphosphine, dimethylphenylphosphine, trio-tolylphosphine, trim-tolylphosphine, tri-p-tolylphosphine, diethylphenylphosphine, dichloro (ethyl ) Phosphine, dichloro (phenyl) phosphine, chlorodiphenylphosphine, trimethylphosphite, triisopropylphosphite, triphenylphosphine It can be exemplified I bet.

  Specific examples of the organometallic complex represented by the general formula [17] include dichlorobis (triphenylphosphine) nickel, dichlorobis (triphenylphosphine) palladium, dichlorobis (triphenylphosphine) platinum, chlorotris (triphenylphosphine) rhodium, dichlorotris. (Triphenylphosphine) osmium, dichlorohydridobis (triphenylphosphine) iridium, dichlorotris (triphenylphosphine) ruthenium, dichlorotetrakis (triphenylphosphine) ruthenium, trichloronitrosylbis (triphenylphosphine) ruthenium, dichlorobis (acetonitrile) bis (Triphenylphosphine) ruthenium, dichlorobis (tetrahydrofuran) bis (triphenylphosphine) rutenium , Chlorohydrido (toluene) tris (triphenylphosphine) ruthenium, chlorohydridocarbonyltris (triphenylphosphine) ruthenium, chlorohydridocarbonyltris (diethylphenylphosphine) ruthenium, chlorohydridonitrosyltris (triphenylphosphine) ruthenium, dichlorotris ( Trimethylphosphine) ruthenium, dichlorotris (triethylphosphine) ruthenium, dichlorotris (tricyclohexylphosphine) ruthenium, dichlorotris (triphenylphosphine) ruthenium, dichlorotris (trimethyldiphenylphosphine) ruthenium, dichlorotris (tridimethylphenylphosphine) ruthenium, Dichlorotris (tri-o-tolylphosphine) ruthenium, Chlorotris (dichloroethyl) ruthenium, dichloro-tris (dichlorophenyl phosphine) ruthenium, dichloro-tris (trimethyl phosphite) ruthenium, dichloro-tris (triphenyl phosphite) ruthenium and the like.

  Specific examples of amine compounds include primary amine compounds such as methylamine, ethylamine, aniline, ethylenediamine, and 1,3-diaminocyclobutane, secondary amine compounds such as dimethylamine, methylisopropylamine, and N-methylaniline, and trimethylamine. , Tertiary amine compounds such as triethylamine, triphenylamine, N, N-dimethylaniline, pyridine, γ-picoline, etc., preferably tertiary amine compounds are used, especially when triethylamine is used. The improvement of the addition rate is remarkable.

  Two or more of these organometallic complexes or amine compounds can be used in combination at any ratio.

  When a known hydrogenation catalyst for hydrogenating the ring-opening metathesis polymer in the present invention is used, the amount of the ring-opening metathesis polymer and the hydrogenation catalyst used is such that the known hydrogenation catalyst is used relative to the ring-opening metathesis polymer. 5 to 50000 ppm, preferably 100 to 1000 ppm. Moreover, when using the hydrogenation catalyst which consists of an organometallic complex and an amine compound, an organometallic complex is 5-50000 ppm with respect to a ring-opening metathesis polymer, Preferably it is 10-10000 ppm, Most preferably, it is 50-1000 ppm. is there. Moreover, an amine compound is 0.1 equivalent-1000 equivalent with respect to the organometallic complex to be used, Preferably it is 0.5 equivalent-500 equivalent, Most preferably, it is 1-100 equivalent.

  A hydrogenation catalyst comprising an organometallic complex and an amine compound can be used in advance by subjecting an organometallic complex and an amine compound to contact treatment. It may be added to the reaction system.

  The solvent used in the hydrogenation reaction of the ring-opening metathesis polymer may be any solvent as long as it is usually used in the hydrogenation reaction, dissolves the ring-opening metathesis polymer and its hydrogenated product, A solvent in which the solvent itself is not hydrogenated is preferable. For example, ethers such as tetrahydrofuran, diethyl ether, dibutyl ether or dimethoxyethane, aromatic hydrocarbons such as benzene, toluene, xylene or ethylbenzene, aliphatic hydrocarbons such as pentane, hexane or heptane, cyclopentane, cyclohexane, methylcyclohexane , Aliphatic cyclic hydrocarbons such as dimethylcyclohexane or decalin, or halogenated hydrocarbons such as methylene dichloride, dichloroethane, dichloroethylene, tetrachloroethane, chlorobenzene or trichlorobenzene, and the like. May be.

  The concentration of the hydrogenation reaction of the ring-opening metathesis polymer in the present invention varies depending on the kind of the ring-opening metathesis polymer, the hydrogenation catalyst, and the solvent and is not uniform, but the concentration of the ring-opening metathesis polymer relative to the solvent is usually It is 0.01g-10kg / L, Preferably it is 0.1g-5kg / L, More preferably, it is the range of 0.5g-1kg / L.

  The hydrogenation reaction of the ring-opening metathesis polymer is carried out at a hydrogen pressure of usually from normal pressure to 30 MPa, preferably from 0.5 to 20 MPa, particularly preferably from 2 to 15 MPa, and the reaction temperature is usually from 0 to 300. The temperature is preferably from room temperature to 250 ° C, particularly preferably from 50 to 200 ° C. The reaction time is usually 1 minute to 50 hours, preferably 10 minutes to 20 hours, and more preferably 30 minutes to 10 hours.

  The hydrogenation of the ring-opening metathesis polymer in the present invention can be produced by isolating the ring-opening metathesis polymer from the ring-opening metathesis polymer solution and then dissolving it again in the solvent. A method of performing a hydrogenation reaction by adding a hydrogenation catalyst comprising the organometallic complex and an amine compound can also be employed.

  After completion of the ring-opening metathesis polymerization or hydrogenation reaction, the ring-opening metathesis catalyst or hydrogenation catalyst remaining in the polymer can be removed by a known method. For example, filtration, adsorption using an adsorbent, addition of an organic acid such as lactic acid, a poor solvent, and water to a solution using a good solvent, and extraction and removal of the system at room temperature or under heating. Examples include a method in which a solvent solution or polymer slurry is contact-treated with a basic compound and an acidic compound and then washed and removed.

  The method for recovering the polymer hydride from the ring-opening metathesis polymer hydrogenated solution is not particularly limited, and a known method can be used. For example, the reaction solution is discharged into a poor solvent under stirring to solidify the polymer hydride, and recovered by filtration, centrifugation, decantation, etc., and steam is blown into the reaction solution to remove the polymer hydride. Examples thereof include a steam stripping method for precipitation and a method for directly removing the solvent from the reaction solution by heating.

  When the hydrogenation method in the present invention is used, the hydrogenation rate can be easily achieved as 90% or more, and can be 95% or more, particularly 99% or more, and the cyclic olefin ring-opening metathesis weight thus obtained can be obtained. The combined hydrogenated product is not easily oxidized and becomes an excellent ring-opening metathesis polymer hydrogenated product.

