TW201634454A - Novel alicyclic ester compound, (meth)acrylic copolymer, and functional resin composition containing same - Google Patents

Abstract

As a chemically amplified resist, the present invention provides a resist and compound having a good balance by which line edge roughness (LER) is improved without impairing basic physical properties inherent in a resist, such as base adhesion properties and resistance to dry etching. Provided are a lactone ester compound represented by general formula (1), a method for producing same, a (meth)acrylic copolymer comprising general formula (1), and a photosensitive resin composition containing same. (In formula (1): R1 denotes a hydrogen atom or a methyl group; R2 denotes a hydrogen atom, an aliphatic alkyl group having 1-10 carbon atoms or an alkyl group having an alicyclic structure having 3-10 carbon atoms; R3 denotes a hydrogen atom, an alkoxycarbonyl group represented by formula (2), an aliphatic alkyl group having 1-10 carbon atoms or an alkyl group having an alicyclic structure having 3-10 carbon atoms; here, R2 and R3 may bond to each other to form an alicyclic structure having 3-10 carbon atoms; and n1 is an integer between 0 and 2.) (In formula (2): R4 denotes an aliphatic alkyl group having 1-13 carbon atoms or an alkyl group having an alicyclic structure having 3-13 carbon atoms; and the dotted line denotes the bonding location in the compound represented by formula (1)).

Description

Novel alicyclic ester compound, (meth)acrylic copolymer, and functional resin composition containing the same

The present invention relates to a novel lactone (meth) acrylate compound suitable for KrF and ArF, F2 excimer laser photoresist, or chemically amplified photoresist materials for X-ray, electron beam, EUV (extreme ultraviolet light), A (meth)acrylic copolymer comprising the novel compound, and a photosensitive resin composition comprising the copolymer.

While the market for memory devices with memory devices has increased, or video sensors for high-resolution cameras for mobile phones or smart phones have expanded, semiconductor devices have a strong desire for further miniaturization. Photolithography is widely used in the manufacture of various electronic devices. In photolithography, miniaturization has been promoted to date by shortening the wavelength of the light source. As a light source, when a short-wavelength light source such as a KrF excimer laser is used, a chemically amplified photoresist is generally used, and a chemically amplified photoresist which is generally used as a solution contains a functional resin of a main component, and a photoacid. Producer, as well as several additives. Among them, the functional resin of the main agent has excellent etching resistance, substrate adhesion, and light source for use. The characteristics of characteristics such as transparency and development speed are extremely important, and the photoresist performance is determined.

The functional resin used for the excimer laser photoresist is generally a polymer having a vinyl compound or an acrylate as a repeating unit. For example, in the photoresist for KrF excimer laser lithography, a hydroxystyrene resin (Patent Document 1) and an ArF excimer laser lithography photoresist have been proposed, and an adamantyl group (methyl group) has been proposed. Acrylate is an acrylic resin which is a basic skeleton (Patent Documents 2 to 6).

In recent years, the lithography process has been further refined, ArF excimer laser lithography has been exposed to immersion exposure, and continuous double-pattern exposure has continued to progress. In addition, we continue to develop various types of lithography using extreme ultraviolet light (EUV), or direct drawing and negative-type imaging under the electron line, which are attracting attention as the next-generation lithography technology. Under such circumstances, it is desired to develop novel functional monomers suitable for miniaturization.

Along with the reduction in circuit width due to miniaturization, the influence on the edge roughness (LER) caused by the diffusion of acid generated by the photoacid generator after exposure gradually becomes more profound. Therefore, in order to prevent the deterioration of LER, a method of controlling acid diffusion is discussed. As an example, a method of using a photoacid generator having a structure having a large skeleton (Non-Patent Document 1) and a method of using a resin containing a monomer having a photoacid generator have been proposed (Patent Document 7 and Non-Patent Document 2) And a method of extending the side portion of the photoresist polymer to be longer than the conventional one, and further inhibiting the diffusion path of the acid (Patent Documents 8 and 9).

However, in order to correspond to more miniaturization, the photoresist is in performance. The improvement is even more indispensable. Although the high-sensitivity ‧ high resolution photoresist is required, if the sensitivity is only increased, the resin that controls the acid diffusion, or the like, may cause a new problem such as a decrease in resolution or a deterioration in LER. The combination with various photoacid generators has also been reviewed and further improved.

[Previous Technical Literature] [Patent Literature]

[Patent Document 1] Japanese Patent Laid-Open Publication No. 2006-243474

[Patent Document 2] Japanese Patent Laid-Open No. 4-39665

[Patent Document 3] Japanese Patent Laid-Open No. Hei 10-319595

[Patent Document 4] Japanese Patent Laid-Open Publication No. 2000-26446

[Patent Document 5] Japanese Patent Laid-Open Publication No. 2003-167346

[Patent Document 6] Japanese Patent Laid-Open Publication No. 2004-323704

[Patent Document 7] Japanese Patent Laid-Open Publication No. 2012-168502

[Patent Document 8] Japanese Patent Laid-Open Publication No. 2005-331918

[Patent Document 9] Japanese Patent Laid-Open Publication No. 2008-129388

[Non-patent literature]

[Non-Patent Document 1] SPIE, 8325-10 (2012)

[Non-Patent Document 2] SPIE, 8322-07 (2012)

[Non-Patent Document 3] Bioorg. Med. Chem Lett. 19 (2009) 3848-3851

[Non-Patent Document 4] Angew. Chem. Int. Ed. 2011, 50, 5331-5334

[Non-Patent Document 5] Angew. Chem. Int. Ed. 2011, 123, 5443-5446

In view of such circumstances, the object of the present invention is to develop a photoresist material for KrF excimer laser, ArF excimer laser, F2 excimer laser, X-ray, electron beam, and EUV lithography without damaging sensitivity. , resolution, substrate adhesion, and etch resistance, which can improve the line edge roughness (LER) photoresist, and provide technically ideal functionality for future enhancement of the integrated density of semiconductor substrate circuits. Resin composition.

For the purpose of solving the above problems, the inventors of the present invention have found through KrF excimer laser, ArF excimer laser, F2 excimer laser, X-ray, electron beam or EUV (extreme ultraviolet light). In the lithography operation performed, a lactone (meth) acrylate compound having a specific structure is a useful compound capable of forming a fine pattern. That is, the present invention is as follows.

A lactone (meth) acrylate compound which is represented by the general formula (1).

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group; R ² represents hydrogen, an aliphatic alkyl group having 1 to 10 carbon atoms, or an alkyl group having an alicyclic structure having 3 to 10 carbon atoms; and R ³ represents Hydrogen, an alkoxycarbonyl group represented by the formula (2), an aliphatic alkyl group having 1 to 10 carbon atoms, or an alkyl group having an alicyclic structure having 3 to 10 carbon atoms; in this case, R ² and R ³ may also be used. Combine with each other to form an alicyclic structure with a carbon number of 3 to 10; n ₁ represents an integer of 0 to 2.)

(In the formula (2), R ⁴ represents an aliphatic alkyl group having 1 to 13 carbon atoms or an alkyl group having an alicyclic structure having 3 to 13 carbon atoms; and a broken line indicates a bond in the compound of the formula (1).)

2. A system of lactone (meth) acrylate compounds such as 1. The method of producing a method of reacting a hydroxylactone compound represented by the general formula (4) with a (meth)acrylic compound represented by the general formula (5).

(In the formula (4), R ² , R ³ and n ₁ are the same as the general formula (1).)

(In the formula (5), R ¹ is the same as in the general formula (1). Further, R ⁵ is a group selected from the group consisting of a hydroxyl group, a halogen atom, and a (meth)acryloxy group.

A (meth)acrylic copolymer having a repeating unit represented by the general formula (6).

(In the formula (6), the same as (1) the R ¹ ~ R ³ and n1-based formula, * represents a binding site-based repeating unit adjacent to the place.)

4. The (meth)acrylic copolymer as in 3., which further has either or both of the repeating units represented by the general formula (7) or (8), and the repeating unit represented by the general formula (9) .

(In the formula (7), R ²¹ represents hydrogen or a methyl group, R ²² represents an alkyl group having 1 to 4 carbon atoms, and R ²³ represents a cycloalkyl group having 5 to 20 carbon atoms or an alicyclic alkyl group, and * points indicate The junction of adjacent repeating units.)

