JP2007045787A - alpha-SUBSTITUTED ACRYLIC ACID NORBORNANYLS, METHOD FOR PRODUCING THE SAME AND COPOLYMER USING THE SAME - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To produce/provide objective specific α-substituted acrylic acid norbornanyls from a substituted norbornene by passing through a substituted norbornanyl alcohol in a high selectivity and yield, and a polymer containing the same as a monomer. <P>SOLUTION: This substituted norbornanyl alcohol is expressed by general formula [4] [wherein, any one of R<SP>2</SP>, R<SP>3</SP>is RfSO<SB>2</SB>NHCH<SB>2</SB>- group (wherein, Rf is a 1-4C perfluoroalkyl) and rest is H]. <P>COPYRIGHT: (C)2007,JPO&INPIT

Description

  The present invention relates to α-substituted norbornanyl acrylates which are compounds useful as monomers corresponding to next-generation photoresists and methods for producing the same, substituted norbornanyl alcohols which are precursors of α-substituted norbornanyl acrylates and the production thereof And polymers containing repeat units derived from α-substituted norbornanyl acrylates.

In recent years, with the development of digital devices such as computers, the processing amount of processing data, 2D and 3D image data has become enormous, and a large-capacity and high-speed memory is required to quickly process such information. And a high performance microprocessor is needed. In addition, with the development of networks such as the Internet, it is predicted that the use of broadband will accelerate further, and the processing capacity required for digital devices will increase further.
In order to achieve this requirement, various device devices typified by semiconductor devices are required to have higher density and higher integration. In particular, the demand for photolithography technology that enables microfabrication is becoming stricter year by year, and the fabrication of DRAMs having an integration density of 1 Gbit or more requires processing technology with a minimum line width of 0.13 microns or less. Correspondingly, photolithography using an ArF excimer laser (193 nm) has begun to be used. Furthermore, for the purpose of processing a fine pattern, development of photolithography and immersion lithography using an F ₂ excimer laser (157 nm) is in progress.
In these wavelength regions, novolak and polyvinylphenol resins conventionally used for resist materials are too light-absorbed and cannot be used. Therefore, acrylic resins (for example, Patent Document 1) and cycloolefin resins (for example, Patent Document 2) have been studied. However, resins with high transparency at the wavelength of F ₂ excimer laser (157 nm) are very limited, and the superiority of fluororesins has become clear. In particular, it has been reported that a resist resin containing a fluorine-based hydroxyl group has excellent properties in hydrophilicity, and is very promising (for example, Non-Patent Documents 1 and 2).
However, the introduction of fluorine atoms improves the transparency in the ultraviolet region, but at the same time brings about a decrease in etching resistance. As for the polymerization reactivity, monomers having a fluorine atom or a trifluoromethyl group directly on the norbornene ring have a low polymerization reactivity and a low yield, and a sufficient molecular weight as a material can be obtained. There were many issues left unanswered. Therefore, the functions that these existing compounds can exhibit are not always sufficient, and it has been desired to create a novel monomer or a raw material thereof that can efficiently provide a superior polymer compound.

On the other hand, in the field of semiconductor device packages, epoxy resin or the like is generally employed. However, in order to reduce thermal stress during mounting on a printed circuit board, an element substrate ( A method of adding fine particles of silicon oxide (SiO ₂ ) having a thermal expansion coefficient close to that of the (Si substrate) is used. However, in the conventional technology, the plastic package with a conventional structure using an epoxy resin that is inferior to metal or ceramics in terms of thermal conductivity has poor heat dissipation characteristics and considerably high thermal resistance. It is disadvantageous in terms of long-term reliability as a power IC or an IC package that operates at high speed. In addition, since the SiO ₂ particles added to the resin to make it low stress are very hard, the thermal stress generated during mounting on a printed circuit board applies a large pressure locally to the element surface, The destruction occurred. That is, in the field of semiconductor packages, a material that has high heat resistance and is difficult to apply thermal stress to the element surface has been demanded (for example, Patent Document 3). Actually, it is difficult to satisfy the required performance with a single semiconductor package material, and various protective films are used in combination. It can be said that the package material and the protective film play a role by making up for each other's drawbacks. A passivation film is used to prevent water and impurities from entering the semiconductor chip, and a buffer coat film is used to alleviate stress concentration generated in the package material. Conventionally, inorganic compounds such as silicon oxide have been the mainstream for thin film materials such as insulating films and protective films used in semiconductors, but now the availability of heat-resistant polymer materials such as polyimide has been recognized, and correlation insulating films It is used for passivation film, buffer coating film, etc.

Further, in response to the recent demand for higher integration and higher speed of semiconductors, materials corresponding to high-speed signal transmission are required. In high-speed transmission, signal propagation delay becomes a problem, but since the propagation delay is proportional to the relative dielectric constant of the material, it is effective to reduce the dielectric constant of the material. At present, fluororesins are known to have a low dielectric constant, and fluorine-containing polyimides are also being studied as one of the promising materials. Resin into which fluorine atoms have been introduced has unique properties such as water repellency and non-adhesive properties of fluorine, and it can sometimes be used for the intended purpose. Sometimes it was difficult. With the advent of new semiconductor application products in recent years, semiconductor packages have also been diversified, and various demands such as downsizing, thinning, and low dielectric constant have been made, and package materials that satisfy these requirements have been desired.
On the other hand, α-substituted norbornanyl acrylates are known to contain various isomers, but there have been few reports on examples of controlling the formation of isomers or taking out single isomers. Not.
Further, it is disclosed that a polymer having a repeating unit derived from a polymerizable ester compound having a sulfonamide structure is excellent in transparency at an excimer laser exposure wavelength, dry etching resistance, and the like (Patent Document 4).
JP-A-10-161313 JP 2000-89463 A JP-A-8-241913 JP 2005-23304 A H. Ito, HD Truong, et al, J. Photopolym. Sci. Technol., 16, 523-536 (2003) Francis Houlihan, Andrew Romano, Ralph R, Dammel, et al, J. Photopolym. Sci. Technol., 16, 581-590 (2003)

The present invention is a resist material or semiconductor device having high transparency in a wide wavelength range from the ultraviolet region to the near infrared region, and having both high adhesion to the substrate, film forming property, and high etching resistance. An object of the present invention is to provide a novel α-substituted norbornanyl alcohol, a α-substituted norbornanyl acrylate derived therefrom, and a method for producing the same, which are used as monomer materials for the packaging material.
Further, in the present invention, it is an important object to provide a specific single α-substituted norbornanyl acrylate among a plurality of isomers. Generally, α-substituted norbornanyl acrylates have many isomers in the production process. Usually, since it contains four or more isomers, it is difficult to design a polymer composition in consideration of the characteristics of each isomer compound.
Furthermore, when used as a photoresist material in practical applications, for example, the dissolution rate in an alkaline developer and the adhesion to the substrate are greatly different from the isomer structure, and the high performance that can be inferred from the structural formula cannot be realized. Many problems that occurred because of the mixture remained.
That is, the present invention produces the desired specific α-substituted norbornanyl acrylates and polymers containing these as monomers from the substituted norbornene via the substituted norbornanyl alcohol with high selectivity and yield. The issue is to provide.

As a result of intensive studies in order to solve the above-mentioned problems, the present inventors have found that a novel α-substituted norbornanyl alcohol having a norbornene ring and a perfluoroalkylsulfonamide structure and a novel derived therefrom. α-Substituted norbornanyl acrylates were found.
This novel fluorine-containing polymer obtained by polymerizing α-substituted norbornanyl acrylates has not only high transparency in a wide wavelength range, but also high adhesion to a substrate and film formability, as well as a norbornene ring. It is expected as a resist material having high etching resistance derived from the structure. Furthermore, the fluorine-containing polymer compound obtained by polymerizing the novel α-substituted norbornanyl acrylates of the present invention has a high heat resistance because it has a cyclic structure in the molecule, and is excellent in being derived from a perfluoroalkylsulfonamide structure. It is expected to have excellent solvent-solubility, coating properties, and excellent film formability and moldability.
In addition, when the fluorine-containing polymer compound obtained by polymerizing the novel α-substituted norbornanyl acrylates of the present invention is used as it is or when a semiconductor device is packaged by adding a curing agent thereto, It is expected that stress on the element substrate is very small and high reliability can be obtained.

In general, as a method of converting an alcohol into an α-substituted acrylic acid ester, (1) dehydration condensation between α-substituted acrylic acid and alcohol, or (2) synthesis by reaction between α-substituted acrylic acid chloride and alcohol. Can do.
The method (1) requires a reaction at a high temperature for a long time for dehydration, and an excess acid needs to be used to bring the equilibrium to the ester side. However, in the reaction under such conditions, the produced α-substituted acrylate ester is likely to be polymerized and cannot be isolated because it exists in the reaction system for a long time at a high temperature.
In the above method (2), it is necessary to move the equilibrium by consuming the acid generated by reacting the α-substituted acrylic acid chloride and the alcohol with the base. There is a problem that the amount of waste increases. Further, in order to remove by-produced salts and the like from the reaction system, it is necessary to perform filtration or water washing or filtration and water washing. That is, as a monomer for use in electronic materials, residual salt causes a defect, and therefore esterification using acid chloride is not desirable.