By the above method, the structural unit [A] represented by the general formula [1] is optionally contained, and the structural unit [B] represented by the general formula [3] and / or the general formula [4] is represented. Consists of at least a structural unit [C] and, if necessary, a structural unit [E] represented by the general formula [7] and, if necessary, a structural unit [F] represented by the general formula [15] And X ¹ of the structural unit [A] represented by the general formula [1], X ² of the structural unit [B] represented by the general formula [3], and the general formula [4]. At least one of X ^{3 in} the structural unit [C] is —O—, and the molar ratio [A] / ([B] and [C]) is 0/100 to 99/1, preferably 20/80. -99/1, and the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is larger than 2.0. It is possible to manufacture smaller hydrogenated ring-opening metathesis polymer.

In the present invention, in the hydrogenated ring-opening metathesis polymer obtained as described above, at least one of the tertiary ester group of the cyclic alkyl in the general formula [2] and / or the ester group in the general formula [8] is used. The structural unit [A] represented by the general formula [1] and the structural unit [B] represented by the general formula [3] and / or the general formula [4] are obtained by decomposing a part into a carboxylic acid. A structural unit [C] represented by the general formula [5], a structural unit [E] represented by the general formula [7] as necessary, and further as necessary. X ¹ of the structural unit [A] represented by the general formula [1] including the structural unit [F] represented by the general formula [15], and the structural unit [B represented by the general formula [3]. little of X ^2, and X ³ in the general formula [4] represented by the structural unit [C] of] 1 is -O-, the constituent molar ratio [A] / ([B] and [C]) is 20/80 to 99/1, and the ratio of the weight average molecular weight Mw to the number average molecular weight Mn A ring-opening metathesis polymer hydrogenated product having (Mw / Mn) larger than 2.0 and smaller than 5.0 can be produced.

  As a method of decomposing at least a part of the cyclic alkyl tertiary ester group in the general formula [2] and / or the ester group in the general formula [8] into a carboxylic acid, a method by hydrolysis and / or An acid decomposition method can be used. The hydrolysis method includes acid hydrolysis in the presence of an acid catalyst such as sulfuric acid, hydrochloric acid, nitric acid, toluenesulfonic acid, trifluoroacetic acid or acetic acid, sodium hydroxide, hydroxylation. Either alkaline hydrolysis performed in the presence of an alkaline catalyst such as potassium or barium hydroxide, or neutral hydrolysis using sodium acetate, lithium iodide or the like instead of acid or alkali can be used. In the hydrolysis method, it is essential that water is present in the system, and the amount of water to be used is equal to or more than an equimolar amount of the ester group to be converted into carboxylic acid, preferably 5 mol times or more, and more preferably. Is 10 mole times or more, most preferably 20 mole times or more. As a method by acid decomposition, an acid such as sulfuric acid, hydrochloric acid, nitric acid, toluenesulfonic acid, trifluoroacetic acid or acetic acid can be used. In the acid decomposition method, water may be present in the system, but it is not essential. The amount of the acid catalyst, alkaline catalyst, neutral hydrolysis catalyst used in the hydrolysis method, and acid used in the acid decomposition method is usually 50 moles per mole of ester group to be converted to carboxylic acid. It is below, Preferably it is the range of 0.00001-30 mol, More preferably, it is the range of 0.001-10 mol.

  The hydrolysis reaction and the acid decomposition reaction in the method of the present invention may use an organic solvent even in an aqueous solvent, but as the organic solvent to be used in particular, alcohols such as methanol and ethanol, ketones such as acetone, tetrahydrofuran, Ethers such as diethyl ether, dibutyl ether, dimethoxyethane and dioxane, aromatic hydrocarbons such as benzene, toluene, xylene and ethylbenzene, aliphatic hydrocarbons such as pentane, hexane, heptane and cyclohexane, carboxylic acids such as acetic acid, nitromethane Nitro compounds such as pyridine, pyridines such as pyridine and lutidine, formamides such as dimethylformamide and the like, and may be mixed with water or alcohols, or may be used only in an organic solvent. Further, two or more of these may be used in combination. The reaction temperature is usually from 0 to 300 ° C, preferably from room temperature to 250 ° C, more preferably from room temperature to 200 ° C. The reaction time is usually 1 minute to 100 hours, preferably 5 minutes to 30 hours, more preferably 10 minutes to 20 hours.

  The embodiment of the hydrolysis reaction and the acid decomposition reaction in the method of the present invention is not particularly limited, and any form may be used as long as the hydrolysis reaction and the acid decomposition reaction can be carried out effectively, such as nitrogen. The present invention may be any of an embodiment under an inert gas, air, or reduced pressure, normal pressure, increased pressure, batch, semi-batch, or continuous.

  Moreover, you may neutralize with an alkali or an acid suitably after a hydrolysis reaction or an acid decomposition reaction. After the hydrolysis reaction or acid decomposition reaction, a method for recovering the polymer from the ring-opening metathesis polymer hydrogenated solution or slurry is not particularly limited, and a known method can be used. For example, in the case of a solution, the reaction solution is discharged into a poor solvent under stirring to precipitate a polymer hydride to form a slurry, which is recovered by filtration, centrifugation, decantation, etc., and steam is blown into the reaction solution. In the case of a slurry, there are a method of directly recovering by a filtration method, a centrifugal separation method, a decantation method, etc. Can be mentioned.

By the above method, the structural unit [A] represented by the general formula [1] is optionally contained, and the structural unit [B] represented by the general formula [3] and / or the general formula [4] is represented. The structural unit [C], the structural unit [D] represented by the general formula [5], the structural unit [E] represented by the general formula [7] as necessary, and the general formula [15 as necessary. X ¹ of the structural unit [A] represented by the general formula [1] and X ^{2 of the} structural unit [B] represented by the general formula [3]. And at least one of X ³ of the structural unit [C] represented by the general formula [4] is —O—, and the constituent molar ratio [A] / ([B] and [C]) is 0 / 100 to 99/1, preferably 20/80 to 99/1, and the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is 2. Larger 5.0 less than the hydrogenated ring-opening metathesis polymer can be obtained.

Furthermore, in the present invention, the structural unit represented by the general formula [1] is obtained by converting the carboxylic acid functional group of the hydrogenated ring-opening metathesis polymer having a carboxylic acid functional group obtained as described above into an ester. Optionally containing [A], a structural unit [B] represented by the general formula [3] and / or a structural unit [C] represented by the general formula [4], and if necessary, a general formula [5] A structural unit [D] represented by the general formula [7] as needed, and a structural unit [F] represented by the general formula [15] as needed. And X ¹ of the structural unit [A] represented by the general formula [1], X ² of the structural unit [B] represented by the general formula [3], and a structure represented by the general formula [4]. at least one of X ³ of the unit [C] is -O-, and its constituent molar ratio [a] / ([B] and [C ) Is 0/100 to 99/1, preferably 20/80 to 99/1, and the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is more than 2.0 and more than 5.0 Small ring-opening metathesis polymer hydrogenates can be produced.