(In the formula (8), R ⁴¹ represents hydrogen or a methyl group, R ₄₂ to R ₄₃ represent an alkyl group having the same or different carbon number of 1 to 4, and R ₄₄ represents an alkyl group having a carbon number of 1 to 4; Or a group of cycloalkyl or alicyclic alkyl groups having 5 to 20 carbon atoms, and * dots represent the combination with adjacent repeating units.)

(In the formula (9), R ⁴¹ represents hydrogen or a methyl group, and R ⁴² to R ⁴⁴ represent a group which may be the same or different selected from the group consisting of hydrogen element, hydroxyl group, methyl group, and ethyl group, * point system Indicates the combination with the adjacent repeating unit.)

5. The (meth)acrylic copolymer according to 4., which comprises 20 to 80 mol% of the repeating unit represented by the above general formula (6), and includes the above-mentioned general formulas (7) and (8) in total. The repeating unit is 20 to 80 mol%, and includes 10 to 50 mol% of the repeating unit represented by the above general formula (9).

A photosensitive resin composition comprising the (meth)acrylic copolymer and the photoacid generator according to any one of 3. to 5.

The lactone (meth) acrylate compound of the present invention is suitable as a raw material of various resin compositions such as various functional polymers having heat resistance, surface hardness, chemical resistance, and lipophilicity. The lactone (meth) acrylate compound of the present invention is particularly useful as a chemical increase for KrF excimer lasers, ArF excimer lasers, F2 excimer lasers, X-rays, electron beams, and EUVs (extreme ultraviolet rays). When the composition of the copolymer of the photoresist is used, the line edge roughness (LER) can be improved without impairing the etching resistance or the substrate adhesion.

Hereinafter, the present invention will be described in more detail. The lactone (meth) acrylate compound of the present invention is represented by the general formula (1).

(In the formula (1), R ¹ represents a hydrogen atom or a methyl group; and R ² represents an aliphatic alkyl group having 1 to 10 carbon atoms or an alkyl group having an alicyclic structure having 3 to 10 carbon atoms, preferably R ² is An aliphatic alkyl group having 1 to 5 carbon atoms or an alkyl group having an alicyclic structure having 3 to 8 carbon atoms, more preferably R ² is an aliphatic alkyl group having 1 to 3 carbon atoms or a fat having 5 to 7 carbon atoms. An alkyl group having a ring structure; R ³ represents an alkoxycarbonyl group represented by the formula (2), an aliphatic alkyl group having 1 to 10 carbon atoms (preferably 1 to 5 carbon atoms), or a carbon number of 3 to 10 ( Preferably, it is an alkyl group having an alicyclic structure of 5 to 8 carbon atoms; in this case, R ² and R ³ may be bonded to each other to form an alicyclic structure having a carbon number of 3 to 10, preferably a carbon number of 5 to 8 The alicyclic structure; n ₁ represents an integer from 0 to 2.)

(In the formula (2), R ⁴ represents an aliphatic alkyl group having 1 to 13 carbon atoms or an alkyl group having an alicyclic structure having 3 to 13 carbon atoms, preferably R ⁴ is an aliphatic alkane having 2 to 8 carbon atoms. a base or an alkyl group having an alicyclic structure having a carbon number of 5 to 10; a broken line indicating a bond with a compound of the formula (1).

The lactone (meth) acrylate compound (1) of the present invention can be specifically exemplified as described below. However, it is not limited to these.

(In the formula (12), R ¹ is a hydrogen atom or a methyl group. Further, R ³ is as exemplified below.)

Further, the dotted line in the formula (13) represents a bond with the compound of the formula (12).

The method for producing a lactone (meth) acrylate compound represented by the general formula (1) of the present invention may, for example, be a reduction reaction of a ketolactone compound represented by the general formula (3). The hydroxylactone compound represented by the general formula (4) is obtained and then reacted with the (meth)acrylic acid compound represented by the general formula (5), but it is not limited thereto.

(In the formula (3), R ² , R ³ and n ₁ are the same as those in the general formula (1).)

(In the formula (4), R ² , R ³ and n ₁ are the same as those in the general formula (1).)

(In the formula (5), R ¹ is the same as in the general formula (1). Further, R ⁵ is a group selected from the group consisting of a hydroxyl group, a halogen atom, and a (meth)acryloxy group, and is preferably a group. For example, a halogen atom such as chlorine.)

The ketolide compound represented by the general formula (3) of the present invention is exemplified below.

(In the formula (14), the R ³ system is the same as in the general formula (1).)

Among these compounds, 1-oxaspiro[4.5]indole-2,6-dione, 7-methyl-1-oxaspiro[4.5]癸-2,6- is used in terms of ease of availability. Diketone, 9-methyl-1-oxaspiro[4.5]indole-2,6-dione, 1-oxaspiro[4.4]indole-2,6-dione, 1-oxaspiro[4.6] The undecane-2,6-dione and the third-stage butyl 2-ethylindenyl-5-oxotetrahydrofuran-2-carboxylate are preferably used, for example, according to Non-Patent Documents 3 to 5. Synthesize the synthesizer.

The hydroxylactone compound represented by the general formula (4) of the present invention can be exemplified as follows.

(In the formula (15), the R ³ system is the same as in the general formula (1).)

The (meth)acrylic compound represented by the general formula (5) of the present invention is exemplified below.

From the viewpoint of the reactivity, it is preferable to use (meth)acrylic acid chloride as a commercially available product, for example, a chlorinated acrylonitrile group (type A0147) manufactured by Tokyo Chemical Industry Co., Ltd., and a methyl chloride group can be obtained. Acrylate based (model M0556) and the like.

Next, a method for producing a lactone (meth) acrylate compound represented by the general formula (1) will be described in detail.

First, the reduction reaction of the ketone lactone compound represented by the general formula (3) will be described. This reaction employs a known reduction reaction, but it is preferred because the reaction by the reduction of the hydride is easy and the yield is good. The reducing agent is added in an amount of from 0.5 to 5.0 mol equivalents, preferably from 0.6 to 3.0 mol equivalents, more preferably from 0.8 to 1.5 mol equivalents, relative to the ketone lactone compound. If it is in the above range, the reaction can be sufficiently carried out, and the yield of the hydroxylactone compound represented by the general formula (4) of the object is also high, which is economically preferable.

As the compound which can be used as a reducing agent, a commercially available product which can be generally obtained can be used. For example, sodium borohydride, hydrogenated triethylborohydride, hydrogenated tri(secondary butyl)borohydride, hydrogenated tri(secondary butyl)borohydride, lithium borohydride, lithium aluminum hydride, hydrogenation double (2-methoxyethoxy)aluminum sodium, diborane, diisobutylaluminum hydride, and the like.

A commercially available product which can be generally obtained can be used as the solvent, and various solvents such as an alcohol, an ether, a hydrocarbon, and a halogen-based solvent can be suitably used insofar as the reaction is not inhibited.

When a reducing agent such as sodium borohydride having a low reducing power is used, an alcohol solvent is preferable, and when a reducing agent such as lithium aluminum hydride having a high reducing power is used, a dehydrating solvent is preferably used. The amount of the solvent is from 1 to 100 parts by mass, preferably from 5 to 10 parts by mass, per part by mass of the ketolide compound represented by the general formula (3).

The reaction temperature and the reaction time are dependent on the concentration of the substrate or the catalyst to be used. Generally, the reaction temperature is -20 ° C to 100 ° C, the reaction time is 1 hour to 10 hours, and the pressure is carried out under normal pressure, reduced pressure or under pressure. Moreover, the reaction system can be suitably selected from batch, semi-batch, continuous, etc. The method of knowing is implemented.

Next, the reaction of the hydroxylactone compound represented by the general formula (4) with the (meth)acrylic compound represented by the general formula (5) will be described.

This reaction can be suitably carried out by an acid anhydride method using (meth)acrylic anhydride or a known esterification reaction by esterification of a dehydrating condensing agent using an acid halide method of (meth)acrylic acid.

However, it is preferred to use an acid anhydride method using (meth)acrylic anhydride or a acid halide method using (meth)acrylic acid chloride, which can be found to inhibit side reactions such as decomposition of an alkoxycarbonyl group bonded to a lactone group. . Further, after the reduction reaction, the ketolide compound represented by the general formula (3) does not separately separate the hydroxylactone compound represented by the general formula (4), and is represented by the general formula (5) ( The reaction of the methyl)acrylic acid compound can still obtain the lactone (meth) acrylate compound of the general formula (1).