Moreover, in order to ensure sufficient purity for use as a monomer, a distillation operation or the like is necessary. However, the α-substituted norbornanyl acrylates of the present invention have a very high boiling point, and are used for distillation. Must be distilled at high temperature under high vacuum. The α-substituted norbornanyl acrylates of the present invention contain a polymerizable group of an α-substituted acrylic acid moiety, which is easily polymerized at a high temperature. Therefore, when distillation at a high temperature is performed, Difficult to separate. In order to facilitate purification, it is necessary to reduce the purification load of α-substituted norbornanyl acrylates by purifying the substituted norbornanyl alcohol as a raw material and using the substituted norbornanyl alcohol. -Like substituted norbornanyl acrylates, high boiling point, high viscosity, difficult to handle compounds.
That is, in the production of substituted norbornanyl alcohols and in the production of α-substituted norbornanyl acrylates that are esterified using them as raw materials, it is necessary to develop a production method that does not generate by-products. At the same time, it was necessary to develop a method for selectively obtaining a specific isomer of interest.

Therefore, the present inventors conducted extensive studies to establish a method for producing substituted norbornanyl alcohol suitable for production on an industrial scale and a method for producing α-substituted norbornanyl acrylates. A by-product by combining a method for producing a substituted norbornanyl alcohol with a low content (first step) and a second step of reacting the substituted norbornanyl alcohol obtained in the first step with an α-substituted acrylic anhydride The present inventors have found that α-substituted norbornanyl acrylates with a low content can be produced with high selectivity and high yield.
Furthermore, the present inventors have found that a single isomer can be obtained by recrystallizing the above-mentioned product containing several isomers with a specific solvent, and have reached the present invention. Moreover, the polymer using these (alpha) -substituted norbornanyl acrylates as a monomer is provided.

［式中、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表される置換ノルボルナニルアルコールである。なお、本願明細書において、脂環族化合物を構成する炭素原子に結合している水素原子は省略してある。従って、Ｒ²、Ｒ³のいずれか一つは、同一炭素原子に２個の水素原子が結合している。 That is, the present invention relates to the general formula [4]

[In the formula, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the remainder is hydrogen. Is an atom. ] The substituted norbornanyl alcohol represented by this. In the present specification, hydrogen atoms bonded to carbon atoms constituting the alicyclic compound are omitted. Accordingly, in any one of R ² and R ³ , two hydrogen atoms are bonded to the same carbon atom.

［式中、Ｒ¹は、水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基を表す。］で表される低級カルボン酸を、一般式［２］

［式中、Ｒ²、Ｒ³のうち、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表される置換ノルボルネンと反応させて、一般式［３］

［式中、Ｒ¹は一般式［１］のＲ¹と同じで、Ｒ²、Ｒ³は一般式［２］のＲ²、Ｒ³と同じ］で表される置換ノルボルナニル類を得て、これを加水分解することを特徴とする、一般式［４］

［式中、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表される置換ノルボルナニルアルコールの製造方法である。 The present invention also provides a general formula [1].

[Wherein, R ¹ represents a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. A lower carboxylic acid represented by the general formula [2]

[Wherein, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the rest It is a hydrogen atom. And a substituted norbornene represented by the general formula [3]

Wherein, R ¹ is the same as R ¹ in the general formula [1], R ^2, R ³ is the general formula [2] R ^2, R ³ identical] to give a substituted norbornanyl compound represented by, This is hydrolyzed and is represented by the general formula [4]

[Wherein, R ^2, R ³ is any one that RfSO ₂ NHCH ₂ - group (., Where, Rf is selected from the group consisting of a carbon number of 1 represents a perfluoroalkyl group having 4 carbon atoms), and the remainder is hydrogen Is an atom. It is a manufacturing method of substituted norbornanyl alcohol represented by this.

[式中、Ｒ⁴は水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基であり、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表されるα−置換アクリル酸ノルボルナニル類である。
また、α−置換アクリル酸ノルボルナニル類が、５−ｅｘｏ−（｛［（トリフルオロメチル）スルホニル］アミノ｝メチル）ビシクロ［２．２．１］ヘプト−２−ｅｘｏ−イル ２−メチルアクリレートであることを特徴とする上記のα−置換アクリル酸ノルボルナニル類である。 The present invention also provides a general formula [6].

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group ( Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. [Alpha] -substituted norbornanyl acrylates represented by the formula:
The α-substituted norbornanyl acrylate is 5-exo-({[(trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-exo-yl 2-methyl acrylate. It is said (alpha) -substituted norbornanyl acrylate characterized by the above-mentioned.

[式中、Ｒ⁴は水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基であり、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表されるα−置換アクリル酸ノルボルナニル類の製造方法である。
第一工程：上記、一般式［４］で表される置換ノルボナニルアルコールを製造する工程。
第二工程：一般式［５］

[式中、Ｒ⁴は水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基である。]で表されるα−置換アクリル酸無水物を、上記第一工程で得られた一般式［４］

［式中、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表される置換ノルボルナニルアルコールと反応させることを特徴とする、一般式［６］

[式中、Ｒ⁴は水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基であり、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表されるα−置換アクリル酸ノルボルナニル類を製造する工程である。
また、本発明は、一般式［５］で表されるα−置換アクリル酸無水物の置換基Ｒ⁴が水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基である、上記α−置換アクリル酸ノルボルナニル類の製造方法である。
更に本発明は、一般式［５］で表されるα−置換アクリル酸無水物の置換基Ｒ⁴が水素原子、メチル基である、上記α−置換アクリル酸ノルボルナニル類の製造方法を提供する。 Further, the present invention comprises the following general formula [6], which comprises the following two steps.

Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 4 carbon atoms having a carbon number of 1, R ^2, R ³ is any one that RfSO ₂ NHCH ₂ - group ( Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. ] The manufacturing method of (alpha) -substituted norbornanyl acrylate represented by this.
1st process: The process of manufacturing the substituted norbonanyl alcohol represented by the said General formula [4].
Second step: General formula [5]

[Wherein, R ⁴ represents a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. An α-substituted acrylic anhydride represented by the general formula [4] obtained in the first step.

[In the formula, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the remainder is hydrogen. Is an atom. And a substituted norbornanyl alcohol represented by the general formula [6]

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group ( Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. ] The process for producing the α-substituted norbornanyl acrylate represented by the formula:
In the present invention, the substituent R ⁴ of the α-substituted acrylic anhydride represented by the general formula [5] is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. This is a method for producing the above-mentioned α-substituted norbornanyl acrylates.
Furthermore, the present invention provides a method for producing the above α-substituted norbornanyl acrylates, wherein the substituent R ⁴ of the α-substituted acrylic anhydride represented by the general formula [5] is a hydrogen atom or a methyl group.

In the production method of the above-mentioned α-substituted norbornanyl acrylates of the present invention, the second step is represented by the following scheme 1, but can be carried out by adding an additive in order to accelerate the reaction. The present invention is the method for producing the above-mentioned α-substituted norbornanyl acrylate, wherein the second step is performed in the presence of an additive comprising an organic sulfonic acid and / or a Lewis acid. Additives used include organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and trifluoromethanesulfonic acid, and Lewis acids such as boron trifluoride, titanium tetrachloride, and tin tetrachloride. At least one acid selected from the group is preferably used.
Furthermore, this invention is a manufacturing method of (alpha) -substituted norbornanyl acrylate characterized by performing the 3rd process recrystallized with a hydrocarbon type solvent after the manufacturing process of the said (alpha) -substituted norbornanyl acrylate.
In the method for producing an α-substituted norbornanyl acrylate of the present invention, the second step is summarized in Scheme 1.

［式中、Ｒ⁴は、水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基であり、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表されるα−置換アクリル酸ノルボルナニル類由来の繰り返し単位を有するゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレン換算重量平均分子量が１，０００〜１００，０００の重合体である。 The polymer of the present invention is obtained by polymerizing an α-substituted norbornanyl acrylate represented by the above general formula [6].

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group. Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. ] The polymer of the polystyrene conversion weight average molecular weights 1,000-100,000 by the gel permeation chromatography (GPC) which has a repeating unit derived from (alpha) -substituted norbornanyl acrylate represented by these is a polymer.