  As a method for converting a carboxylic acid functional group into an ester, a usual method can be applied. For example, esterification by dehydration condensation reaction with alcohols, esterification by ortho-alkylating agents, esterification by addition of olefins in the presence of acids, and halides using organic basic compounds. Esterification by a condensation reaction or alkoxyalkyl esterification by addition of an alkyl vinyl ether. Examples of the method include esterification by converting a carboxylic acid to an acid halide using thionyl chloride or the like, and then contacting with an alcohol, and a method of esterifying by contacting a metal salt of a carboxylic acid with a halide.

  As alcohols used in esterification by dehydration condensation reaction with alcohols, any alcohol usually used for esterification can be used, for example, methanol, ethanol, 1-propanol, 2-propanol, 1-butanol, 2-butanol, tert-butanol, 1-pentanol, tert-amyl alcohol, 3-methyl-3-pentanol, 3-ethyl-3-pentanol, cyclopentanol, cyclopentanemethanol, 1- Methylcyclopentanol, 1-ethylcyclopentanol, cyclohexanol, cyclohexylmethanol, dicyclohexylmethanol, tricyclohexylmethanol, 1-methylcyclohexanol, norborneol, 1-adamantanol, 2-adap Pentanol, aliphatic alcohols such as 2-methyl-2-adamantanol, and 1-adamantane methanol is preferred. The amount of these alcohols used is usually 100 mol or less, preferably in the range of 1 to 50 mol, more preferably in the range of 2 to 30 mol, with respect to 1 mol of the carboxylic acid to be converted into the ester. Esterification by dehydration condensation reaction with alcohols is usually performed in the presence of an acid. Examples of such an acid include hydrogen halides such as hydrogen chloride gas, sulfuric acid, phosphoric acid, hydrochloric acid, or Mineral acids such as hydrobromic acid, solid acids such as heteropoly acid or Nafion, p-toluenesulfonic acid, trifluoroacetic acid, propionic acid, malonic acid, oxalic acid, chlorosulfonic acid / pyridine salt, trifluoroacetic acid / pyridine salt Organic acids such as sulfuric acid / pyridine salt or p-toluenesulfonic acid / pyridine salt, or Lewis acid such as boron fluoride etherate. The amount of these acids used is usually 10 mol or less, preferably in the range of 0.00001 to 2 mol, more preferably 0.001 to 0.5 mol, relative to 1 mol of the carboxylic acid to be converted into the ester. Range. Alternatively, a method using an acidic ion exchange resin, for example, a method of refluxing a solvent using a Soxhlet extractor containing a desiccant such as anhydrous magnesium sulfate or molecular sieve, a method of coexisting a dehydrating agent such as DCC, and a large excess A method such as a method using alcohol can also be used.

  As the alkylating agent used in esterification with an ortho-alkylating agent, any alkylating agent usually used for esterification of carboxylic acid can be used, for example, diazoalkanes such as diazomethane, or triethyl orthoformate, for example. Or tricarboxy orthocarboxylate such as trimethyl orthoacetate is preferable. The amount of these alkylating agents used is usually 50 mol or less, preferably in the range of 1 to 30 mol, more preferably in the range of 2 to 20 mol, with respect to 1 mol of the carboxylic acid to be converted into the ester. .

  As olefins used in esterification by addition of olefins in the presence of an acid, any olefins usually used for esterification can be used, for example, 2-methylpropene, 2-methyl-1- Butene, 2-ethyl-1-butene, 2-methyl-2-butene, 3-methyl-2-pentene, 1-methyl-1-cyclopentene, 1-methyl-1-cyclohexene, methylenecyclopentane, methylenecyclohexane and ethylidene Aliphatic alkenes such as cyclohexane are preferred. The amount of these olefins to be used is usually 100 mol or less, preferably in the range of 1 to 50 mol, more preferably in the range of 2 to 30 mol, with respect to 1 mol of the carboxylic acid to be converted into the ester. Esterification by addition of olefins is performed in the presence of an acid. Examples of such an acid include hydrogen halides such as hydrogen chloride gas, mineral acids such as sulfuric acid, phosphoric acid, hydrochloric acid, and hydrobromic acid. , Solid acid such as heteropolyacid or Nafion, p-toluenesulfonic acid, trifluoroacetic acid, propionic acid, malonic acid, oxalic acid, chlorosulfonic acid / pyridine salt, trifluoroacetic acid / pyridine salt, sulfuric acid / pyridine salt or p- Examples thereof include organic acids such as toluenesulfonic acid and pyridine salt, and Lewis acids such as boron fluoride etherate. The amount of these acids used is usually 10 mol or less, preferably in the range of 0.00001 to 2 mol, more preferably 0.001 to 0.5 mol, relative to 1 mol of the carboxylic acid to be converted into the ester. Range.

  Examples of alkyl vinyl ethers used in alkoxyalkyl esterification by addition of alkyl vinyl ethers include methyl vinyl ether, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n -Butyl vinyl ether, sec-butyl vinyl ether, tert-butyl vinyl ether, isooctyl vinyl ether, decyl vinyl ether, dodecyl vinyl ether, cyclohexyl vinyl ether, 2-ethylhexyl vinyl ether, tert- Pentyl vinyl ether, octadecyl vinyl ether, cesyl vinyl ether, 2-methoxyethyl vinyl ether, vinyl-2- (2-ethoxyethoxy) ethyl ether, ethylene glycol butyl vinyl ether, tert Preferred are amyl vinyl ethers or alkoxy-substituted, unsubstituted or cyclic alkyl vinyl ethers such as 2,3-dihydrofuran, 3,4-dihydro-2H-pyran, and 1,4-dioxene. Furthermore, among these, ethyl vinyl ether, n-propyl vinyl ether, isopropyl vinyl ether, n-butyl vinyl ether, 2,3-dihydrofuran, and 3,4-dihydro-2H-pyran are more preferable. The amount of these alkyl vinyl ethers to be used is usually 50 mol or less, preferably in the range of 1 to 30 mol, more preferably in the range of 2 to 20 mol, relative to 1 mol of the carboxylic acid to be converted into an ester. It is a range.