With respect to the hydroxylactone compound represented by the general formula (4), the (meth)acrylic compound represented by the general formula (5) is used in an amount of from 0.5 to 100 mol equivalents, preferably from 1 to 20 mol equivalents, more preferably. Use 1.2 to 5 molar equivalents. If it is within the range, the reaction can be sufficiently carried out, and the yield of the lactone (meth) acrylate compound represented by the general formula (1) of the object is also high, which is economically preferable.

The lactone represented by the general formula (1) is obtained by reacting the hydroxylactone compound represented by the general formula (4) of the present invention with the (meth)acrylic compound represented by the general formula (5). As the solvent used for the acrylate compound, a commercially available product which can be generally obtained can be used. In the range which does not inhibit the above reaction, for example, an alcohol, an ether, a hydrocarbon, or a halogen solvent can be suitably used. And a variety of solvents. Since water hinders the reaction, it is preferred to use a dehydrating solvent.

The reaction temperature and reaction time are dependent on the substrate concentration or the catalyst used, but generally can be carried out at a reaction temperature of -20 ° C to 100 ° C, a reaction time of 1 hour to 10 hours, and a pressure under normal pressure, reduced pressure or under pressure. . Further, the reaction can be carried out by a known method such as batch type, semi-batch type, or continuous type.

Further, a polymerization inhibitor may be added to a series of reactions, and a commercially available product which can be generally obtained can be used. For example, 2,2,6,6-tetramethyl-4-hydroxypiperidin-1-yloxy, N-nitrosophenylhydroxylamine ammonium salt, N-nitrosophenylhydroxylamine aluminum salt , N-nitroso-N-(1-naphthyl)hydroxylamine ammonium salt, N-nitrosodiphenylamine, N-nitroso-N-methylaniline, nitros naphthol, p- a nitroso compound such as nitrosophenol, N,N'-dimethyl-p-nitrosoaniline, a sulfur-containing yellow compound such as phenothiazine, methylene blue or 2-mercaptobenzimidazole, N, N' -diphenyl-p-phenylenediamine, N-phenyl-N'-isopropyl-p-phenylenediamine, 4-hydroxydiphenylamine, amine phenol, etc., hydroxyl group Quinoline, hydroquinone, methylhydroquinone, p-benzoquinone, hydroquinone monomethyl ether, etc., p-methoxyphenol, 2,4-dimethyl-6-t-butylphenol, Phenols such as catechol, 3-s-butylcatechol, 2,2-methylenebis-(6-t-butyl-4-methylphenol), N-hydroxyimine, etc. Examples of the quinones such as imines, cyclohexane oxime, p-fluorene dioxime, and dialkylthiodipropionates. The amount of addition is 0.001 to 10 parts by mass, preferably 0.01 to 1 part by mass, per 100 parts by mass of the (meth)acrylic compound represented by the general formula (5).

a lactone represented by the general formula (1) obtained by the reaction (A) The acrylate compound can be isolated or purified by a known purification method, that is, filtration, concentration, distillation, extraction, crystallization, recrystallization, column chromatography, activated carbon, or the like, or a combination thereof. In the method, the purification is performed as a high purity monomer as desired.

The (meth)acrylic acid copolymer can be obtained by copolymerizing a lactone (meth) acrylate compound represented by the general formula (1) of the present invention. The (meth)acrylic copolymer is a functional resin used for photoresist.

The (meth)acrylic copolymer of the present invention has a repeating unit represented by the general formula (6) derived from the general formula (1). Further, it is preferable since the copolymer containing at least one kind of the repeating unit represented by the general formulas (7) to (8) and the repeating unit represented by the general formula (9) can improve the resist performance. Further, the (meth)acrylic copolymer may contain a structure represented by the general formula (9) or the general formulas (10) to (11) as a repeating unit.

(In the formula (6), R ¹ to R ³ and n ₁ are the same as in the formula (1), and the * point indicates the combination with the adjacent repeating unit.)

(In the formula (7), R ²¹ represents hydrogen or a methyl group, R ²² represents an alkyl group having 1 to 4 carbon atoms, and R ²³ represents a cycloalkyl group or an alicyclic alkyl group having 5 to 20 carbon atoms; The combination with the adjacent repeating unit.)

Preferably, R ²² represents an alkyl group having 1 to 3 carbon atoms, and R ²³ represents a cycloalkyl group having 5 to 10 carbon atoms or an alicyclic alkyl group.

(In the formula (8), R ³¹ represents hydrogen or a methyl group, and R ³² to R ³³ are the same or may be an alkyl group having a carbon number of 1 to 4, and R ³⁴ represents an alkyl group selected from a carbon number of 1 to 4. a group of a group of a cycloalkyl group or an alicyclic alkyl group having 5 to 20 carbon atoms, and any two of R ³² to R ³⁴ may be bonded to each other to form an alicyclic structure having a carbon number of 2 to 20, * The point system indicates the combination with the adjacent repeating unit.)

Preferably, R ²² represents an alkyl group having 1 to 3 carbon atoms, and R ²³ is a cycloalkyl group having 5 to 10 carbon atoms or an alicyclic alkyl group. Further, the alicyclic structure may include a plurality of rings such as an adamantyl group.

(In the formula (9), R ⁴¹ represents hydrogen or a methyl group, and R ⁴² to R ⁴⁴ are the same or may be a group different from a group selected from a hydrogen element, a hydroxyl group, a methyl group or an ethyl group, * point It is the combination with the adjacent repeating unit.)

(In the formula (10), R ⁵¹ represents hydrogen or a methyl group, R ⁵² represents a methyl group, an ethyl group, n ₅₁ represents 0 to 2, n ₅₂ represents 1 to 3, and * points represent a combination with an adjacent repeating unit. .)

(In the formula (11), R ⁶¹ represents hydrogen or a methyl group, R ⁶² represents a methylene group (-CH ₂ -) or an oxa (-O-) group, and R ⁶³ is the same or may be a hetero-hydroxy group or a halogen. a group, a nitrile group, a carboxylic acid group, a carboxylic acid alkyl group having 1 to 4 carbon atoms, an alkoxide group having 1 to 4 carbon atoms, n ₆₁ representing 0 to 2, and * points indicating a combination with adjacent repeating units .)

The monomer raw material of the repeating unit represented by the general formula (7) may, for example, be 2-methyl-2-(methyl)propenyloxyadamantane or 2-ethyl-2-(methyl)propene. Alkoxyadamantane, 2-isopropyl-2-(methyl)propene decyloxyadamantane, 2-n-propyl-2-(methyl)propene decyloxyadamantane, 2-n-butyl 2-(methyl)propenyloxy adamantane, 1-methyl-1-(methyl)propenyloxycyclopentane, 1-ethyl-1-(methyl)propenyloxy ring Pentane, 1-methyl-1-(methyl)propenyloxycyclohexane, 1-ethyl-1-(methyl)propenyloxycyclohexane, 1-methyl-1-(A) Acryloxycycloheptane, 1-ethyl-1-(methyl)propenyloxycycloheptane, 1-methyl-1-(methyl)propenyloxycyclooctane, 1- Ethyl-1-(methyl)propenyloxycyclooctane, 2-ethyl-2-(methyl)propenyloxyl-hydrogen-1,4:5,8-dimethylnaphthalene, 2- Ethyl-2-(methyl) propylene decyloxydecane and the like. Commercial products can be used for these single systems, and products of Osaka Organic Chemical Industry Co., Ltd. can be easily obtained.

The monomer raw material of the repeating unit represented by the general formula (8) may, for example, be 2-cyclohexyl-2-(methyl)propenyloxypropane or 2-(4-methylcyclohexyl)-2- (Meth)propylene oxypropane, 2-adamantyl-2-(methyl)propenyloxypropane, 2-(3-(1-hydroxy-1-methylethyl)adamantyl)- 2-(Methyl) propylene decyloxypropane or the like. These single systems can be used as commercially available products, and products such as Dell products can be easily obtained.

The monomer raw material which is a repeating unit represented by the general formula (9) may, for example, be 1-(meth)acryloxylated adamantane or 3-hydroxy-1-(methyl)propenyloxyadamantane. , 3,5-dihydroxy-1-(methyl)propenyloxyadamantane, 3,5-dimethyl-1-(methyl)propenyloxyadamantane, 5,7-dimethyl- 3-hydroxy-1-(methyl)propenyloxy adamantane, 7-methyl-3,5-dihydroxy-1-(methyl)propenyloxyadamantane, 3-ethyl-1-( Methyl)propenyloxyadamantane, 5-ethyl-3-hydroxy-1-(methyl)propenyloxyadamantane, 7-ethyl-3,5-dihydroxy-1-(methyl) Propylene methoxy adamantane and the like. Commercial products can be used for these single systems, and products such as Mitsubishi Gas Chemical Co., Ltd., and Dell products can be easily obtained.