［式［８］から式［１１］において、Ｒ⁵は水素原子、メチル基、トリフルオロメチル基あるいはヒドロキシメチル基を表し、式［９］から式［１１］において、Ｒ⁶はＲ⁵とは独立にメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｔ−ブチル基、２−メチルプロピル基、１−メチルプロピル基、メトキシメチル基、エトキシメチル基、エトキシエチル基を表し、ｎは０〜１の整数を、ｍは１〜２の整数をそれぞれ表す。］で表される少なくとも１つの繰り返し単位とを有するゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレン換算重量平均分子量が１，０００〜１００，０００の共重合体である。 The copolymer of the present invention comprises (I) a repeating unit represented by the above general formula [7], and (II) a general formula [8] to a general formula [11].

[In the formulas [8] to [11], R ⁵ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group. In the formulas [9] to [11], R ⁶ represents R ^5. Independently methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, t-butyl group, 2-methylpropyl group, 1-methylpropyl group, methoxymethyl group, ethoxymethyl group, ethoxyethyl Represents a group, n represents an integer of 0 to 1, and m represents an integer of 1 to 2, respectively. ] A copolymer having a polystyrene-reduced weight average molecular weight of 1,000 to 100,000 by gel permeation chromatography (GPC) having at least one repeating unit represented by the formula:

［式［１２］及び式［１３］において、Ｒ⁵は、水素原子、メチル基、トリフルオロメチル基あるいはヒドロキシメチル基を表し、式［１２］において、Ａは単結合、炭素数１から炭素数１０の直鎖状もしくは分岐状のアルキレン基又は炭素数４から炭素数２０の脂環式炭化水素基、アルキレングリコール基、アルキレンエステル基を表し、式［１３］において、Ｚは２〜４価の有機基を表し、Ｔは単結合又は炭素数１から炭素数３の２価の有機基を表し、ｐは１〜３の整数を表す。］で表される少なくとも１つの繰り返し単位とを有するゲルパーミエーションクロマトグラフィ（ＧＰＣ）によるポリスチレン換算重量平均分子量が１，０００〜１００，０００の共重合体である。 The copolymer of the present invention comprises (I) a repeating unit represented by the above general formula [7], (III) a general formula [12] and a general formula [13].

[In Formula [12] and Formula [13], R ⁵ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. In Formula [12], A is a single bond, having 1 to carbon atoms. 10 represents a linear or branched alkylene group or an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an alkylene glycol group, or an alkylene ester group. In the formula [13], Z is a divalent to tetravalent group. T represents an organic group, T represents a single bond or a divalent organic group having 1 to 3 carbon atoms, and p represents an integer of 1 to 3. ] A copolymer having a polystyrene-reduced weight average molecular weight of 1,000 to 100,000 by gel permeation chromatography (GPC) having at least one repeating unit represented by the formula:

According to the present invention, a desired α-substituted norbornanyl acrylate can be produced from a substituted norbornene through a substituted norbornanyl alcohol with a high selectivity and yield.
Polymers and copolymers containing repeating units derived from α-substituted norbornanyl acrylates of the present invention are active radiation, particularly ArF excimer laser (wavelength 193 nm), F ₂ excimer laser (wavelength 157 nm) represented by far. As a chemically amplified resist resin that is sensitive to ultraviolet rays, it is possible to provide resists with excellent dry etching resistance and pattern shape as well as characteristics such as resist transparency, high sensitivity and resolution, which are the basic performance of resists. .

［式中、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］及び一般式［６］で表されるα−置換アクリル酸ノルボルナニル類（以下、単にα−置換アクリル酸ノルボルナニル類という場合もある）

[式中、Ｒ⁴は水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基であり、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］は、ノルボルネン環とパーフルオロアルキルスルホンアミド構造を有する新規な含フッ素環状化合物である。 Hereinafter, the present invention will be described in detail. Substituted norbornanyl alcohol represented by the general formula [4] of the present invention (hereinafter sometimes simply referred to as substituted norbornanyl alcohol)

[In the formula, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the remainder is hydrogen. Is an atom. And α-substituted norbornanyl acrylates represented by the general formula [6] (hereinafter also referred to simply as α-substituted norbornanyl acrylates)

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group ( Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. ] Is a novel fluorine-containing cyclic compound having a norbornene ring and a perfluoroalkylsulfonamide structure.

Rf in the RfSO ₂ NHCH ₂ — group is a perfluoroalkyl group having 1 to 4 carbon atoms, and is a trifluoromethyl group, a perfluoroethyl group, a perfluoropropyl group, or a perfluorobutyl group. Among these, a trifluoromethyl group and a perfluoroethyl group are preferable, and a trifluoromethyl group is particularly preferable.

In general, it is known that with an increase in the fluorine content, an improvement in transparency and a decrease in refractive index are induced in a wide wavelength region from the ultraviolet region to the near infrared region. On the other hand, a decrease in adhesion to the substrate and a decrease in film formability are induced with an increase in the fluorine content, and it has been difficult to achieve both high transparency and low refractive index.
However, since the compounds represented by the general formula [4] and the general formula [6] have a perfluoroalkylsulfonamide structure, the polymer compound derived from the general formula [6] has high adhesion to the substrate, It is fully expected to have high film-forming properties.
The cyclic norbornene skeleton is preferable because it contributes to the etching resistance necessary for the resist material, and the glass transition temperature (Tg) of the polymer compound derived therefrom is increased by introducing a cyclic structure in the molecule. Can do. It is also possible to adjust Tg by adjusting the ratio of the cyclic structure contained in the polymer compound. Tg is an important factor for the acid diffusion rate of a chemically amplified positive resist, and is an important factor for reducing or adjusting the thermal expansion coefficient in the field of semiconductor device packaging materials and buffer coatings.

The substituted norbonanyl alcohol represented by the general formula [4] can be introduced into a polymer compound having a carboxylic acid or an ether group by a post-reaction, and can be expected to exhibit the above characteristics. Moreover, the α-substituted norbornanyl acrylate represented by the general formula [6] is useful as a monomer for polymerizing a polymer compound.
Furthermore, in the present invention, the α-substituted norbornanyl acrylates shown in claim 5 and having a specific structure, 5-exo-({[(trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2 .1] Hept-2-exo-yl 2-methyl acrylate can be provided as a single isomer.
Generally, α-substituted norbornanyl acrylates have many isomers in the production process and contain four or more isomers. This isomer has a great influence on the position, spread and conformation of the acidic amide group in the side chain structure. When used as a photoresist material, which is a practical application, the dissolution rate in an alkaline developer and the adhesion to the substrate are important design points. However, the 5-exo-({[(trifluoro The combination of exo / exo represented by methyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-exo-yl 2-methyl acrylate can arrange an acidic amide group most effectively. It is.

［式中、Ｒ¹は、水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基を表す。］で表される低級カルボン酸を、一般式［２］

［式中、Ｒ²、Ｒ³のうち、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表される置換ノルボルネンと反応させて、一般式［３］

［式中、Ｒ¹は一般式［１］のＲ¹と同じで、Ｒ²、Ｒ³は一般式［２］のＲ²、Ｒ³と同じ］で表される置換ノルボルナニル類を得て、これを加水分解することにより、一般式［４］

［式中、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表される置換ノルボルナニルアルコールの製造工程である。 Next, the production method of the α-substituted norbornanyl acrylates of the present invention will be described in detail.
The production method of the α-substituted norbornanyl acrylate represented by the general formula [6] of the present invention comprises the following two steps. The following first step is a method for producing a substituted norbornanyl alcohol represented by the general formula [4] of the present invention.
First step: General formula [1]

[Wherein, R ¹ represents a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. A lower carboxylic acid represented by the general formula [2]

[Wherein, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the rest It is a hydrogen atom. And a substituted norbornene represented by the general formula [3]

Wherein, R ¹ is the same as R ¹ in the general formula [1], R ^2, R ³ is the general formula [2] R ^2, R ³ identical] to give a substituted norbornanyl compound represented by, By hydrolyzing this, general formula [4]

[In the formula, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the remainder is hydrogen. Is an atom. ] The manufacturing process of substituted norbornanyl alcohol represented by this.

[式中、Ｒ⁴は水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基である。]で表されるα−置換アクリル酸無水物を、上記第一工程で得られた一般式［４］

［式中、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表される置換ノルボルナニルアルコールと反応させることを特徴とする、一般式［６］

[式中、Ｒ⁴は水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基であり、Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。］で表されるα−置換アクリル酸ノルボルナニル類を製造する工程である。 Second step: General formula [5]

[Wherein, R ⁴ represents a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. An α-substituted acrylic anhydride represented by the general formula [4] obtained in the first step.