  Alkoxyalkyl esterification by addition of alkyl vinyl ethers is usually carried out in the presence of an acid. Examples of such an acid include hydrogen halides such as hydrogen chloride gas, sulfuric acid, phosphoric acid, hydrochloric acid, Or a mineral acid such as hydrobromic acid, a solid acid such as heteropoly acid or Nafion, or p-toluenesulfonic acid, trifluoroacetic acid, propionic acid, malonic acid, oxalic acid, chlorosulfonic acid / pyridine salt, trifluoroacetic acid / Organic acids such as pyridine salt, sulfuric acid / pyridine salt or p-toluenesulfonic acid / pyridine salt are exemplified, among which hydrogen chloride gas, hydrochloric acid, trifluoroacetic acid, trifluoroacetic acid / pyridine salt, p-toluenesulfonic acid / Pyridine salts or sulfuric acid / pyridine salts are preferably used. These acids can be used singly or in combination of two or more and simultaneously or sequentially. The amount of these acid catalysts to be used is usually 10 mol or less, preferably 0.00001 to 2 mol, more preferably 0.001 to 0.5 mol per mol of carboxylic acid to be converted into an ester. The range of moles.

  In the method of converting a carboxylic acid functional group into an ester in the method of the present invention, a solvent is usually used. These solvents are not uniform depending on the method used, the type of the target ester, etc., and either an aqueous solvent or an organic solvent may be used. Particularly, organic solvents used include alcohols such as methanol and ethanol. , Ketones such as acetone, ethers such as tetrahydrofuran, diethyl ether, dibutyl ether, dimethoxyethane, dioxane, aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, fats such as pentane, hexane, heptane, cyclohexane, decalin Aromatic hydrocarbons, methylene chloride, dichloroethane, tetrachloroethane, halogenated hydrocarbons such as chloroform, chlorobenzene and orthodichlorobenzene, carboxylic acids such as acetic acid, nitro compounds such as nitromethane, pyridines such as pyridine and lutidine, dimethyl It is like formamide such as formamide, be mixed with water or an alcohol may, or may be used only in organic solvents. Further, two or more of these may be used in combination. The reaction temperature is usually from 0 to 200 ° C, preferably from 10 to 150 ° C, more preferably from room temperature to 200 ° C. The reaction time is usually 1 minute to 100 hours, preferably 5 minutes to 30 hours, more preferably 10 minutes to 20 hours.

  The embodiment of the method for converting a carboxylic acid functional group to an ester in the method of the present invention is not particularly limited, and may be any form as long as the method can effectively carry out the conversion of a carboxylic acid functional group to an ester. The embodiment may be any embodiment under an inert gas such as nitrogen, under air, or under reduced pressure, normal pressure, pressurization, batch, semi-batch, or continuous.

  Further, after converting the carboxylic acid functional group to an ester, it may be appropriately neutralized with an alkali or an acid. After converting the carboxylic acid functional group to an ester, the method for recovering the polymer from the ring-opening metathesis polymer hydrogenated solution or slurry is not particularly limited, and a known method can be used. For example, in the case of a solution, the reaction solution is discharged into a poor solvent under stirring to precipitate a polymer hydride to form a slurry, which is recovered by filtration, centrifugation, decantation, etc., and steam is blown into the reaction solution. In the case of a slurry, there are a method of directly recovering by a filtration method, a centrifugal separation method, a decantation method, etc. Can be mentioned.

By the above method, the structural unit [A] represented by the general formula [1] is optionally contained, and the structural unit [B] represented by the general formula [3] and / or the general formula [4] is represented. Structural unit [C], structural unit [D] represented by general formula [5] as necessary, further structural unit [E] represented by general formula [7] as needed, and further as needed X ¹ of the structural unit [A] represented by the general formula [1], including the structural unit [F] represented by the general formula [15], and the structural unit [B represented by the general formula [3] at least one of X ³ of X ^2, and general formula [4] represented by the structural unit [C] of] Although -O-, and its constituent molar ratio [a] / ([B] and [C] ) Is 0/100 to 99/1, preferably 20/80 to 99/1, and the ratio of the weight average molecular weight Mw to the number average molecular weight Mn (Mw / M ) Is large 5.0 less than the hydrogenated ring-opening metathesis polymer than 2.0 is obtained.

  The hydrogenated ring-opening metathesis polymer in the present invention is useful as a base polymer for photoresist. For example, it 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.

  In the present invention, the structural unit [A] represented by the general formula [1], the structural unit [B] represented by the general formula [3] and / or the structural unit [C] represented by the general formula [4]. The molar ratio [A] / ([B] and [C]) of the structural units is 20/80 to 99/1. Here, the structural unit [A] contains a cyclic alkyl tertiary ester group which is a group decomposed by an acid generated from a photosensitizer during exposure, and is developed with an alkaline aqueous solution after exposure to form a resist pattern. The structural units [B] and [C] are necessary for exhibiting adhesion to a substrate to be processed such as a silicon substrate. When the molar ratio [A] / ([B] and [C]) is less than 20/80, development is insufficient, and when it exceeds 99/1, adhesion to the substrate to be processed is not exhibited. In addition, the structural unit [D] represented by the general formula [5] contains a carboxylic acid group, improves adhesion to a substrate to be processed such as a silicon substrate, and improves solubility in a solvent. can do. Furthermore, the molar ratio ([A] + [B] + [C]) / [D] of the structural units [A], [B] and [C] to the structural unit [D] is 100/0 to 20 In the range of / 80, it is preferable for improving the wetting tension at the time of development with an aqueous alkali solution after exposure and solving the development unevenness. The fact that these structural units are within this range 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 ring-opening metathesis polymer hydrogenated product can form a uniform smooth coating film by increasing the solubility or dissolution rate in a polar solvent when preparing a resist composition. Further, when the structural unit [E] is included in addition to the structural units [A] and [B] and / or [C], the structural unit [A] includes an ester group having a different reactivity from the ester group. Therefore, the resolvability during exposure can be freely controlled, which is useful. In this case, the preferred molar ratio of structural units ([A] + [B] + [C]) / [E] is in the range of 100/0 to 40/60.

In particular, X ¹ of the structural unit [A] represented by the general formula [1], X ² of the structural unit [B] represented by the general formula [3], and a structure represented by the general formula [4]. The ring-opening metathesis polymer hydrogenated product in which at least one of X ³ of the unit [C] is —O— and the other is —CH ₂ — is used for adhesion to a substrate to be treated such as a silicon substrate, alkali There is an effect of improving wet tension at the time of development with an aqueous solution and further improving solubility in polar organic solvents such as ketones and alcohols used in the step of applying a resist material to a silicon wafer. In addition, the affinity for water is improved, and the developability for a release agent (or developer) such as an alkaline aqueous solution after exposure is also improved.

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

  In addition, the physical property value of the polymer obtained in the Example was measured with the following method.

  Average molecular weight: Using GPC, the obtained cyclic olefin-based ring-opening metathesis polymer, the polymer hydrogenated product was dissolved in tetrahydrofuran, 830-RI and 875-UV manufactured by JASCO Corporation as a detector, and Shodexk- as a column. The molecular weight was calibrated with polystyrene standards at room temperature at a flow rate of 1.0 ml / min using 805,804,803,802.5.