The monomer raw material of the repeating unit represented by the general formula (10) may, for example, be α-(meth)acryloxy-γ-butyrolactone or β-(meth)acryloxy-γ- Butyrolactone, (meth) propylene decyl pantolactone, and the like. Commercially available products can be used as the single system, and products such as Osaka Organic Chemical Industry Co., Ltd. can be easily obtained.

The monomer raw material of the repeating unit represented by the general formula (11) may, for example, be 2-(methyl)propenyloxy-5-oxo-4-oxatricyclo[4.2.1.0 ^3,7 ]. Decane, 7 or 8-(meth)propenyloxy-3-oxo-4-oxatricyclo[5.2.1.0 ^2,6 ]decane, 9-(methyl)propenyloxy-3 -oxo-2-oxa-6-oxa-tricyclo[4.2.1.0 ^4,8 ]decane, 2-(methyl)propenyloxy-5-oxo-4-oxa-8- Oxatricyclo[4.2.1.0 ^3,7 ]decane, 2-(methyl)propenyloxy-9-methoxycarbonyl-5-oxo-4-oxatricyclo[4.2.1.0 ^{3, 7} ] decane, 2-(methyl)propenyloxy-5-oxo-4-oxatricyclo[4.2.1.0 ^3,7 ]decane-6-carbonitrile, and the like. These single systems can be used as commercially available products, and products such as Dell products can be easily obtained.

The repeating unit represented by the general formulas (7) and (8) has a function of dissociation due to an acid. That is, the repeating unit represented by the general formulae (7) and (8) reacts with an acid generated from a photo-acid generator at the time of exposure to form a carboxylic acid group, so that the copolymer can be converted into an alkali-soluble. In the (meth)acrylic copolymer of the present invention, a repeating unit having such a structure and properties is defined as an acid dissociable group.

The repeating unit represented by the general formula (9) can improve solvent solubility, substrate adhesion, and affinity for an alkali developing solution. In particular, the repeating unit having a hydroxyl group is preferable because the effect of improving the resolution is high. In the (meth)acrylic copolymer of the present invention, a repeating unit having such a structure and properties is defined as a polar group.

The repeating unit represented by the general formulae (10) and (11) has a lactone group, and the solvent solubility, the substrate adhesion, and the affinity for the alkali developing solution can be improved. In the (meth)acrylic copolymer of the present invention, a repeating unit having such a configuration and properties is defined as a lactone group.

Further, since the repeating unit represented by the general formula (6) also has a lactone, it belongs to a lactone group.

The copolymerization ratio of the (meth)acrylic copolymer includes 20 to 80 mol%, preferably 30 to 60 mol%, of the repeating unit represented by the general formula (6).

When the polymer includes the repeating unit represented by the general formulas (7) to (11), the polymer includes, in total, at least one type of repeating units represented by the general formulas (7) to (8) of 20 to 80 mol%, Preferably, it comprises 40 to 60 mol%. The repeating unit represented by the general formula (9) is 10 to 50 mol%, preferably 15 to 40 mol%.

When the above polymer contains the repeating unit represented by the general formulas (10) to (11), it contains 5 to 40 mol% of the total composition. Since it has a lactone group as in the general formula (6), it can be used in place of one part of the general formula (6), but if the repeating unit represented by the general formula (6) is less than 20 mol% in the total composition, It is not good because LER will deteriorate.

Next, the polymerization reaction of the (meth)acrylic copolymer will be described. The polymerization reaction is carried out by dissolving a monomer which is a repeating unit in a solvent, adding a catalyst, and heating or cooling. The reaction conditions can be arbitrarily set depending on the kind of the initiator, the starting method of heat or light, temperature, pressure, concentration, solvent, additives, etc., and the polymerization of the (meth)acrylic copolymer of the present invention can be used. Radical polymerization of a radical generating agent such as azoisobutyronitrile or a peroxide, or a known method such as ion polymerization using a catalyst such as an alkyllithium or a Grignard reagent.

As a solvent used for the polymerization reaction, a commercially available product which can be generally obtained can be used. Various solvents such as an alcohol, an ether, a hydrocarbon, and a halogen solvent can be suitably used, for example, insofar as the reaction is not inhibited.

The (meth)acrylic copolymer obtained from the polymerization can be purified by a known method. Specifically, it can be combined with ultrafiltration, crystallization, precision filtration, acid washing, and water having a conductivity of 10 mS/m or less, followed by washing and extraction.

The (meth)acrylic copolymer of the present invention has a weight average molecular weight (hereinafter also referred to as "Mw") in terms of polystyrene measured by gel permeation chromatography (GPC) of 1,000 to 500,000, preferably 3,000. ~100,000. Further, the ratio (Mw/Mn) of the Mw of the (meth)acrylic copolymer to the number average molecular weight (hereinafter also referred to as "Mn") measured by GPC is 1 to 10, preferably 1~5. If the ratio is large, the photoresist performance such as sensitivity, resolution, and roughness is deteriorated, which is not preferable. Further, in the present invention, the (meth)acrylic copolymer may be used singly or in combination of two or more.

The (meth)acrylic copolymer and the photoacid generator of the present invention are photosensitive resin compositions.

The photoacid generator is preferably selected from the range of the thickness range of the photoresist coating film and its own light absorption coefficient from the wavelength of the light which can be exposed to light, and the acid generator which is a chemically amplified photoresist composition.

For example, in the field of far ultraviolet rays, examples of the photoacid generator that can be used include an onium salt compound, a sulfonium imide compound, an anthraquinone compound, a sulfonate compound, a quinonediazide compound, and a diazomethane compound. It is possible to use commercially available products which are generally available. Among them, KrF excimer lasers or EUVs and electron lines are also suitable as sulfonium salts such as sulfonium salts, sulfonium salts, phosphonium salts, diazonium salts, pyridinium salts and the like. Specifically, triphenylsulfonium Trifluoromethanesulfonate, triphenylsulfonium nonafluorobutyrate, triphenylsulfonium hexafluorobutyrate, triphenylsulfonium naphthalenesulfonate, (hydroxyphenyl)benzylmethylsulfonate , diphenylsulfonium trifluoromethanesulfonate, diphenylsulfonium sulfonate, diphenylphosphonium dodecyl benzene sulfonate, diphenyl sulfonium hexafluorobutyrate, etc., photoacid generator They may be used alone or in combination of two or more.

The photoacid generator is used in an amount of 0.1 to 20 parts by mass, preferably 0.5 to 15 parts by mass, per 100 parts by mass of the photosensitive resin composition.

The photosensitive resin composition can also be used by being dissolved in a solvent. As the solvent to be used, a commercially available product which can be generally obtained can be used. Examples thereof include linear ketones such as 2-pentanone and 2-hexanone, cyclic ketones such as cyclopentanone and cyclohexanone, propylene glycol monomethyl ether acetate, and propylene glycol monoethyl ether B. Ethylene glycol monoalkyl ether acetates such as propylene glycol monoalkyl acetates such as acid esters, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, and propylene glycol monomethyl Ethylene glycol monoalkyl ethers such as ether, propylene glycol monoethyl ether, ethylene glycol monoalkyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, diethylene glycol dimethyl ether And diethylene glycol alkyl ethers such as diethylene glycol diethyl ether, esters such as ethyl acetate and ethyl lactate, alcohols such as cyclohexanol and 1-octanol, and ethyl carbonate. Γ-butyrolactone and the like. As such a solvent, the above may be used alone or in combination of two or more. The amount of use of the solvent is from 100 to 5,000 parts by mass, preferably from 1,000 to 2,000 parts by mass, per 100 parts by mass of the photosensitive resin composition.

Further, the photosensitive resin composition may further contain an acid diffusion controlling agent.