[In the formula, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the remainder is hydrogen. Is an atom. And a substituted norbornanyl alcohol represented by the general formula [6]

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group ( Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. ] The process for producing the α-substituted norbornanyl acrylate represented by the formula:

First, the first step will be described. The first step can be performed in a batch reactor. The reaction conditions will be described below, but this does not prevent changes in the reaction conditions that can be easily adjusted by those skilled in the art in each reaction apparatus.
The substituted norbornanyl alcohol represented by the general formula [4] is obtained by first reacting the lower carboxylic acid represented by the general formula [1] with the substituted norbornene represented by the general formula [2]. It can manufacture by hydrolyzing this, after manufacturing substituted norbornanyl represented by these. At this time, the obtained substituted norbornanyl alcohol represented by the general formula [4] is a mixture containing isomers. Each may be separated and purified and used for the reaction, but there is no problem if it is used as an isomer mixture.
The substituted norbornene represented by the general formula [2] is synthesized by subjecting allylamine and cyclopentadiene to Diels-Alder reaction in the presence or absence of a Lewis acid catalyst to synthesize aminomethylnorbornene (Japanese Patent Laid-Open No. Sho 56- 139543), which is known to be obtained by reaction with trifluoromethanesulfonic anhydride or trifluoromethanesulfonyl halide (Kas'yan, AO, Maletina, II, et al, Zhurnal Organicheskoi Khimii, 31 ( 3), 357-64 (1995)).

One of R ² and R ³ in the substituted norbornanyl alcohol represented by the general formula [4] is an RfSO ₂ NHCH ₂ — group, and the remainder is a hydrogen atom.
In the first step of the present invention, formic acid, acetic acid, propionic acid, trifluoroacetic acid, pentafluoropropionic acid is generally used as the lower carboxylic acid used in the reaction for obtaining the substituted norbornanyl represented by the general formula [3]. However, formic acid is particularly preferable from the viewpoint of economy. The amount of the lower carboxylic acid is 1 to 20 moles, preferably 5 to 17 moles, more preferably 7 to 13 moles relative to 1 mole of the substituted norbornene. When the amount of the lower carboxylic acid is less than 1 mol relative to 1 mol of the substituted norbornene, both the selectivity of the reaction and the yield of the target product are reduced. When the amount exceeds 20 mol, the lower carboxylic acid not involved in the reaction increases. It is not preferable from the aspect of increasing economical and environmental burdens.
The reaction temperature at the time of implementing is 0-250 degreeC, 20-200 degreeC is preferable and 50-160 degreeC is more preferable. When the temperature is lower than 0 ° C., the reaction rate is extremely slow and it is not a practical production method. On the other hand, if it exceeds 250 ° C., the raw material substituted norbornene or the product substituted norbornanyl may be decomposed, which is not preferable.
In this reaction, no solvent is preferable, but a solvent can also be used. Although there is no special restriction | limiting in the kind of solvent which can be used, Hydrocarbons, such as aromatic compounds, such as benzene, toluene, xylene, and mesitylene, octane, heptane, and hexane, can be used. These may be used alone or in combination with a plurality of solvents.
When using a solvent for this reaction, the solvent amount of the solvent to be used is 0.2-50 g with respect to 1 g of substituted norbornene, preferably 0.5-20 g, more preferably 1-10 g. If the amount of solvent exceeds 50 g with respect to 1 g of substituted norbornene, it is not economically preferable from the viewpoint of productivity.

In the first step of the present invention, water and alkali are used in the reaction for producing the substituted norbornanyl alcohol represented by the general formula [4] by hydrolyzing the substituted norbornanyl represented by the general formula [3]. . In general, an inorganic alkali can be used as the alkali to be used, and sodium hydroxide and potassium hydroxide are particularly preferable. The amount of alkali used is 1 to 10 moles, preferably 1 to 5 moles, more preferably 1 to 3 moles per mole of substituted norbornanyls. When the amount of alkali is less than 1 mole per 1 mole of substituted norbornanyl, the reaction does not proceed sufficiently, the yield of the target product decreases, and when it exceeds 10 moles, the alkali not involved in the reaction increases, and the economy It is not preferable from the viewpoint of increase in environmental and environmental load.
Moreover, the quantity of the water to be used is 0.1-10g with respect to 1g of substituted norbornanyl, 0.5-5g is preferable and 1-3g is more preferable. When the amount of water is less than 0.1 g with respect to 1 g of substituted norbornanyl, the reaction does not proceed sufficiently, the yield of the target product decreases, and when the amount exceeds 10 g, the amount of extraction solvent used for isolation is small. It is unfavorable in terms of increase in economic and environmental burdens.
The reaction temperature at the time of implementing is 0-200 degreeC, 20-170 degreeC is preferable and 50-120 degreeC is more preferable. When the temperature is lower than 0 ° C., the reaction rate is extremely slow and it is not a practical production method. Moreover, when it exceeds 200 degreeC, since the substituted norbornanyl of a raw material or the substituted norbornanyl alcohol of a product may decompose | disassemble, it is unpreferable.
A solvent can be used in this reaction. There are no particular restrictions on the type of solvent that can be used, but aromatic compounds such as benzene, toluene, xylene, and mesitylene, ether solvents such as diethyl ether, methyl-t-butyl ether, diisopropyl ether, and tetrahydrofuran, methylene chloride, and chloroform A halogen-based solvent such as carbon tetrachloride is preferable, and these may be used alone or in combination with a plurality of solvents.
When using a solvent for this reaction, the solvent amount of the solvent to be used is 0.1-20 g with respect to 1 g of substituted norbornene, 0.2-10 g is preferable, and 0.5-5 g is more preferable. If the amount of solvent exceeds 50 g with respect to 1 g of substituted norbornene, it is not economically preferable from the viewpoint of productivity.
The reactor that performs the reaction in the first step is made of tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass lined inside, glass container, or stainless steel. preferable.

The method for carrying out the first step of the present invention is not limited, but details will be described with respect to an example of a desirable embodiment. Into a reactor that can withstand the reaction conditions, charged raw materials are substituted norbornene and lower carboxylic acid, and the reaction is allowed to proceed by heating from outside while stirring. The consumption of the raw material is monitored by sampling or the like, it is confirmed that the reaction is completed, and the reaction liquid is cooled.
The obtained reaction solution was washed with water, charged with a substituted norbornanyl compound represented by the general formula [3], a solvent, water and potassium hydroxide in a reactor that can withstand the reaction conditions, and heated from the outside while stirring. Allow the reaction to proceed. The consumption of the raw material is monitored by sampling or the like, it is confirmed that the reaction is completed, and the reaction liquid is cooled. Separation of the organic layer, addition of an inorganic acid to the aqueous layer until pH 3 is achieved, extraction with an organic solvent, and distillation of the organic solvent to obtain a substituted norbornanyl alcohol represented by the general formula [4] Can do.
The substituted norbornanyl alcohol represented by the general formula [4] produced by this reaction may be purified by applying a known method, but a sufficiently high purity substituted norbornanyl alcohol can be obtained. Therefore, in the case of using as the raw material for the second step, there is no need for purification.
The substituted norbornanyl alcohol obtained by this reaction is an isomer mixture, but can be used as a raw material for the second step without separation.

Next, the second step will be described. The second step can also be carried out in a batch reactor. The reaction conditions will be described below, but this does not prevent changes in the reaction conditions that can be easily adjusted by those skilled in the art in each reaction apparatus.
The α-substituted norbornanyl acrylate represented by the general formula [6] includes a substituted norbornanyl alcohol represented by the general formula [4] and an α-substituted acrylate anhydride represented by the general formula [5]. It can be synthesized by reacting.
The substituent R ⁴ of the α-substituted acrylic acid represented by the general formula [5] of the raw material used is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. .
These α-substituted acrylic anhydrides can be synthesized by a known method. When R ⁴ is hydrogen, methyl group or the like, it can be easily obtained as a reagent. Further, for example, when R ⁴ is CF ₃ , it can be easily synthesized by performing a CO insertion reaction (Heck reaction) using Pd as a catalyst for 2-bromo-1,1,1-trifluoropropene. Known (for example, JP-A-59-21648).

The amount of the α-substituted acrylic anhydride used in this reaction is 0.5 to 3.0 mol, preferably 0.7 to 2.0 mol, relative to 1 mol of the substituted norbornanyl alcohol. -1.6 mol is more preferable. When the amount of the α-substituted acrylic anhydride is less than 0.5 mol relative to 1 mol of the substituted norbornanyl alcohol, both the selectivity of the reaction and the yield of the target product are reduced. The amount of α-substituted acrylic anhydride not involved in the reaction increases, which is not preferable from the viewpoint of increasing the burden on the environment due to economic and waste increase.
In addition, an additive can be added to accelerate the reaction, thereby reducing the reaction temperature. Lowering the reaction temperature is effective in suppressing by-products. Additives used include organic sulfonic acids such as methanesulfonic acid, ethanesulfonic acid, p-toluenesulfonic acid, benzenesulfonic acid, and trifluoromethanesulfonic acid, and Lewis acids such as boron trifluoride, titanium tetrachloride, and tin tetrachloride. At least one acid selected from the group is preferably used.
The amount of the additive used in this reaction is 0.00005 to 0.1 g, preferably 0.0001 to 0.01 g, preferably 0.0005 to 0.005 g, relative to 1.0 g of the substituted norbornanyl alcohol as the substrate. Is more preferable. When the amount of the additive is less than 0.00005 g with respect to 1.0 g of the substituted norbornanyl alcohol of the substrate, both the conversion rate of the reaction and the yield of the target product are lowered, and if it exceeds 0.1 g, the reaction is not involved. This is economically undesirable because the amount of the additive increases.