Hydrogenation rate: Powder of cyclic olefin-based ring-opening metathesis polymer hydrogenated product was dissolved in deuterated chloroform, and 270 MHz- ¹ HNMR, δ = 4.0-6.5 ppm of main chain carbon-carbon The magnitude at which the peak attributed to the double bond decreases due to the hydrogenation reaction was calculated. The film thickness was measured by scanning the entire spin-coated film with DEKTAK III manufactured by Nippon Vacuum Technology Co., Ltd. Further, the amount of carboxylic acid was measured by neutralization titration using bromothymol blue as an indicator.

[Example 1]
3,6-epoxy-1,2,3,6-tetrahydrophthalide (4.33 g, 28.5 mmol) and 8- (1′-ethylcyclopentoxy) as cyclic olefin monomers in a 300 ml Schlenk flask under nitrogen Carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (8.56 g, 28.5 mmol) was dissolved in 100 ml of tetrahydrofuran (hereinafter referred to as THF). This 1,5-hexadiene 0.37ml of (3.2 mmol) was added as a chain transfer agent, stirred, then _{^{Mo (N-2,6-Pr i}} 2 C 6 H 3) ring-opening metathesis polymerization catalyst (CHCMe ₂ Ph) (OCMe (CF ₃ ) ₂ ) ₂ (40 mg, 0.052 mmol) was added and stirred at room temperature for 1 hour. Thereafter, 3,6-epoxy-1,2,3,6-tetrahydrophthalide (4.33 g, 28.5 mmol), 8- (1′-ethylcyclopentoxy) carbonyltetracyclo [4. 4.0.1 ^2,5 . 1 ^7,10] -3-dodecene (8.56 g, 28.5 mmol) and 1,5-hexadiene 0.74 ml (6.4 mmol) of the ring-opening metathesis polymerization catalyst _{^{Mo (N-2,6-Pr i}} 2 C ₆ H ₃ ) (CHCMe ₂ Ph) (OCMe (CF ₃ ) ₂ ) ₂ (40 mg, 0.052 mmol) was simultaneously added to the polymerization solution and stirred at room temperature for another hour. Then, butyraldehyde (38 mg, 0.53 mmol) was added and stirred for 30 minutes.

In a 500 ml autoclave, this ring-opening metathesis polymer solution, chlorohydridocarbonyltris (triphenylphosphine) ruthenium (20 mg, 0.02 mmol) and triethylamine (1 mg, 0.01 mmol) prepared in advance as a hydrogenation catalyst in THF (20 ml) The solution was added and a hydrogenation reaction was performed at 125 ° C. for 8 hours under a hydrogen pressure of 8.1 MPa, and then the temperature was returned to room temperature to release hydrogen gas. The hydrogenated product of the ring-opening metathesis polymer is added to methanol to precipitate the hydrogenated product of the ring-opening metathesis polymer, separated by filtration and vacuum-dried, and then dried in a white powder form. 25.4g was obtained. As for the hydrogenation rate calculated from ¹ H-NMR of the obtained ring-opening metathesis polymer hydrogenated product, no peak attributed to the proton of the main chain olefin was observed, and the hydrogenation rate was 100%. The measured polystyrene standard weight average molecular weight Mw was 25000, and Mw / Mn was 3.68. The composition ratio of the structural units [A] / [B] of the obtained polymer was 50/50.
The ¹ H-NMR spectrum (270 MHz, solvent is deuterated chloroform) of the hydrogenated ring-opening metathesis polymer obtained in Example 1 is shown in FIG.

  The polymer thus obtained was dissolved in cyclohexanone to prepare two types of solutions of 5% by mass and 10% by mass, and a film was formed on a silicon wafer by spin coating. When a 5 mass% solution was applied at 3000 rpm and dried, a uniform 0.25 μm film was obtained. Further, at 10% by mass, a film having a uniform thickness of 0.49 μm was obtained.

[Comparative Example 1]
In Example 1, 3,6-epoxy-1,2,3,6-tetrahydrophthalide (1.08 g, 7.12 mmol) and 8- (1′-ethylcyclopentoxy) carbonyltetracyclo were used as cyclic olefin monomers. [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (2.14 g, 7.12 mmol) was dissolved in 25 ml of THF. 1 at room temperature was added a ^Mo to as ring-opening metathesis polymerization catalyst _{(N-2,6-Pr i 2} C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 (218mg, 0.285mmol) Stir for hours. Then, butyraldehyde (62 mg, 0.86 mmol) was added and stirred for 30 minutes. The obtained polymerization solution was hydrogenated 100% in the same manner as in Example 1 to obtain 3.3 g of a hydrogenated ring-opening metathesis polymer having an Mw of 23200 and Mw / Mn of 1.21 as measured by GPC. When a film was formed by spin coating in the same manner as in Example 1, a 5 mass% solution was applied at 3000 rpm and dried to obtain a uniform 0.28 μm film, but at 10 mass%, a part of 0.55 μm was obtained. A non-uniform film in which interference fringes are observed was obtained. The narrow range is considered to have a narrower range of conditions for obtaining a uniform film than the wide molecular weight distribution.

[Example 2]
20.0 g of the hydrogenated ring-opening metathesis polymer obtained in Example 1 was added to a 1000 ml toluene solution of 5.0 ml of trifluoroacetic acid in a 2000 ml eggplant-shaped flask and stirred at 70 ° C. for 2 hours to remove the solvent. Thereafter, the product was further dissolved in THF, added to methanol, precipitated, filtered, and vacuum dried to obtain 18.2 g of a hydrogenated ring-opening metathesis polymer in which an ester group was partially eliminated in the form of a white powder. The composition ratio of the obtained polymer structural units [A] / [B] / [D] was 35/50/15, Mw measured by GPC was 23000, and Mw / Mn was 3.69.

  The polymer thus obtained was formed in the same manner as in Example 1. When a 5 mass% solution was applied at 3000 rpm and dried, a uniform 0.26 μm film was obtained. A film having a uniform thickness of 0.50 μm was obtained at 10% by mass.

[Comparative Example 2]
Using the hydrogenated ring-opening metathesis polymer obtained in Comparative Example 1, 3.0 g, the ring-opening metathesis polymer hydrogenated, in which the ester group was partially eliminated by the same method as in Example 2, .4 g was obtained. The composition ratio of the obtained polymer structural units [A] / [B] / [D] was 36/50/14, Mw measured by GPC was 21700, and Mw / Mn was 1.30.

  The polymer thus obtained was formed in the same manner as in Example 1. When a 5 mass% solution was applied at 3000 rpm and dried, a uniform 0.24 μm film was obtained. Further, at 10% by mass, a non-uniform film in which interference fringes were observed in a part of 0.47 μm was obtained. The narrow range is considered to have a narrower range of conditions for obtaining a uniform film than the wide molecular weight distribution.