The acid diffusion control agent has a control for the production of the acid generator by exposure. The diffusion phenomenon of the acid photoresist in the film inhibits the adverse chemical reaction in the non-exposure field. As the acid diffusion controlling agent, it is preferred that the nitrogen-containing organic compound whose alkalinity does not change is exposed or exposed in the step of forming the photoresist pattern. As such a nitrogen-containing organic compound, a commercially available product which can be generally obtained can be used. For example, n-hexylamine, n-heptylamine, n-octylamine, or the like, monoalkylamines; dialkylamines such as di-n-butylamine; triethylamine; Trialkylamines; triethanolamine, tripropanolamine, tributylolamine, tripentylamine, trihexylamine, etc. substituted triolamines, trimethoxyethylamine, trimethoxypropyl a trialkoxyalkylamine such as an amine, trimethoxybutylamine or triethoxybutylamine; aniline, N,N-dimethylaniline, 2-methylaniline, 3-methylaniline, An aromatic amine such as 4-methylaniline, 4-nitroaniline or diphenylamine; an amine compound such as ethylenediamine, formamide, N,N-dimethylformamide, N,N - a guanamine compound such as dimethylacetamide or N-methylpyrrolidone; a urea compound such as urea; an imidazole such as imidazole or benzimidazole; a pyridine such as pyridine or 4-methylpyridine; It is also possible to cite 1,4-dioxinbicyclo[2.2.2]octane and the like.

The amount of the photosensitive resin composition to be used is 15 parts by mass or less, preferably 0.001 to 10 parts by mass, more preferably 0.005 to 5 parts by mass per 100 parts by mass of the photosensitive resin composition.

Further, the photosensitive resin composition of the present invention may contain various additives such as a surfactant, a quencher, a sensitizer, a halo preventing agent, a storage stabilizer, and an antifoaming agent as necessary.

A method of forming a photoresist pattern using the photosensitive resin composition of the present invention will be described. By spin coating the photosensitive resin composition A coating means such as cloth, dip coating, or roll coating is applied to a substrate such as a ruthenium wafer, metal, plastic, glass, or ceramic to form a photoresist film. After the film is formed, heat treatment at a temperature of about 50 ° C to 200 ° C is suitably performed, and exposure is performed through a predetermined mask pattern.

The thickness of the coating film (photoresist film) is 0.01 to 5 μm, preferably 0.02 to 1 μm, more preferably 0.02 to 0.1 μm. The exposure system can utilize light of various wavelengths. For example, as the light source, far ultraviolet rays such as an F ₂ excimer laser (wavelength 157 nm), an ArF excimer laser (wavelength 193 nm), or a KrF excimer laser (wavelength 248 nm) can be cited. , EUV (wavelength 13nm), X-ray, electronic wire, etc. The exposure conditions such as the amount of exposure are appropriately selected depending on the composition of the photosensitive resin composition, the type of each additive, and the like.

In order to stably form a high-precision fine pattern, it is preferable to carry out heat treatment for 30 seconds or more at a temperature of 50 to 200 ° C after the exposure. When the temperature is less than 50 ° C, the variation in sensitivity varies depending on the type of the substrate, which is not preferable.

The final step is carried out by alkaline imaging solution at 10 to 200 ° C for 10 to 200 seconds, preferably at 20 to 25 ° C for 15 to 1200 seconds to form a prescribed photoresist pattern.

As the alkali developing solution, a commercially available product which can be generally obtained can be used. For example, alkali metal hydroxides, ammonia water, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diguanidine bicyclo-[5.4 .0] a basic compound such as 7-undecene or 1,5-diindole bicyclo-[4.3.0]-5-nonane, used as 0.0001 to 10% by mass, preferably used as 0.01 to 5 mass. %, better used as 0.1~3 mass% alkaline water Solution. Further, the developing solution composed of the alkaline aqueous solution may further contain a water-soluble organic solvent or a surfactant.

According to the present invention, it is possible to provide excellent adhesion to a substrate, and to provide an alkali-soluble photoresist, and to form a fine pattern with high precision.

[Examples]

Hereinafter, the present invention will be specifically described by way of examples, but the present invention can be appropriately modified as long as the effects of the invention can be attained. Further, in the examples, the purity and yield of the novel (meth)acrylic compound were determined by gas chromatography (GC), and the structure was confirmed by ¹ H and ¹³ C-NMR. The measurement conditions of the GC are as follows. In addition, the parts and % of the examples are parts by mass and % by mass unless otherwise specified.

<GC condition>

Column: TC-17 (0.53mmI.D.×30m), injection temperature: 280°C, oven temperature: 70°C (1 minute hold)→10°C/min temperature rise→280°C (10 minutes hold), detector: FID, mobile phase: 氦.

[Synthesis Example 1]

Synthesis of <1-(cyclohex-1-en-1-yl)pyrrolidine>

Cyclohexanone (manufactured by Tokyo Chemical Industry Co., Ltd.: C0489) 9.8 g (100 mmol), benzene 34.4 g, pyrrolidine 8.5 were added to a 100 mL round bottom flask equipped with a stirrer, a thermometer, a Dairy condenser, and a Dean-Stark tube. g (120 mmol), the solution was heated to 74 ° C and stirred for 4 hours. The temperature of the solution was allowed to stand to 40 ° C, and concentrated by an evaporator to obtain 15.0 g of 1-(cyclohex-1-en-1-yl)pyrrolidine. It is used directly in the next step without further purification.

[Synthesis Example 2]

Synthesis of <3-(2-oxocyclohexyl)propanoic acid ethyl ester>

The 1-(cyclohexyl)-1-en-1-yl)pyrrolidine obtained in Synthesis Example 1 was added to a 100 mL round bottom flask equipped with a stirrer, a thermometer, and a Daicel condenser. 15.0 g (99.2 mmol), 15.0 g (150 mmol) of ethyl acrylate, and 37.8 g of tetrahydrofuran. The temperature of the solution was heated to 70 ° C and stirred for 6 hours. After the solution temperature was allowed to stand to 40 ° C, 6.5 g of ion-exchanged water was added, and the solution temperature was maintained at 20 to 30 ° C and stirred for 15 hours. The reaction solution was transferred to a separatory funnel, and 80 g of diisopropyl ether was added thereto, and 150 g of a 5 mass% sulfuric acid aqueous solution was added thereto for washing, and 60 g of ion-exchanged water was further washed twice. Concentration by an evaporator gave 18.2 g of ethyl 3-(2-oxocyclohexyl)propane acid. It is used directly in the next step without further purification.

[Synthesis Example 3]

Synthesis of <3-(oxocyclohexyl)propane acid>

To a 100 mL round bottom flask equipped with a stirrer, a thermometer, and a Daimler condenser, 18.2 g (91.8 mmol) of 3-(oxocyclohexyl)propane acid ethyl group obtained in Synthesis Example 2, and a 10% by mass aqueous sodium hydroxide solution 60 g were added. (Sodium hydroxide 6.0 g). The temperature of the solution was made 40 ° C and stirred for 1 hour. After the reaction liquid was allowed to stand at 30 ° C, 100 g of heptane and 60 g of ion-exchanged water were added, and the mixture was transferred to a separatory funnel, and the mixture was shaken well, and the aqueous layer was recovered. 85.5% by mass of phosphoric acid and 150 g of toluene were added to the water layer, and after swaying well, the separation was carried out. Machine layer and water layer. To the aqueous layer, 150 g of toluene was further added, and the organic layer was recovered after being satisfactorily shaken. The recovered organic layer was mixed, and 50 g of ion-exchanged water was added thereto for washing. 200 g of heptane was added and the temperature of the solution was cooled to 0 ° C, and the crystals were precipitated and stirred for 2 hours. The suction filtration was carried out using a 5C filter paper, and the recovered crystal was washed twice using ice-cold heptane 30 g. This crystal was dried under reduced pressure at 40 ° C to obtain 10.9 g of 3-(oxocyclohexyl)propane acid (yield 69.7%).

[Synthesis Example 4]

Synthesis of <1-oxaspiro[4,5]indole-2,6-dione>

To a 1 L round bottom flask equipped with a stirrer, a thermometer, a Daimler condenser, and a liquid transfer pump, 30.0 g (176 mmol) of 3-(oxocyclohexyl)propane acid obtained in Synthesis Example 3 and tetrabutylammonium iodide 13.1 were added. g (35.4 mmol) and ethyl acetate 320 g. The temperature of the solution was kept at 50 to 60 ° C, and 22.0 g (194 mmol) (0.18 g / min) of 30% hydrogen peroxide water was added dropwise over 2 hours using a liquid transfer pump. After the completion of the dropwise addition, the mixture was stirred for 30 minutes, and allowed to stand to cool to a temperature of 20 to 30 °C. The reaction solution was transferred to a separatory funnel, and washed with 250 g of a 20% by mass aqueous sodium sulfite solution. Further, 200 g of ethyl acetate was added to the separated aqueous layer to extract an organic layer. The recovered organic layer was washed with 200 g of ion-exchanged water. And this was washed twice. The organic layer was concentrated using an evaporator, and the weight of the solution was made into 65 g. After cooling at 0 ° C for 24 hours, the precipitated crystals were recovered by filtration. The recovered crystals were dried under reduced pressure at 40 ° C to obtain 19.1 g of 1-oxaspiro[4,5]indole-2,6-dione (yield 64.5%).