The reaction temperature for carrying out this reaction is 0 to 200 ° C, preferably 20 to 180 ° C, more preferably 50 to 160 ° C. When the temperature is lower than 0 ° C., the reaction rate is extremely slow and it is not a practical production method. On the other hand, if it exceeds 200 ° C., the raw material α-substituted acrylic anhydride or the product α-substituted norbornanyl acrylate is polymerized, which is not preferable.
In this reaction, no solvent is preferable, but a solvent can also be used. There are no particular restrictions on the type of solvent that can be used, but aromatic compounds such as benzene, toluene, xylene, and mesitylene, ether solvents such as diethyl ether, methyl-t-butyl ether, diisopropyl ether, and tetrahydrofuran, methylene chloride, and chloroform And halogen-based solvents such as carbon tetrachloride are preferable, and these may be used alone or in combination with a plurality of solvents.
When using a solvent for this reaction, the solvent amount of the solvent to be used is 0.2-50 g with respect to 1 g of substituted norbornanyl alcohol, preferably 0.5-20 g, more preferably 1.0-10 g. preferable. When the amount of the solvent exceeds 50 g with respect to 1 g of the substituted norbornanyl alcohol, it is not economically preferable from the viewpoint of productivity.

The reaction of the present invention may be carried out in the presence of a polymerization inhibitor for the purpose of preventing polymerization of the α-substituted acrylic anhydride or the product α-substituted norbornanyl acrylate. The polymerization inhibitors used are 2,5-di-t-butylhydroquinone, 1,2,4-trihydroxybenzene, 2,5-bistetramethylbutylhydroquinone, leucoquinizarin, and nonflex F (N, N′-di- 2-naphthyl-p-phenylenediamine), nonflex H (N, N′-dinaphthyl-p-phenylenediamine), nonflex DCD (4,4′-bis (α, α′-dimethylbenzyl) diphenylamine / 4, 4 'dicumyl-diphenylamine), nonflex MBP (2,2'-methylene-bis (4-methyl-6-tert-butylphenol), ozonone 35 (N- (1-methylheptyl) -N'-phenyl-p- Phenylenediamine), phenothiazine, 2-methoxyphenothiazine, tetraethylthiuram disulfide, 1,1 At least selected from diphenyl-2-picrylhydrazyl, 1,1-diphenyl-2-picrylhydrazine, Q-1300 (N-nitrosophenylhydroxylamine), Q1301 (N-nitrosophenylhydroxylamine aluminum salt) One kind of compound is preferred.
The above polymerization inhibitor is a commercial product and can be easily obtained. The amount of the polymerization inhibitor used in the present invention is usually from 0.000005 to 0.1 mol, preferably from 0.00001 to 0.05 mol, based on 1 mol of the substituted norbonanyl alcohol as a raw material. 0001-0.03 mol is more preferable. Even if the amount of the polymerization inhibitor exceeds 0.1 mol with respect to 1 mol of the substituted norbonanyl alcohol as a raw material, there is no significant difference in the ability to prevent polymerization, which is economically undesirable.
The reactor for the reaction of the second step of the present invention is made of tetrafluoroethylene resin, chlorotrifluoroethylene resin, vinylidene fluoride resin, PFA resin, glass lined inside, glass container, or stainless steel Is preferred.

The method for carrying out this reaction is not limited. A general method is to add a solvent, a raw material substituted norbornanyl alcohol, an α-substituted acrylic anhydride and a polymerization inhibitor to a reactor that can withstand the reaction conditions, and heat the reaction from outside while stirring. . The consumption of the raw material is monitored by sampling or the like, it is confirmed that the reaction is completed, and the reaction liquid is cooled.
A sufficient amount of an aqueous potassium hydroxide solution and an extraction solvent are added to neutralize the by-produced α-substituted acrylic acid and the product α-substituted norbornanyl acrylates and dissolve in the aqueous layer, and the mixture is sufficiently stirred. The organic layer is separated, an inorganic acid is added to the aqueous layer until pH 3 is obtained, extraction is performed with an extraction solvent, and the extraction solvent is distilled off to obtain an α-substituted norbornanyl acrylate represented by the general formula [6]. Obtainable.

In this reaction, a mixture of isomers can be used as the raw material substituted norbornanyl alcohol. The reaction product in that case is also obtained as a mixture of the corresponding α-substituted norbornanyl acrylates, [6a] (R ² = RfSO ₂ NHCH ₂ — group, R ³ = H), and [6b] (R ² = H, R ³ = RfSO ₂ NHCH ₂ -group). Further, considering the exo and endo isomerism of norbornene, a mixture of 8 isomers is obtained.
In the present invention, it is possible to provide a monomer for resist as a mixture of isomers without isolating isomers. However, if there is a purpose to further increase the required performance, a single isomer should be used. Is preferably employed. In the case where only a specific isomer is isolated from these mixtures, a technique such as column chromatography can be used.
As a method for industrially obtaining a specific isomer, in the present invention, by adding a third step of recrystallizing the obtained isomer mixture with a hydrocarbon solvent, [6b] (R ² = H, R ³ = RfSO ₂ NHCH ₂ -group). The hydrocarbon solvent is not particularly limited, but pentane, hexane, heptane and the like are preferable, and hexane is particularly preferable from the viewpoint of availability.

Actually, [6a] (R ² = RfSO ₂ NHCH ₂ — group, R ³ = H) and [6b] (R ² = H, R ³ = RfSO ₂ ) obtained by the production process of an α-acrylic acid norbornene derivative. Hexane was gradually added to the isomer mixture of (NHCH ₂ -group) to precipitate crystals, followed by filtration and drying under reduced pressure to obtain not only [6b], which is one of the positional isomers, but also stereoisomerism. Physically, exo-, exo-form 5-exo-({[(trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-exo-yl 2-methylacrylate is It was selectively obtained with a purity of 99.9% (see Example 2 described below).
This time, it is possible to obtain an exo-, exo-form (see Example 3 described later) with high purity by a relatively easy method of recrystallization, which can be expected to be particularly effective due to the dissolution rate when it is made into a polymer. Thus, a single isomer can be used as a monomer for producing a polymer compound.

式中、Ｒ⁴は、水素原子、メチル基、エチル基、又は炭素数１から炭素数４のパーフルオロアルキル基であり、特に水素原子、メチル基が好ましい。
Ｒ²、Ｒ³は、いずれか一つがＲｆＳＯ₂ＮＨＣＨ₂−基（ここで、Ｒｆは、炭素数１から炭素数４のパーフルオロアルキル基を表す。）であり、残りが水素原子である。ここで、Ｒｆは、トリフルオロメチル基、パーフルオロエチル基が好ましく、特にトリフルオロメチル基が好ましい。 The polymer and copolymer of the present invention will be described in detail below.
The polymer of the present invention is obtained by polymerizing α-substituted norbornanyl acrylates represented by the above general formula [6], and is derived from α-substituted norbornanyl acrylates represented by the general formula [7]. It is a polymer having a polystyrene-reduced weight average molecular weight of 1,000 to 100,000 by gel permeation chromatography (GPC) having units.

In the formula, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and particularly preferably a hydrogen atom or a methyl group.
One of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the remainder is a hydrogen atom. Here, Rf is preferably a trifluoromethyl group or a perfluoroethyl group, and particularly preferably a trifluoromethyl group.

式［８］から式［１１］において、Ｒ⁵は水素原子、メチル基、トリフルオロメチル基あるいはヒドロキシメチル基であり、特に水素原子、メチル基が好ましい。
また、式［９］から式［１１］において、Ｒ⁶はＲ⁵とは独立にメチル基、エチル基、ｎ−プロピル基、ｉ−プロピル基、ｎ−ブチル基、ｔ−ブチル基、２−メチルプロピル基、１−メチルプロピル基、メトキシメチル基、エトキシメチル基、エトキシエチル基であり、式［１１］においては特にｔ−ブチル基が好ましい。ｎは０又は１の整数、ｍは１又は２の整数である。
式［８］から式［１１］の繰り返し単位は、それぞれ共重合体中単独で又は２種以上が存在することができる。
なお、式［８］から式［１１］の繰り返し単位は、それぞれ対応するα−置換アクリル酸誘導体の重合性不飽和結合が開裂することで得られる。 The copolymer of the present invention comprises (I) a repeating unit represented by the general formula [7] and (II) at least one repeating unit represented by the general formula [8] to the general formula [11]. It is a copolymer having a polystyrene-reduced weight average molecular weight of 1,000 to 100,000 by gel permeation chromatography (GPC).