[Example 3]
3,6-epoxy-1,2,3,6-tetrahydrophthalide (8.66 g, 57.0 mmol), 8- (1′-ethylcyclopentoxy) as a cyclic olefin monomer in a 300 ml Schlenk flask under nitrogen Carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (17.12 g, 57.0 mmol) and 0.74 ml (6.4 mmol) of 1,5-hexadiene were dissolved in 200 ml of THF. ^W a _{(N-2,6-Pr i 2} C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 (17mg, 0.02mmol) was added thereto as a ring-opening metathesis polymerization catalyst, at room temperature After stirring for 10 minutes, a solution of 68 mg (0.08 mol) of the same catalyst in THF was further added, and the mixture was further stirred at room temperature for 1 hour. Then, butyraldehyde (26 mg, 0.36 mmol) was added and stirred for 30 minutes.

  Hydrogenation was performed in the same manner as in Example 1 to obtain 25.6 g of a white powdered ring-opening metathesis polymer hydrogenated product having a hydrogenation rate of 100%. The polystyrene standard converted Mw measured by GPC was 10200, and Mw / Mn was 3.20. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 50/50.

  The obtained polymer was formed in the same manner as in Example 1. When a 5% by mass solution was applied at 3000 rpm and dried, a uniform 0.21 μm film was obtained. A film having a uniform thickness of 0.42 μm was obtained at 10% by mass.

[Example 4]
3,6-epoxy-1,2,3,6-tetrahydrophthalide (8.70 g, 57.2 mmol) and 8- (1′-ethylcyclopentoxy) as cyclic olefin monomers in a 300 ml Schlenk flask under nitrogen Carbonyltetracyclo [4.4.0.1 ^2,5 . 1 ^7,10 ] -3-dodecene (17.18 g, 57.2 mmol) and 0.74 ml (6.4 mmol) of 1,5-hexadiene were dissolved in 200 ml of THF. _{^{Mo (N-2,6-Pr i}} 2 C 6 H 3) to a ring-opening metathesis polymerization catalyst _{(CHCMe 2 Ph) (OCMe (} CF 3) 2) 2 (23mg, 0.03mmol) and W (N- _{^{2,6-Pr i 2 C 6 H}} 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 (60mg, was stirred for 1 hour at room temperature was added a THF solution of 0.07 mmol). Then, butyraldehyde (13 mg, 0.18 mmol) was added and stirred for 30 minutes.

  Hydrogenation was performed in the same manner as in Example 1 to obtain 25.6 g of a white powdered ring-opening metathesis polymer hydrogenated product having a hydrogenation rate of 100%. The polystyrene standard converted Mw measured by GPC was 14300, and Mw / Mn was 3.10. Moreover, the composition ratio of the structural unit [A] / [B] of the obtained polymer was 50/50.

  The obtained polymer was formed in the same manner as in Example 1. When a 5% by mass solution was applied at 3000 rpm and dried, a uniform 0.22 μm film was obtained. A film having a uniform thickness of 0.44 μm was obtained at 10% by mass.

[Comparative Example 3]
In Comparative Example 1, using ^Mo as ring-opening metathesis polymerization catalyst _{(N-2,6-Pr i 2} C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 and 400 mg (0.522 mmol) Except that, polymerization was performed in the same manner as in Comparative Example 1, and hydrogenation was performed to obtain 3.2 g of a white powdered ring-opening metathesis polymer hydrogenated product having a hydrogenation rate of 100%. Mw measured by GPC was 12800, and Mw / Mn was 1.23. When a film was formed by spin coating in the same manner as in Example 1, a 5% by mass solution was applied at 3000 rpm and dried to obtain a uniform 0.17 μm. However, at 10% by mass, a non-uniform film in which interference fringes were observed in a part of 0.45 μm was obtained. The narrow range is considered to have a narrower range of conditions for obtaining a uniform film than the wide molecular weight distribution.

[Example 5]
In Example 4, W (N-2,6-Me ₂ C ₆ H ₃ ) (thf) (OCMe ₂ CF ₃ ) ₂ Cl ₂ (49 mg, 0.07 mmol) as a ring-opening metathesis polymerization catalyst, 0. 03Mmol, and ^{_{W (N-2,6-Pr i}} 2 C 6 H 3) (CHCMe 2 Ph) (OCMe (CF 3) 2) 2 (60mg, 0.07mmol) using the toluene solution of the chain transfer agent Except that 1.06 ml (9.2 mmol) of 1,5-hexadiene was used, polymerized and then hydrogenated to form a white powder with 100% hydrogenation rate. 24.2 g of metathesis polymer hydrogenated product was obtained. The polystyrene standard conversion Mw measured by GPC was 25400, and Mw / Mn was 4.32. The composition ratio of the structural units [A] / [B] of the obtained polymer was 50/50.

  The obtained polymer was formed in the same manner as in Example 4. When a 5 mass% solution was applied at 3000 rpm and dried, a uniform 0.28 μm film was obtained. A film having a uniform thickness of 0.54 μm was obtained at 10% by mass.

  Furthermore, 18.2 g of a hydrogenated ring-opening metathesis polymer from which an ester group was partially eliminated was obtained. The compositional ratio of the obtained polymer structural units [A] / [B] / [D] was 40/50/10, Mw measured by GPC was 24800, and Mw / Mn was 4.69.

  The polymer thus obtained was formed in the same manner as in Example 1. When a 5 mass% solution was applied at 3000 rpm and dried, a uniform 0.28 μm film was obtained. A film having a uniform thickness of 0.54 μm was obtained at 10% by mass.

In addition, the resolution in the KrF excimer laser exposure was evaluated using the polymers of Examples and Comparative Examples as base resins. To 80 parts by mass of each polymer, 1 part by mass of an acid generator (PAG1) represented by the following general formula [18], 0.078 parts by mass of tributylamine as a basic compound, and 640 parts by mass of cyclohexanone as a solvent were mixed. Next, they were filtered through a Teflon (registered trademark) filter (pore size: 0.2 μm) to obtain a resist material. A resist solution was spin-coated on a silicon wafer coated with an antireflection film (DUV 30, 55 nm, manufactured by Nissan Chemical Industries), and a heat treatment was performed at 130 ° C. for 90 seconds to form a resist film having a thickness of 485 nm. This was exposed using a KrF excimer laser stepper (Nikon, NA = 0.5), subjected to a heat treatment at 110 ° C. for 90 seconds, and then a 2.38% tetramethylammonium hydroxide aqueous solution was used. Paddle development was performed for 2 seconds to form a 1: 1 line and space pattern. In the exposure dose (optimum exposure dose = Eop, mJ / cm ² ), which is obtained by observing a cleaved developed wafer with a cross-sectional SEM (scanning electron microscope) and resolving a 0.30 μm line and space 1: 1. The minimum line width (μm) of the separated line and space was defined as the resolution of the evaluation resist. In addition, the shape of the pattern at that time is classified into one of rectangular, round head, T-top, forward taper, and reverse taper. Moreover, the solvent used all contained 0.05 mass% of FC-430 (Sumitomo 3M Co., Ltd. product).