[Synthesis Example 5]

Synthesis of <6-hydroxy-1-oxaspiro[4,5]nonan-2-one>

A 1-L three-necked round bottom flask equipped with a stirrer and a thermometer was charged with 1-oxaspiro[4,5]indole-2,6-dione 9.70 g (57.2 mmol) obtained in Synthesis Example 4, and 453 g of methanol. The temperature of the solution was kept at 20 to 30 °C. 2.60 g (68.7 mmol) of sodium borohydride was added, and the temperature of the solution was maintained at 20 to 30 and stirred for 5 hours. Thereafter, the solvent was concentrated in vacuo using an evaporator. After adding 100 g of ethyl acetate and transferring it to a 2 L separatory funnel, the organic layer was washed with 100 g of a 5 mass% sulfuric acid aqueous solution, and after washing with 100 g of ion-exchanged water, the organic layer was collected. The solvent was concentrated in vacuo, and purified by silica gel column chromatography (eluent solvent: ethyl acetate/hexane = 1/1 (v/v), Rf value: 0.43), and the solvent was evaporated in vacuo to obtain colorless and transparent. Liquid 6-hydroxy-1-oxaspiro[4,5]nonan-2-one 7.76 g (yield 80.0%).

[Example 1]

Synthesis of <2-oxo-1-oxaspiro[4,5]fluoren-6-yl methacrylate

6-hydroxy-1-oxaspiro[4,5]nonan-2-one obtained in Synthesis Example 5 was added to a 100 mL three-necked round bottom flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel. Methyl), 4.15 g (41.1 mmol) of triethylamine, 4.83 mg (0.0242 mmol) of phenothiazine, 20.5 g of 1,2-dichloroethane, and the temperature of the solution was kept at 5 to 10 °C. 3.76 g (36.0 mmol) of methacrylic acid chloride was added to the dropping funnel, and it dropped to the reaction liquid. The temperature of the solution was raised to 70 ° C and stirred for 8 hours. After the solution temperature was changed to room temperature and 50 g of 1,2-dichloroethane was added, 30 g of ion-exchanged water was added thereto to quench. The reaction solution was transferred to a 2 L separatory funnel, and the organic layer was collected, and then washed with 30 g of a 5% sodium hydrogencarbonate aqueous solution and 30 g of ion-exchanged water, and the organic layer was collected. The solvent was concentrated in vacuo, and purified by silica gel column chromatography (eluent solvent: ethyl acetate/hexane = 1/10 (v/v), Rf: 0.12). 5.88 g (yield 95.3%) of 1--1-oxaspiro[4,5]non-6-yl methacrylate was used as a pale yellow liquid. The stereoisomer ratio was 3:1.

Stereo isomers ^1: 1 H-NMR Spectrum _{(CDCl 3): δ1.43 ~ 2.69ppm} (12H, m, cyclohexane ring, a butyrolactone ring of methylene), 2.05ppm (3H, s, A Methyl propylene group, 4.80 ppm (1H, m, methine ring of cyclohexane ring), 5.56 ppm (1H, s, methacryl fluorenyl double bond), 6.00 ppm (1H, s, A Acryl fluorenyl double bond). ¹³ C-NMR spectrum (CDCl ₃ ): 15.2 ppm, 18.5 ppm, 19.3 ppm, 24.4 ppm, 25.6 ppm, 28.0 ppm, 72.3 ppm, 82.8 ppm, 122.9 ppm, 132.9 ppm, 163.1 ppm, 173.3 ppm

Stereoisomer 2: ¹ H-NMR spectrum (CDCl ₃ ): δ 1.43~2.69ppm (12H, m, cyclohexane ring, methylene group of butyrolactone ring), 2.05ppm (3H, s, A Methyl propylene group, 4.93 ppm (1H, m, methine ring of cyclohexane ring), 5.60 ppm (1H, d, methacryl fluorenyl double bond), 6.08 ppm (1H, d, A Acryl fluorenyl double bond). ¹³ C-NMR spectrum (CDCl ₃ ): 15.2 ppm, 18.9 ppm, 20.4 ppm, 25.1 ppm, 26.0 ppm, 28.0 ppm, 72.3 ppm, 83.2 ppm, 123.6 ppm, 133.1 ppm, 163.2 ppm, 173.8 ppm

[Synthesis Example 6]

Synthesis of <4-(third-stage butoxycarbonyl)-5-oxohexanoic acid>

3L round bottom flask equipped with a blender, thermometer, and dropping funnel 80.0 g (506 mmol) of tetrabutyl acetacetate (manufactured by Tokyo Chemical Industry Co., Ltd.: A0816) and 722 mL of tetrahydrofuran were added, and the inside of the flask was subjected to nitrogen substitution. A third stage potassium butoxide potassium 3.41 g (30.4 mmol) was added and the system was kept at 0 to 10 ° C in an ice-cooled system. 37.0 g (430 mmol) of methyl acrylate was added dropwise thereto over 20 minutes, and after the completion of the dropwise addition, the liquid temperature was adjusted to 20 to 30 ° C and stirred for 2 hours. The system was kept at 0 to 10 ° C again by ice-cooling, and 1.0 L (100 g of sodium hydroxide) of a 10% by mass aqueous sodium hydroxide solution was added thereto, and the mixture was stirred for 20 hours. The reaction solution was transferred to a separatory funnel, and 500 g of a washed aqueous layer of diisopropyl ether was added. After repeating this three times, the aqueous layer was transferred to a round bottom flask and ice-cooled to maintain it at 0 to 10 °C. 520 g of 1N hydrochloric acid was added and transferred to a separating funnel, and extraction was performed with 800 mL of ethyl acetate. Repeat this 2 times. The recovered organic layer was washed with 350 g of saturated brine and concentrated with an evaporator. It was dried under reduced pressure at 40 ° C to obtain 92.5 g of 4-(tert-butoxycarbonyl)-5-oxohexanoic acid (yield: 79.4%).

[Synthesis Example 7]

<Synthesis of a third-stage butyl 2-ethenyl-5-oxotetrahydrofuran-2-carboxylate>

A 2 L round bottom flask equipped with a stirrer, a thermometer, a Daimler condenser, and a liquid transfer pump was charged with 92.5 g (402 mmol) of 4-(third-butoxycarbonyl)-5-oxohexanoic acid obtained in Synthesis Example 6. There were 26.2 g (70.8 mmol) of tetrabutylammonium iodide and 640 g of ethyl acetate. The temperature of the solution was kept at 50 to 60 ° C, and 37.1 g (389 mmol) (0.21 g / min) of 35% hydrogen peroxide water was added dropwise over 3 hours using a liquid transfer pump. After the completion of the dropwise addition, the mixture was stirred for 30 minutes, and allowed to stand to cool to a temperature of 20 to 30 °C. The reaction solution was transferred to a separatory funnel, and 325 g of a 20% by mass aqueous sodium sulfite solution was added thereto for washing. Further, 300 mL of ethyl acetate was added to the separated aqueous layer to extract an organic layer. The recovered organic layer was washed with 500 g of a 5 mass% sodium hydrogencarbonate aqueous solution, and then washed with 500 g of saturated brine. The organic layer was concentrated using an evaporator to obtain 50.8 g. It is used directly in the next step without further purification.