In the formulas [8] to [11], R ⁵ is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and particularly preferably a hydrogen atom or a methyl group.
In the formulas [9] to [11], R ⁶ is independently of R ^{5 a} methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a t-butyl group, 2- A methylpropyl group, a 1-methylpropyl group, a methoxymethyl group, an ethoxymethyl group, and an ethoxyethyl group, and in the formula [11], a t-butyl group is particularly preferable. n is an integer of 0 or 1, and m is an integer of 1 or 2.
The repeating units of the formulas [8] to [11] may be present alone or in combination of two or more in the copolymer.
The repeating units of the formulas [8] to [11] can be obtained by cleaving the polymerizable unsaturated bond of the corresponding α-substituted acrylic acid derivative.

式［１２］及び式［１３］において、Ｒ⁵は、水素原子、メチル基、トリフルオロメチル基あるいはヒドロキシメチル基であり、特に水素原子、メチル基が好ましい。 Another copolymer of the present invention includes (I) a repeating unit represented by the above general formula [7], and (III) at least one repeating unit represented by the general formula [12] and the general formula [13]. It is a copolymer having a polystyrene-reduced weight average molecular weight of 1,000 to 100,000 by gel permeation chromatography (GPC).

In Formula [12] and Formula [13], R ⁵ is a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and particularly preferably a hydrogen atom or a methyl group.

In the formula [12], A represents a single bond, a linear or branched alkylene group having 1 to 10 carbon atoms, an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an alkylene glycol group, or an alkylene ester. In particular, a linear, branched or cyclic alkyl group having 1 to 10 carbon atoms is preferable. Preferable specific examples of the formula [12] include the following general formulas [12-1], [12-2], and [12-3].

In the formula [13], Z represents a divalent to tetravalent organic group. Examples of the organic group include a linear, branched, or alicyclic hydrocarbon group.
As the linear or branched hydrocarbon group, a linear or branched hydrocarbon group having 1 to 12 carbon atoms is preferable. Specific examples include methane, ethane, propane, butane, isobutane, and the like. Examples are derived divalent to tetravalent hydrocarbon groups.
The alicyclic hydrocarbon group is preferably an alicyclic hydrocarbon group having 6 to 20 carbon atoms. Specific examples thereof include cyclohexane, bicyclo [2.2.1] heptane, adamantane, and tricyclo [5.2. .1.0 ^2,6] decane, tetracyclo [6.2.1.1 ^{3,6. 0,7} ] 2-4 tetravalent alicyclic hydrocarbon group derived from dodecane.
Among the divalent organic groups represented by Z, ethane, propane, isopropane, butane, isobutane, cyclohexane, bicyclo [2.2.1] heptane, tetracyclo [6.2.1.1 ^3,6 . 0 ^2,7] a divalent to tetravalent organic group derived from dodecane are preferable.
In the formula [13], T represents a single bond or a divalent organic group having 1 to 3 carbon atoms, specifically, a divalent organic group derived from a single bond, methane, ethane, propane, isopropane or the like. A hydrocarbon group is mentioned. Among these, a single bond, a methylene group, an ethylene group and the like are preferable. Moreover, in Formula [13], n represents the integer of 1-3 and 1 or 2 is preferable.

Specific examples of the formula [13] include methacrylic acid hydroxymethyl ester, methacrylic acid 1-hydroxyethyl ester, methacrylic acid 2-hydroxyethyl ester, methacrylic acid 1-hydroxypropyl ester, methacrylic acid 2-hydroxypropyl ester, methacrylic acid. 3-hydroxypropyl ester, methacrylic acid 3-hydroxyadamantan-1-yl ester, methacrylic acid 3-hydroxyethyladamantan-1-yl ester, methacrylic acid 3,5-dihydroxyadamantan-1-yl ester, methacrylic acid 3,5 -Dihydroxyethyladamantan-1-yl ester, methacrylic acid 3,5,7-trihydroxyadamantan-1-yl ester, methacrylic acid 3,5,7-trihydroxyethyladamantane-1 Yl ester, methacrylic acid 5-hydroxybicyclo [2.2.1] heptan-2-yl ester, methacrylic acid 5-hydroxymethylbicyclo [2.2.1] heptan-2-yl ester, 5-hydroxymethyl methacrylate Bicyclo [2.2.1] heptane-2-methyl ester, methacrylic acid 8-hydroxytetracyclo [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-3-yl ester, 8-hydroxymethyltetracyclomethacrylic acid [6.2.1.1 ^3,6 . 0 ^2,7 ] dodecan-3-yl ester, 8-hydroxytetracyclomethacrylic acid [6.2.1.1 ^3,6 . 0 ^2,7] dodecane-3-methacrylic acid esters such as methyl esters.
Among these, methacrylic acid 2-hydroxyethyl ester, methacrylic acid 3-hydroxyadamantan-1-yl ester, and methacrylic acid 3-hydroxyethyladamantan-1-yl ester are preferable.
Formula [13] may be present alone or in combination of two or more in the copolymer.

When the copolymer of the present invention forms a positive photosensitive resin composition, the repeating unit (a) represented by the general formula [7] and the general formulas [9], [10] and [11] The acid dissociable group-containing repeating unit (b) represented by at least one of the above, (b), the repeating unit (a), the repeating unit (b), and the repeating unit (c) represented by the formula [8] preferable.
The ratio is 10 to 80 mol%, preferably 20 to 70 mol% of the repeating unit (b), preferably 1 to 70 mol%, preferably 3 to 70 mol% of the repeating unit (b) with respect to the total amount of all repeating units. 60 mol%: The repeating unit (C) is 0 to 60 mol%, preferably 0 to 50 mol%.
When the content of the repeating unit (a) is less than 20 mol%, the developability as a resist tends to be lowered, and when it exceeds 70 mol%, the resolution is deteriorated and the solubility in a resist solvent tends to be lowered. . If the content of the repeating unit (b) is less than 1 mol%, the resolution tends to decrease, and if it exceeds 70 mol%, the resolution tends to deteriorate, and the content of the repeating unit (c) When the rate exceeds 60 mol%, the developability tends to be lowered.

When forming a negative photosensitive resin composition, the copolymer of the present invention is represented by the repeating unit (a) represented by the general formula [7] and at least one of the formulas [12] and [13]. It is preferable that the structure includes the repeating unit (d).
The ratio is 10 to 80 mol%, preferably 20 to 70 mol% of the repeating unit (a), preferably 20 to 90 mol%, preferably 30 to 80 mol% of the repeating unit (d) with respect to all repeating units. It is.
If the content of the repeating unit (a) is less than 10 mol%, the solubility in the developer tends to deteriorate, and if it exceeds 80 mol%, the solubility of the radiation irradiated portion is too high and the resolution tends to deteriorate and swell. is there. When the content of the repeating unit (d) is less than 20 mol%, the crosslinking degree of the radiation irradiated part is insufficient and the resolution tends to deteriorate, and when the content of the repeating unit (d) exceeds 90 mol% While developability falls, it exists in the tendency for a radiation irradiation part to swell.

The polymer and copolymer of the present invention are, for example, radical polymerization of a polymerizable unsaturated monomer corresponding to each repeating unit such as hydroperoxides, dialkyl peroxides, diacyl peroxides, and azo compounds. It can manufacture by using an initiator and superposing | polymerizing in a suitable solvent in presence of a chain transfer agent as needed.
Examples of the solvent used for the polymerization include alkanes such as n-pentane, n-hexane, n-heptane, n-octane, n-nonane, and n-decane; cyclohexane, cycloheptane, cyclooctane, decalin, Cycloalkanes such as norbornane; aromatic hydrocarbons such as benzene, toluene, xylene, ethylbenzene, cumene; halogenated hydrocarbons such as chlorobutanes, bromohexanes, dichloroethanes, hexamethylene dibromide, chlorobenzene; ethyl acetate , Saturated carboxylic acid esters such as n-butyl acetate, i-butyl acetate and methyl propionate; ketones such as 2-butanone, 4-methyl-2-pentanone and 2-heptanone; tetrahydrofuran, dimethoxyethanes, diethoxy List AEs such as ethanes Can.
These solvents can be used alone or in admixture of two or more.
Moreover, the reaction temperature in the said superposition | polymerization is 40-120 degreeC normally, Preferably it is 50-90 degreeC, and reaction time is 1-48 hours normally, Preferably it is 1-24 hours.