  When the resist film was formed and evaluated for performance at a polymer concentration of 5% by mass, the resolution was 0.24 μm and the edge was a sharp rectangle, and there was no problem.

The hydrogenated ring-opening metathesis polymer of the present invention and its production method are excellent in heat resistance, heat decomposition resistance, light transmittance, etc., and are used as a photoresist film for semiconductor microfabrication using ultraviolet rays or far ultraviolet rays. It is a polymer having the property of being easy to use, and is extremely valuable industrially.

The 1H-NMR spectrum (270 MHz, a solvent is deuterated chloroform) of the hydrogenated product of the ring-opening metathesis polymer obtained in Example 1 is shown.

Claims (27)

The following general formula [1]

(In the formula, at least one of R ^{1 to} R ⁴ is represented by the following general formula [2]:

(In the formula, a chain line represents a bond. R ⁵ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, R ⁶ represents a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, W ¹ Represents a single bond or a K + divalent hydrocarbon group having 1 to 10 carbon atoms, Z represents a divalent hydrocarbon group having 2 to 15 carbon atoms, and forms a single ring or a bridged ring together with the carbon atoms to be bonded. k is 0 or 1.) is a functional group having a cyclic alkyl tertiary ester group, and the others are each independently a hydrogen atom, a linear, branched or cyclic group having 1 to 20 carbon atoms. An alkyl group, halogen, linear, branched or 1 to 20 carbon atoms A halogenated alkyl group, a linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, a linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, and a carbon number 2 to 20 Linear, branched or cyclic alkylcarbonyloxy group, arylcarbonyloxy group having 6 to 20 carbon atoms, linear, branched or cyclic alkylsulfonyloxy group having 1 to 20 carbon atoms, and 6 to 20 carbon atoms An arylsulfonyloxy group, a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a linear, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, ¹ is -O- or -CR ⁷ ₂ - (R ⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), and may be the same or different j represents 0 or an integer of 1 to 3; A structural unit [A] represented by the following general formula [3]

(Wherein R ^{8 to} R ¹¹ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and X ² is —O— or —CR ¹² ₂ —. (R ¹² represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms, and may be the same or different. M represents an integer of 0 or 1 to 3). Structural unit [B] and / or the following general formula [4]

(Wherein R ^{13 to} R ¹⁶ are each independently a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, and X ³ is —O— or —CR ¹⁷ ₂ —. (R ¹⁷ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms) and may be the same or different, and ^one of Y ¹ and Y ² is — (C═O). And the other is —CR ¹⁸ ₂ — (R ¹⁸ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms.) N is an integer of 0 or 1 to 3. X ¹ of the structural unit [A] represented by the general formula [1] and at least the structural unit [B] represented by the general formula [3]. X ^2, and at least one of X ³ of general formula [4] represented by the structural unit [C] is -O-, and its constituent molar ratio of A] / ([B] and [C]) is 0/100 to 99/1, and the ratio (Mw / Mn) of the weight average molecular weight Mw to the number average molecular weight Mn is greater than 2.0 and 5.0. A ring-opening metathesis polymer hydrogenated product characterized by being smaller. Structural molar ratio of the structural unit [A] represented by the general formula [1] to the structural unit [B] represented by the general formula [3] and the structural unit [C] represented by the general formula [4] [ The ring-opening metathesis polymer hydrogenated product according to claim 1, wherein A] / ([B] and [C]) is 25/75 to 90/10. Structural molar ratio of the structural unit [A] represented by the general formula [1] to the structural unit [B] represented by the general formula [3] and the structural unit [C] represented by the general formula [4] [ The ring-opening metathesis polymer hydrogenated product according to claim 1, wherein A] / ([B] and [C]) is 30/70 to 85/15. X ¹ of the structural unit [A] represented by the general formula [1], X ² of the structural unit [B] represented by the general formula [3], and a structural unit [C] represented by the general formula [4] The ring-opening metathesis polymer hydrogenated product according to any one of claims 1 to ³ , wherein at least one of X ³ is -O- and the other is -CH _2- . The functional group having the tertiary ester group of the cyclic alkyl represented by the general formula [2] selected as at least one of R ^{1 to} R ⁴ of the general formula [1] is a 1-alkylcyclopentyl ester or 1-alkyl The ring-opening metathesis polymer hydrogenated product according to any one of claims 1 to 4, which is a norbornyl ester or a 2-alkyl-2-adamantyl ester. General formula [2] hydrogenated ring-opening metathesis polymer according to any one of claims 1 to 5 W ¹ is a single bond. The following general formula [5]

(In the formula, at least one of R ^{19 to} R ²² is represented by the following general formula [6].

(In the formula, a chain line represents a bond. R ²³ represents a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, W ² represents a single bond or a q + 2 valent hydrocarbon group having 1 to 10 carbon atoms, and q is 0 or 1 is a functional group having a carboxylic acid group, and the others are each independently a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, halogen, carbon number. 1-20 linear, branched or cyclic halogenated alkyl groups, 1-20 carbon linear, branched or cyclic alkoxy groups, 2-20 carbon linear, branched or cyclic Alkoxyalkyl group, straight chain having 2 to 20 carbon atoms, branched Or a cyclic alkylcarbonyloxy group, an arylcarbonyloxy group having 6 to 20 carbon atoms, a linear, branched or cyclic alkylsulfonyloxy group having 1 to 20 carbon atoms, an arylsulfonyloxy group having 6 to 20 carbon atoms, Is selected from a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a linear, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms, and X ⁴ is —O— or —CR ²⁴ ₂ — (R ²⁴ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), which may be the same or different. p represents 0 or an integer of 1 to 3. The ring-opening metathesis polymer hydrogenated product according to any one of claims 1 to 6, which optionally contains a structural unit [D] represented by General Formula [5] for Structural Unit [A] Represented by General Formula [1], Structural Unit [B] Represented by General Formula [3], and Structural Unit [C] Represented by General Formula [4] The ring-opening metathesis weight according to claim 7, wherein the structural molar ratio ([A] + [B] + [C]) / [D] of the structural unit [D] represented by the formula is from 100/0 to 20/80. Combined hydrogenated product. 9. The ring-opening metathesis polymer hydrogenated product according to claim 7, wherein X ^{4 in the} general formula [5] is —O— or —CH ₂ —. The ring-opening metathesis polymer hydrogenated product according to any one of claims 7 to 9, wherein W ^{2 in the} general formula [6] is a single bond. The following general formula [7]

(In the formula, at least one of R ^{25 to} R ²⁸ is represented by the following general formula [8]:

(In the formula, a chain line represents a bond. R ²⁹ is a hydrogen atom, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms, a linear, branched or cyclic group having 2 to 10 carbon atoms. An alkoxyalkyl group or a linear, branched or cyclic acyl group having 1 to 10 carbon atoms, R ³⁰ is a linear or branched alkyl group having 1 to 10 carbon atoms, or a carbon number having 2 to 10 carbon atoms. A linear, branched or cyclic alkoxyalkyl group, a linear, branched or cyclic alkyl halide group having 1 to 20 carbon atoms, W ³ is a single bond or an s + 2 valent group having 1 to 10 carbon atoms. Represents a hydrocarbon group. S is 0 or 1.) is a functional group having a carboxylic acid ester group, and the others are each independently a hydrogen atom, a straight chain having 1 to 20 carbon atoms, branched. Or cyclic alkyl group, halogen, C1-20 Chain, branched or cyclic halogenated alkyl group, linear, branched or cyclic alkoxy group having 1 to 20 carbon atoms, linear, branched or cyclic alkoxyalkyl group having 2 to 20 carbon atoms, C2-C20 linear, branched or cyclic alkylcarbonyloxy group, C6-C20 arylcarbonyloxy group, C1-C20 linear, branched or cyclic alkylsulfonyloxy group An arylsulfonyloxy group having 6 to 20 carbon atoms, a linear, branched or cyclic alkoxycarbonyl group having 2 to 20 carbon atoms, or a linear, branched or cyclic alkoxycarbonylalkyl group having 3 to 20 carbon atoms is selected from group, X ⁵ is -O- or -CR ³¹ ₂ - a (R ³¹ represents a hydrogen atom or a linear or branched alkyl group having 1 to 10 carbon atoms), the But it may be different. r represents 0 or an integer of 1 to 3. The ring-opening metathesis polymer hydrogenated product according to any one of claims 1 to 10, further comprising a structural unit [E] represented by: General Formula [7] for Structural Unit [A] Represented by General Formula [1], Structural Unit [B] Represented by General Formula [3], and Structural Unit [C] Represented by General Formula [4] The ring-opening metathesis weight according to claim 11, wherein the structural molar ratio ([A] + [B] + [C]) / [E] of the structural unit [E] represented by the formula is from 100/0 to 40/60. Combined hydrogenated product. The ring-opening metathesis polymer hydrogenated product according to claim 11 or 12, wherein X ^{5 in the} general formula [7] is -O- or -CH _2- . The ring-opening metathesis polymer hydrogenated product according to any one of claims 11 to 13, wherein W ^{3 in the} general formula [8] is a single bond. The ring-opening metathesis polymer hydrogenated product according to any one of claims 1 to 14, which has a polystyrene-reduced weight average molecular weight of 500 to 1,000,000 as measured by GPC. The following general formula [9]

(Wherein R ^{1 to} R ⁴ , X ¹ , and j are the same as defined in the general formula [1] of claim 1), the cyclic olefin monomer represented by the following general formula is optionally used. [10]

(Wherein R ^{8 to} R ¹¹ , X ² , and m are the same as defined in general formula [3] of claim 1) and / or the following general formula [11 ]

(Wherein, R ^{13 to} R ¹⁶ , X ³ , Y ¹ , Y ² and n are the same as defined in the general formula [4] of claim 1). and X ¹ in the general formula [9], at least one of X ³ of X ^2, and of general formula [10] [11] Although -O-, and polymerizing them in ring-opening metathesis catalyst, The method for producing a hydrogenated product of a ring-opening metathesis polymer according to claim 1, wherein hydrogenation is performed under a hydrogenation catalyst. The cyclic olefin monomer represented by the general formula [9], the general formula [10] and / or the general formula [11] is opened at least in two or more stages with a polymer component having a high molecular weight and a polymer component having a low molecular weight. The method for producing a hydrogenated product of a ring-opening metathesis polymer according to claim 16, wherein polymerization is performed with a metathesis polymerization catalyst and then hydrogenation is performed under a hydrogenation catalyst. A polymer component having a high molecular weight and a low molecular weight by coexisting at least two kinds of polymerization catalysts for the cyclic olefin monomer represented by the general formula [9], the general formula [10] and / or the general formula [11]. The method for producing a hydrogenated product of a ring-opening metathesis polymer according to claim 16, wherein the polymer component is polymerized and then hydrogenated under a hydrogenation catalyst. Charge molar ratio of the cyclic olefin monomer represented by the general formula [9], the cyclic olefin monomer represented by the general formula [10], and the cyclic olefin monomer represented by the general formula [11] The method for producing a hydrogenated ring-opening metathesis polymer according to any one of claims 16 to 18, wherein is 0/100 to 99/1. Charge molar ratio of the cyclic olefin monomer represented by the general formula [9], the cyclic olefin monomer represented by the general formula [10], and the cyclic olefin monomer represented by the general formula [11] The method for producing a hydrogenated ring-opening metathesis polymer according to any one of claims 16 to 18, wherein is 25/75 to 90/10. X ¹ of the cyclic olefin monomer represented by the general formula [9], X ² of the cyclic olefin monomer represented by the general formula [10], and a cyclic olefin monomer represented by the general formula [11] at least one of X ³ of the body but -O-, and others -CH ₂ - method of manufacturing a hydrogenated ring-opening metathesis polymer according to any one of claims 16 to 20 is. The functional group having the tertiary ester group of the cyclic alkyl represented by the general formula [2] selected as at least one of R ^{1 to} R ^{4 in} the general formula [9] is 1-alkylcyclopentyl ester, 1-alkylnor The method for producing a hydrogenated ring-opening metathesis polymer according to any one of claims 16 to 21, which is a bornyl ester or a 2-alkyl-2-adamantyl ester. The hydrogenated ring-opening metathesis polymer according to any one of claims 16 to 22, wherein after hydrogenation, at least part of the tertiary ester group of the cyclic alkyl in the general formula [2] is decomposed into a carboxylic acid group. Manufacturing method. Furthermore, the following general formula [12]

(Wherein R ^{25 to} R ²⁸ , X ⁵ , and r are the same as defined in the general formula [7] according to claim 11), and the cyclic olefin monomer represented by claim 16 to 23 is used. The manufacturing method of the ring-opening metathesis polymer hydrogenated substance as described in any one. The method for producing a hydrogenated ring-opening metathesis polymer according to claim 24, wherein after hydrogenation, at least a part of the ester group is decomposed into a carboxylic acid group. The method for producing a hydrogenated ring-opening metathesis polymer according to any one of claims 16 to 25, wherein the ring-opening metathesis catalyst is a living ring-opening metathesis catalyst. 27. The method for producing a hydrogenated ring-opening metathesis polymer according to any one of claims 16 to 26, wherein the polymerization is carried out with a ring-opening metathesis catalyst in the presence of an olefin or a diene.

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