[Synthesis Example 8]

<Synthesis of tert-butyl butyl 2-(1-hydroxyethyl)-5-oxotetrahydrofuran-2-carboxylate>

Add a 3L four-neck round bottom flask equipped with a blender and thermometer 40.4 g (177 mmol) of the third-stage butyl 2-ethinyl-5-oxotetrahydrofuran-2-carboxylate obtained in Example 8 and 1333 g of tetrahydrofuran were obtained, and the temperature of the solution was maintained at 5 to 10 °C. Sodium borohydride 8.02 g (212 mmol) was added and stirred for 4 hours. 300 g of a 20% by mass aqueous ammonium chloride solution was added without causing the solution temperature to exceed 20 °C. The solution was transferred to a 5 L separatory funnel, and 486 g of ethyl acetate was added to extract an organic layer. The aqueous layer was transferred again to a separatory funnel, and 486 g of ethyl acetate was added to extract the organic layer again. The organic layer was transferred to a separatory funnel, and the organic layer was washed with 400 g of a 5% aqueous sodium hydrogencarbonate solution and 400 g of ion-exchanged water. The solvent was concentrated in vacuo, and purified by silica gel column chromatography (solvent: chloroform / ethyl acetate = 4/1 (v/v), Rf: 0.28) to obtain a third butyl 2 by distilling off solvent. 25.7 g (yield 63.1%) of (1-hydroxyethyl)-5-oxotetrahydrofuran-2-carboxylate as a pale yellow liquid.

[Embodiment 2]

<Synthesis of tert-butyl butyl 2-(1-methylpropenyloxy)ethyl-5-oxotetrahydrofuran-2-carboxylate>

Equipped with a blender, thermometer, reflux cooler, drip funnel A 200 mL three-necked round bottom flask was charged with a third-stage butyl 2-(1-hydroxyethyl)-5-oxotetrahydrofuran-2-carboxylate, 9.73 g (42.3 mmol), and triethylamine 12.0 g (118 mmol). Phthathiazine 84.0 mg (0.420 mmol), N-nitrosophenylhydroxylamine aluminum salt 5.00 mg (0.0114 mmol), 1,2-dichloroethane 48.7 g, and the solution temperature was maintained at 5-10 °C. To the dropping funnel, 11.0 g (106 mmol) of methacrylic acid chloride was added, and the mixture was dropped into the reaction liquid. The temperature of the solution was raised to 53 ° C and stirred for 8 hours. The solution temperature was set to room temperature, and 50 g of ion-exchanged water was added to quench. The solution was transferred to a 500 mL separatory funnel, and the organic layer was collected, and then washed with 50 g of ion-exchanged water to collect an organic layer. The solvent was concentrated in vacuo, and purified by silica gel column chromatography (eluent solvent: ethyl acetate/hexane = 1/3 (v/v), Rf value: 0.32) to obtain a white solid. Grade butyl 2-(1-methylpropenyloxy)ethyl-5-oxotetrahydrofuran-2-carboxylate 10.6 g (yield 84.4%). The stereoisomer ratio was 6:1.

Stereo isomers ^1: 1 H-NMR Spectrum _{(CDCl 3): δ1.27 (3H} , d, C H 3 -CH (-O-) C -), 1.42ppm (9H, s, t- butyl) , 1.90 (3H, s, methyl methacryloyl methyl), 2.24-2.60 ppm (4H, m, butylene lactone ring methylene), 5.38 ppm (1H, m, CH ₃ -C H (- O-) C-), 5.58 ppm (1H, d, methacryl fluorenyl double bond), 6.10 ppm (1H, d, methacryl fluorenyl double bond). ¹³ C-NMR spectrum (CDCl ₃ ): 10.6 ppm, 15.2 ppm, 24.5 ppm, 24.7 ppm, 24.8 ppm, 68.5 ppm, 80.5 ppm, 84.5 ppm, 123.6 ppm, 132.7 ppm, 162.9 ppm, 163.2 ppm, 172.6 ppm

Stereoisomer 2: ¹ H-NMR spectrum (CDCl ₃ ): δ 1.29 (3H, d, C H ₃ -CH(-O-)C-), 1.42 ppm (9H, s, t-butyl) , 1.90 (3H, s, methyl methacryloyl methyl), 2.24-2.60 ppm (4H, m, butylene lactone ring methylene), 5.38 ppm (1H, m, CH ₃ -C H (- O-) C-), 5.64 ppm (1H, d, methacryl fluorenyl double bond), 6.19 ppm (1H, d, methacryl fluorenyl double bond). ¹³ C-NMR spectrum (CDCl ₃ ): 11.1 ppm, 16.1 ppm, 24.5 ppm, 24.7 ppm, 24.8 ppm, 68.8 ppm, 80.9 ppm, 84.9 ppm, 124.0 ppm, 133.3 ppm, 164.4 ppm, 165.4 ppm, 172.7 ppm

[Synthesis Example 9]

Synthesis of <1-ethyl-1-methylpropenyloxycyclohexane>

To a 500 mL three-necked round bottom flask equipped with a stirrer, a thermometer, a reflux condenser, and a dropping funnel, 1-ethylcyclohexanol (manufactured by Tokyo Chemical Industry Co., Ltd.: E1136), 12.8 g (100 mmol), and triethylamine (20.3 g) were added. 200 mmol), phenazine 199 mg (1.00 mmol), 1,2-dichloroethane 100 g, and the temperature of the solution was maintained at 5 to 10 °C. 20.7 g (200 mmol) of methacrylic acid chloride was added to the dropping funnel, and the mixture was dropped into the reaction liquid. The temperature of the solution was raised to 50 ° C and stirred for 8 hours. Set the solution temperature to room temperature and add 100 g of ion-exchanged water was quenched. The solution was transferred to a 500 mL separatory funnel, and the organic layer was collected, and then washed with 100 g of ion-exchanged water to collect an organic layer. The solvent was concentrated in vacuo, and purified by silica gel column chromatography, and then evaporated to afford the solvent of 1-ethyl-1-methylpropenyloxycyclohexane (yield: 82.4%).

[Example 3]

<Resin Synthesis Example 1>

2-oxo-1-oxaspiro[4,5]non-6-ylmethacrylate (hereinafter, monomer A1) obtained in Example 1 was 4.15 g, 2-ethyl-2-methylpropene醯oxyadamantane (manufactured by Tokyo Chemical Industry Co., Ltd.: E0909) (hereinafter, monomer B1) 4.02 g, 3-hydroxy-1-adamantyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.: HADM) (hereinafter, single 1.1 g of the compound C1) and 0.74 g of azobisisobutyronitrile were dissolved in 100 mL of tetrahydrofuran, and the reaction temperature was maintained at 55 ° C under a nitrogen atmosphere to carry out polymerization for 24 hours (the monomer addition ratio was A1/B1/C1 = 40/40/20 mol%). After the polymerization, the reaction solution was dropped into 500 mL of n-hexane to coagulate and purify the resulting resin, and the resulting white powder was filtered using a membrane filter and washed with n-hexane (1000 mL). The white powder was recovered, and dried overnight at 40 ° C under reduced pressure to obtain 6.32 g of methacrylic acid copolymer P1.

[Example 4]

<Resin Synthesis Example 2>

3.11 g of monomer A1, 1-ethyl-1-methyl obtained in Synthesis Example 9 3-propenyloxycyclohexane (hereinafter, monomer B2) 3.18 g, 2-methylpropenyloxy-2-(3-(2-hydroxy-2-propyl)-1-adamantyl)propane (manufactured by Mitsubishi Gas Chemical Co., Ltd.: ADPM) (hereinafter, monomer B3) 1.95 g, 3,5-dihydroxy-1-adamantyl methacrylate (manufactured by Mitsubishi Gas Chemical Co., Ltd.: DHADM) (hereinafter, monomer C2) 1.53 g, 0.74 g of azobisisobutyronitrile was dissolved in tetrahydrofuran 82 mL, and the reaction temperature was maintained at 55 ° C under a nitrogen atmosphere, and polymerization was carried out for 24 hours (monomer addition ratio was A1/B2/B3/C2=30). /40/15/15 mole %). After the polymerization, the reaction solution was dropped into 500 mL of n-hexane to coagulate and purify the resin, and the resulting white powder was filtered using a membrane filter, and washed with n-hexane (1000 mL). The white powder was recovered, and dried overnight at 40 ° C under reduced pressure to obtain 6.77 g of methacrylic acid copolymer P2.

[Example 5]

<Resin Synthesis Example 3>

The third-stage butyl 2-(1-methylpropenyloxy)ethyl-5-oxotetrahydrofuran-2-carboxylate (hereinafter, monomer A2) obtained in Example 2 was 3.13 g, 3.35 g. Monomer B1, 1.42g of monomer C1g, azobisisobutyronitrile 0.49g was dissolved in tetrahydrofuran 79mL, the reaction temperature was maintained at 55 ° C under nitrogen atmosphere, and polymerization was carried out for 24 hours (monomer addition ratio was A2/B1/C1=35/45/20 mol%). After the polymerization, the reaction solution was dropped into 500 mL of n-hexane to coagulate and purify the resin, and the resulting white powder was filtered using a membrane filter, and washed with n-hexane (1000 mL). The white powder was recovered, and dried under reduced pressure at 40 ° C for one night to obtain 4.94 g of methyl group. Acrylic copolymer P3.