The weight average molecular weight in terms of polystyrene (hereinafter referred to as “Mw”) by gel permeation chromatography (GPC) of the polymer and copolymer of the present invention is 1,000 to 100,000, preferably 2,000 to 70, 000, more preferably 2,000 to 20,000. In this case, if the Mw of the polymer is less than 1,000, the heat resistance when used as a resist tends to be reduced, whereas if it exceeds 100,000, the developability when used as a resist is reduced.
Further, the ratio (Mw / Mn) of Mw of the polymer or copolymer of the present invention to polystyrene-reduced number average molecular weight (hereinafter referred to as “Mn”) by gel permeation chromatography (GPC) is usually 1 to 1. 5, preferably 1-3.
The polymer and copolymer of the present invention preferably have less impurities such as halogen and metal, thereby further improving the sensitivity, resolution, process stability, pattern shape, etc. when used as a resist. . Examples of the purification method of the polymer of the present invention include chemical purification methods such as washing with water and liquid-liquid extraction, and combinations of these chemical purification methods with physical purification methods such as ultrafiltration and centrifugation. Can be mentioned.
The polymer and copolymer of the present invention are particularly suitable as a resin component of a radiation-sensitive resin composition useful as a chemically amplified resist used for fine processing by radiation such as far ultraviolet rays such as ArF excimer laser. Can be used.

  A positive radiation-sensitive resin composition can be obtained by combining the polymer or copolymer of the present invention with an acid generator which is a component that generates an acid upon irradiation with radiation, and further, a negative composition can be obtained by combining with a crosslinking agent. A type radiation sensitive resin composition is obtained.

EXAMPLES Hereinafter, although an Example demonstrates this invention in detail, this invention is not limited to these embodiments. Here, “%” of the composition analysis value represents “area%” of the organic component excluding the solvent component obtained by collecting a part of the reaction mixture and measuring by gas chromatography.
Moreover, each measurement and evaluation of the polymer and copolymer of the present invention were performed as follows.
(1) Monomer content and Mw of each polymer
In ¹² C-NMR analysis using “JNM-EX270” manufactured by JEOL Ltd., CDCL ₃ was used as a measurement solvent. In addition, Mw was monodispersed under the analysis conditions of a GPC column (2 G2000HXL, 1 G3000HXL, 1 G4000HXL) manufactured by Tosoh Corporation, with a flow rate of 1.0 ml / min, elution solvent tetrahydrofuran, and column temperature of 40 ° C. It was measured by gel permeation chromatography (GPC) using polystyrene as a standard.
(2) Dissolution rate (hereinafter referred to as DR)
Using RDA-808RB manufactured by Risotech Japan Co., Ltd., an alkaline developer of tetramethylammonium hydroxide aqueous solution (2.38%) used in a normal photoresist process was used.
(3) Dry etching resistance The test sample solution was applied onto a silicon wafer by spin coating, and dried to form a resist film having a film thickness of 500 nm using a dry etching apparatus (Pinnacle 8000) manufactured by PMT, and an etching gas. Is CF ₄ , the gas flow rate is 75 sccm, the pressure is 2.5 mTorr, the output is 2500 W, dry etching is performed, the etching rate is measured, and the relative value to the etching rate of the coating film made of the resin used in Comparative Example 1 Thus, the relative etching rate was evaluated. It means that it is excellent in dry etching tolerance, so that an etching rate is small.

Example 1
In a 500 ml three-necked flask equipped with a stirrer and a reflux condenser, 205 g (4.45 mol) of formic acid, N- (bicyclo [2.2.1] hept-5-en-2-ylmethyl) 1,1 , 1-trifluoromethanesulfonamide 113.6g (0.445mol) was put, and it heated and stirred at 130 degreeC.
After 4 hours, the composition was measured by gas chromatography. The reaction conversion rate of N- (bicyclo [2.2.1] hept-5-en-2-ylmethyl) 1,1,1-trifluoromethanesulfonamide was It was 98%. The reaction solution was cooled and then washed twice with 227 ml of water to obtain 120 g of crude 5-({[(trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-yl formate. It was. This was transferred to a 500 ml three-necked flask equipped with a stirrer and a reflux condenser, 240 ml of water, 89.3 g (1.6 mol) of potassium hydroxide and 120 g of isopropyl ether were added, and the mixture was heated and stirred at 80 ° C.
After 1 hour, the composition was measured by gas chromatography. The reaction conversion of 5-({[(trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-yl formate was 99. % Or more.

After cooling the reaction solution, the organic layer was separated into two layers, and 5% aqueous hydrochloric acid was added to the resulting aqueous layer until pH 3 was reached. It moved to the separating funnel, 120 g of isopropyl ether was added and extracted.
Isopropyl ether is distilled off from the obtained organic layer, and 1,1,1-trifluoro-N-[(5-hydroxybicyclo [2.2.1] hept-2-yl) methyl] methane, which is the target product. 105 g of sulfonamide was obtained.
When the composition was examined by gas chromatography, the purity of 1,1,1-trifluoro-N-[(5-hydroxybicyclo [2.2.1] hept-2-yl) methyl] methanesulfonamide was 99.5. % (1,1,1-trifluoro-N-[(5-exo-hydroxybicyclo [2.2.1] hept-2-exo-yl) methyl] methanesulfonamide 80.0%, other isomer 19 The yield was 85.9%.

The NMR analysis results are shown below.
¹ H-NMR (solvent: CDCl ₃ , reference material: TMS); δ1.02 (ddd, J = 4.8,4.8, 13.2, 1H), 1.24 (dddd, J = 1.3, 1.3, 1.3, 10.6, 1H), 1.31 (dd, J = 2.6, 8.7, 1H), 1.36 (ddd, J = 2.6, 4.1, 13.2, 1H), 1.52 (dd, J = 4.8, 8.7, 1H), 1.56 (dd, J = 3.0, 10.5 , 1H), 1.67 (dd, J = 6.4, 13.2, 1H), 2.14 (d, J = 4.1, 1H), 2.18 (d, J = 4.5, 1H), 3.04 (m, 1H), 3.07 (m, 1H), 3.78 (dd, J = 2.6, 6.4, 1H), 5.23 (m, 1H), 7.95 (s, 1H)
¹⁹ F-NMR (solvent: CDCl ₃ , reference material: CCl ₃ F); δ-77.7 (s, 3F)

Example 2
In a 500 ml three-necked flask equipped with a stirrer and a reflux condenser, 78.7 g (0.42 mol) of methacrylic anhydride, 0.10 g (1.0 mmol) of methanesulfonic acid, 1,1,1 -Trifluoro-N-[(5-hydroxybicyclo [2.2.1] hept-2-yl) methyl] methanesulfonamide (105 g, 0.39 mol) and nonflex MBP (0.05 g) were added at 80 ° C. And stirred with heating.
After 3 hours, the composition was measured by gas chromatography, whereby 1,1,1-trifluoro-N-[(5-hydroxybicyclo [2.2.1] hept-2-yl) methyl] methanesulfonamide was reacted. The conversion rate was 99% or more. After cooling the reaction solution, a solution consisting of 50 g (0.9 mol) of potassium hydroxide and 200 ml of water was added and stirred well, and then 150 g of isopropyl ether was added to separate the two layers. To the obtained aqueous layer, 5% aqueous hydrochloric acid was added until pH 3 was reached. It moved to the separating funnel, 150 g of isopropyl ether was added and extracted.
Isopropyl ether was distilled off from the obtained organic layer, and 5-({[(trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-yl 2-methyl acrylate and 6- ( A mixture of {[(trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-yl 2-methyl acrylate was obtained.
Hexane was gradually added to this mixture to precipitate crystals, and after filtration, dried under reduced pressure, 53.3 g of crystals were obtained. The composition was examined by NMR and gas chromatography, and was found to be 99.9% pure 5-exo-({[(trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-exo-yl. It was 2-methyl acrylate. The yield was 40%.

The NMR analysis results are shown below.
¹ H-NMR (solvent: CDCl ₃ , reference material: TMS); δ 0.57 (ddd, J = 2.2, 4.6, 13.2, 1H), 0.85 (ddd, J = 1.2, 2.4, 10.6, 1H), 0.96 ( ddd, J = 2.2, 8.5, 13.2, 1H), 1.08 (m, 1H), 1.25 (m, 1H), 1.28 (ddd, J = 1.2, 3.0, 3.9 ,, 1H), 1.46 (ddd, J = 1.2 , 2.4, 7.1, 1H), 1.72 (m, 1H), 1.80 (dd, J = 1.5, 1.7, 3H), 2.09 (m, 1H), 2.50 (dd, J = 7.2, 13.2, 1H), 2.62 ( m, 1H), 4.53 (ddd, J = 1.2, 3.0, 7.1, 1H), 5.11 (dd, J = 5.3, 5.6, 1H), 5.22 (dd, J = 1.7, 1.7, 1H), 6.07 (dd, (J = 1.5, 1.7, 1H)
¹⁹ F-NMR (solvent: CDCl ₃ , reference material: CCl ₃ F); δ-77.8 (s, 3F)

Examples 3-6, Comparative Example 1
5-({[(Trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-yl 2-methyl acrylate and 6-({[(trifluoromethyl ) Sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-yl 2-methyl acrylate monomer (hereinafter referred to as M-1), and 5-exo-({ [(Trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-exo-yl 2-methyl acrylate (hereinafter referred to as M-2) as a single monomer is used for the following polymerization reaction. went. The monomers used are shown below.