[Embodiment 6]

<Resin Synthesis Example 4>

2.68 g of monomer A2, 2.06 g of monomer B2, 1.92 g of monomer C2, 1.13 g of monomer C3, and azobisisobutyronitrile 0.49 g were dissolved in tetrahydrofuran 78 mL, and the reaction temperature was maintained under a nitrogen atmosphere. The polymerization was carried out at 55 ° C for 24 hours (monomer addition ratio was A2 / B2 / C2 / C3 = 30 / 35 / 20 / 15 mol%). After the polymerization, the reaction solution was dropped into 500 mL of n-hexane to coagulate and purify the resin, and the resulting white powder was filtered using a membrane filter, and washed with n-hexane (1000 mL). The white powder was recovered, and dried overnight at 40 ° C under reduced pressure to obtain 5.45 g of methacrylic acid copolymer P4.

[Embodiment 7]

<Photoresistance evaluation 1>

100 parts by mass of each of the methacrylic acid copolymers P1, P2, P3, and P4 obtained in Examples 3 to 6 and triphenylsulfonium nonafluorobutane sulfonate (TPS-109, manufactured by Cuihua Chemical Co., Ltd.) The solvent was dissolved in a propylene glycol monomethyl ether acetate solvent so as to have a copolymer concentration of 6.3% by mass to prepare photosensitive resin compositions R1, R2, R3, and R4. After coating an anti-reflection film (ARC-29 manufactured by Nissan Chemical Co., Ltd.) on a ruthenium wafer (manufactured by Wanxiang Silicon-Peak Electronics Co., Ltd.), the resist resin composition was spin-coated on the anti-reflection film. A photosensitive layer having a thickness of 100 nm was formed. After prebaking on a hot plate at a temperature of 90 ° C for 60 seconds, use An electron beam drawing device (ELS-7700 manufactured by Elionix Co., Ltd.) irradiated the photosensitive layer with a line and a space pattern of a half pitch of 100 nm (eight lines). It is then baked at a specified temperature (PEB) for 90 seconds. Next, development was carried out by a 0.3 M aqueous solution of tetramethylammonium hydroxide for 60 seconds, and rinsed with pure water to obtain a line and space pattern.

[Comparative Example 1]

In place of the monomer A1, 2-oxohexahydro-2H-3,5-methylcyclopenta[ b ]furan-6-ylmethacrylate (manufactured by Dell Inc.: MNBL) was used instead (hereinafter, monomer A4) Other than 3.63 g, the same operation as in Example 3 was carried out (the monomer addition ratio was A4/B1/C1 = 40/40/20 mol%), and 6.81 g of the methacrylic acid copolymer P5 was obtained.

[Comparative Example 2]

In addition to the substitution of the monomer A1, the α-methacryloxy-γ-butyrolactone (manufactured by Osaka Organic Chemical Industry Co., Ltd.: GBLMA) (hereinafter, monomer A3) was 2.76 g, and the other system and Example 3 were used. The same operation was carried out (monomer addition ratio was A3/B1/C1 = 40/40/20 mol%), and 5.69 g of methacrylic acid copolymer P6 was obtained.

<Photoresistance evaluation 2>

The same operation as in the photoresist performance evaluation 1 was carried out, except that the methacrylic acid copolymers P1, P2, P3, and P4 were replaced, and the P5 obtained in Comparative Example 1 was used to prepare the photosensitive resin composition R5, and the comparative example 2 was used. Obtained P6 is prepared into a photosensitive resin composition R6. Further, in these photosensitive resin compositions R5 and R6, the photoresist performance was evaluated in the same manner as in the photoresist performance evaluation 1.

The line and space patterns obtained were observed using FE-SEM, and the resolution and line edge roughness (LER) were measured. The results are shown in Table 4. When the LER value of each photosensitive resin composition under the same degree of resolution is compared, the photosensitive resin composition R5 and R6 which are the same as the structure and composition of the lactone and the same as R1 and R3, respectively, are known. The LER values of the objects R1 and R3 are small. The repeating units A1 and A2 included in the photosensitive resin compositions R1 and R3 are three-dimensional high-volume structures, compared to the repeating units A3 and A4 included in R5 and R6. Therefore, it is considered that the diffusion of the acid which is dissociated at the time of electron beam drawing is suppressed, and as a result, the roughness can be successfully reduced.

The results of the photosensitive resin compositions R2 and R4 are shown in Table 5. Although the copolymer composition of the photosensitive resin composition R2 and R4 is different from the above R1 and R3, the photosensitive resin compositions R2 and R4 also exhibit good results similar to those of the photosensitive resin compositions R1 and R3. . In other words, it was confirmed that the photosensitive resin compositions R2 and R4 also achieved excellent resolution and a small LER value. The result is also considered to be related to the photosensitive tree. The reason why the LER values of the lipid compositions R1 and R3 are smaller than the LER values of R5 and R6 are considered to be mainly due to the difference in the height of the solid volume of the repeating unit.

Claims (6)

a lactone (meth) acrylate compound which is represented by the general formula (1); In the formula (1), R ¹ represents a hydrogen atom or a methyl group; R ² represents hydrogen, an aliphatic alkyl group having 1 to 10 carbon atoms, or an alkyl group having an alicyclic structure having 3 to 10 carbon atoms; and R ³ represents hydrogen; An alkoxycarbonyl group represented by the formula (2), an aliphatic alkyl group having 1 to 10 carbon atoms, or an alkyl group having an alicyclic structure having 3 to 10 carbon atoms; in this case, R ² and R ³ may be mutually Combining to form an alicyclic structure having a carbon number of 3 to 10; n ₁ represents an integer of 0 to 2; In the formula (2), R ⁴ represents an aliphatic alkyl group having 1 to 13 carbon atoms or an alkyl group having an alicyclic structure having 3 to 13 carbon atoms; and a broken line indicates a bond in the compound of the formula (1). A process for producing a lactone (meth) acrylate compound according to claim 1, which has a hydroxylactone compound represented by the general formula (4) and a (meth) acrylate compound represented by the general formula (5) The step of carrying out the reaction; In the formula (4), R ² , R ³ and n ₁ are the same as those in the general formula (1); In the formula (5), R ¹ is the same as in the general formula (1); and R ⁵ is a group selected from the group consisting of a hydroxyl group, a halogen atom and a (meth) acryloxy group. a (meth)acrylic copolymer which is a repeating unit represented by the general formula (6); In the formula (6), R ¹ to R ³ and n ₁ are the same as those in the formula (1), and the * point indicates the combination with the adjacent repeating unit. The (meth)acrylic copolymer of claim 3, which further has any one or both of the repeating units represented by the general formula (7) or (8), and a repeating unit represented by the general formula (9); In the formula (7), R ²¹ represents hydrogen or a methyl group, R ²² represents an alkyl group having 1 to 4 carbon atoms, and R ²³ represents a cycloalkyl group having 5 to 20 carbon atoms or an alicyclic alkyl group, and * points are expressed by a junction of adjacent repeating units; In the formula (8), R ⁴¹ represents hydrogen or a methyl group, R ₄₂ to R ₄₃ are the same or may be an alkyl group having a carbon number of 1 to 4, and R ₄₄ is an alkyl group selected from a carbon number of 1 to 4. Or a group of a group of 5 to 20 carbon atoms of a cycloalkyl group or an alicyclic alkyl group, and * dots represent a combination with adjacent repeating units; In the formula (9), R ⁴¹ represents hydrogen or a methyl group, and R ⁴² to R ⁴⁴ are the same or may be differently represented by a group selected from the group consisting of a hydrogen element, a hydroxyl group, a methyl group and an ethyl group, * point It is the combination with the adjacent repeating unit. The (meth)acrylic copolymer of claim 4, which comprises 20 to 80 mol% of the repeating unit represented by the above general formula (6), and includes the total of the general formulas (7) and (8) The repeating unit is 20 to 80 mol%, and contains 10 to 50 mol% of the repeating unit represented by the above general formula (9). A photosensitive resin composition comprising the requirements of items 3 to 5 A (meth)acrylic copolymer and a photoacid generator according to any one of them.