  Monomer [M-1] to Monomer [M-4] are mixed so as to have a total amount of 30 g at the charged molar ratio shown in Table 1, and dissolved in 60 g of 2-butanone. A solution prepared by adding 1.46 g of azobisisobutyronitrile is purged with nitrogen for 10 minutes and prepared in a dropping funnel. Place 60 g of 2-butanone into a 500 ml three-necked flask and purge with nitrogen for 10 minutes. After purging with nitrogen, the inside of the three-necked flask was immersed in an oil bath while stirring with a magnetic stirrer and maintained at 80 ° C., and the prepared solution was dropped into the dropping funnel over 3 hours, and further heated for 3 hours. After completion of the polymerization, the polymerization solution is cooled to 30 ° C. or less by water cooling, charged into 1000 g of n-heptane, and the precipitated white powder is separated by filtration. The filtered white powder was dissolved in 100 g of 2-butanone, poured into 1000 g of n-heptane, washed by repeated filtration and collected three times, filtered, dried at 50 ° C. for 17 hours, A white powder polymer and copolymer were obtained. The polymerization results and the properties of the polymer and copolymer are shown in Table 1.

表１に示すように、モノマー（Ｍ−１）、（Ｍ−２）双方共に酸性アミド基の効果である溶解速度は得られるが、単一モノマー（Ｍ−２）にした場合、より高い溶解効果が発現する。また、モノマー（Ｍ−１）、（Ｍ−２）双方共にモノマー（Ｍ−４）に対して高いドライエッチング耐性を有する。

As shown in Table 1, both the monomers (M-1) and (M-2) have a dissolution rate that is an effect of the acidic amide group, but higher solubility is obtained when a single monomer (M-2) is used. The effect is manifested. Further, both the monomers (M-1) and (M-2) have high dry etching resistance to the monomer (M-4).

Examples 7-12, Comparative Examples 2-3
The following [M-2] and [M-5] to [M-9] were mixed at a charging molar ratio shown in Table 2 so that the total amount was 30 g, and dissolved in 60 g of 2-butanone. A solution prepared by adding 1.46 g of 2,2-azobisisobutyronitrile is purged with nitrogen for 10 minutes, and placed in a dropping funnel. Put 60 g of 2-butanone into a 500 mL three-necked flask and purge with nitrogen for 10 minutes. After purging with nitrogen, the inside of the three-necked flask was immersed in an oil bath while stirring with a magnetic stirrer and kept at 80 ° C., and the prepared solution was dropped into the dropping funnel over 3 hours, and further heated for 3 hours. After completion of the polymerization, the polymerization solution is cooled to 30 ° C. or less by cooling with water, charged into 1000 g of n-heptane, and the precipitated white powder is separated by filtration. The filtered white powder was dissolved in 100 g of 2-butanone, poured into 1000 g of n-heptane, washed by repeated filtration and collected three times, filtered, dried at 50 ° C. for 17 hours, A white powder copolymer was obtained. The polymerization results are shown in Table 2.

  The fluorine-containing polymer and copolymer obtained by polymerizing novel α-substituted norbornanyl acrylates have high transparency in a wide wavelength range from the ultraviolet region to the near infrared region, and are applied to the substrate. It is expected to be a resist material having both high adhesion and film-forming properties and high etching resistance. Moreover, the fluorine-containing polymer compound of the present invention is expected as a suitable semiconductor device package material.

Claims (14)

General formula [4]

[In the formula, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the remainder is hydrogen. Is an atom. ] The substituted norbornanyl alcohol represented by this.   The substituted norbornanyl alcohol according to claim 1, wherein Rf is a trifluoromethyl group. General formula [1]

[Wherein, R ¹ represents a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. A lower carboxylic acid represented by the general formula [2]

[Wherein, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the rest It is a hydrogen atom. And a substituted norbornene represented by the general formula [3]

Wherein, R ¹ is the same as R ¹ in the general formula [1], R ^2, R ³ is the general formula [2] R ^2, R ³ identical] to give a substituted norbornanyl compound represented by, This is hydrolyzed and is represented by the general formula [4]

[Wherein, R ^2, R ³ is any one that RfSO ₂ NHCH ₂ - group (., Where, Rf is selected from the group consisting of a carbon number of 1 represents a perfluoroalkyl group having 4 carbon atoms), and the remainder is hydrogen Is an atom. ] The manufacturing method of substituted norbornanyl alcohol represented by these. General formula [6]

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group ( Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. Α-substituted norbornanyl acrylates represented by the formula: The α-substituted norbornanyl acrylate according to claim 4, wherein R ² is a hydrogen atom and R ³ is a CF ₃ SO ₂ NHCH ₂ -group.   In Claim 5, alpha-substituted norbornanyl acrylate is 5-exo-({[(trifluoromethyl) sulfonyl] amino} methyl) bicyclo [2.2.1] hept-2-exo-yl 2-methyl. Α-Substituted norbornanyl acrylates which are acrylates. General formula [6] consisting of the following two steps

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group ( Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. ] The manufacturing method of the alpha-substituted norbornanyl acrylate represented by this.
First step: General formula [1]

[Wherein, R ¹ represents a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. A lower carboxylic acid represented by the general formula [2]

[Wherein, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the rest It is a hydrogen atom. And a substituted norbornene represented by the general formula [3]

[Wherein, R ¹ represents a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is RfSO ₂ NHCH ₂ — A group (wherein Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the remainder is a hydrogen atom. Substituted norbornenes represented by general formula [4] are obtained by hydrolysis.

[In the formula, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the remainder is hydrogen. Is an atom. ] The process of manufacturing substituted norbornanyl alcohol represented by these.
Second step: General formula [5]

[Wherein, R ⁴ represents a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms. An α-substituted acrylic anhydride represented by the general formula [4] obtained in the first step.

[In the formula, any one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group (where Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms), and the remainder is hydrogen. Is an atom. And a substituted norbornanyl alcohol represented by the general formula [6]

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group ( Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. ] The process of manufacturing the alpha-substituted norbornanyl acrylate represented by this. The method for producing an α-substituted norbornanyl acrylate according to claim 7, wherein R ⁴ is a hydrogen atom or a methyl group. The method for producing an α-substituted norbornanyl acrylate according to claim 7 or 8, wherein Rf is a trifluoromethyl group.   The method for producing an α-substituted norbornanyl acrylate according to any one of claims 7 to 9, wherein the second step is performed in the presence of an additive comprising an organic sulfonic acid and / or a Lewis acid.   A method for producing an α-substituted norbornanyl acrylate, wherein a third step of recrystallization with a hydrocarbon solvent is further performed after the production step of claim 7. General formula [7]

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group. Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. ] The polymer whose polystyrene conversion weight average molecular weights are 1,000-100,000 by the gel permeation chromatography (GPC) which has a repeating unit derived from (alpha) -substituted norbornanyl acrylate represented by these. (I) General formula [7]

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group. Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. A repeating unit derived from an α-substituted norbornanyl acrylate represented by:
(II) From general formula [8] to general formula [11]

[In the formulas [8] to [11], R ⁵ represents a hydrogen atom, a methyl group, a trifluoromethyl group or a hydroxymethyl group, and in the formulas [9] to [11], R ⁶ represents R ⁵ and Are independently methyl, ethyl, n-propyl, i-propyl, n-butyl, t-butyl, 2-methylpropyl, 1-methylpropyl, methoxymethyl, ethoxymethyl, ethoxy Represents an ethyl group, n represents an integer of 0 to 1, and m represents an integer of 1 to 2, respectively. ] The copolymer whose polystyrene conversion weight average molecular weight is 1,000-100,000 by the gel permeation chromatography (GPC) which has at least 1 repeating unit represented by these. (I) General formula [7]

[Wherein, R ⁴ is a hydrogen atom, a methyl group, an ethyl group, or a perfluoroalkyl group having 1 to 4 carbon atoms, and one of R ² and R ³ is an RfSO ₂ NHCH ₂ — group. Here, Rf represents a perfluoroalkyl group having 1 to 4 carbon atoms, and the remainder is a hydrogen atom. A repeating unit derived from an α-substituted norbornanyl acrylate represented by:
(III) General formula [12] and General formula [13]

[In Formula [12] and Formula [13], R ⁵ represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group. In Formula [12], A is a single bond, having 1 to carbon atoms. 10 represents a linear or branched alkylene group or an alicyclic hydrocarbon group having 4 to 20 carbon atoms, an alkylene glycol group, or an alkylene ester group. In the formula [13], Z is a divalent to tetravalent group. T represents an organic group, T represents a single bond or a divalent organic group having 1 to 3 carbon atoms, and p represents an integer of 1 to 3. ] The copolymer whose polystyrene conversion weight average molecular weight is 1,000-100,000 by the gel permeation chromatography (GPC) which has at least 1 repeating unit represented by these.