KR20120000533A - Actinic ray-sensitive or radiation-sensitive resin composition, and resist film and pattern forming method for using the same - Google Patents

Abstract

PURPOSE: An active ray-sensitive or radiation-sensitive resin composition, a resist film using the same, and a method for forming patterns are provided to improve the out gas performance in an exposing process, the line-edge-roughness, the pattern shape, the resolution, and the sensitivity of the composition. CONSTITUTION: An active ray-sensitive or radiation-sensitive resin composition includes a resin. The resin includes a first repeating unit and a second repeating unit. The first repeating unit includes an ionic structure part which generates an acid anion to the side chain of the resin by being decomposed based on irradiation by an active ray or radiation. The second repeating unit is represented by chemical formula I. The cation of the ionic structure part is diaryliodium cation which is represented by chemical formula A1. A resist film is formed based on the composition.

Description

ACTINIC RAY-SENSITIVE OR RADIATION-SENSITIVE RESIN COMPOSITION, AND RESIST FILM AND PATTERN FORMING METHOD FOR USING THE SAME}

The present invention is directed to an actinic ray-sensitive or radiation-sensitive resin composition, which is preferably used for ultra-microlithography processes such as the production of ultra-LSI and high-capacity microchips, and other photopublishing processes, and a resist film and pattern forming method using the same. It is about.

Conventionally, in the manufacturing process of semiconductor devices, such as IC and LSI, the microprocessing by the lithography using a photoresist composition is performed. In recent years, as the integration of integrated circuits has increased, there has been a demand for the formation of ultrafine patterns in the submicron region or the quarter micron region. As a result, a tendency of shortening wavelength is seen as the exposure wavelength is also from g line to i line and KrF excimer laser light. In addition, lithography using electron beams, X-rays, or EUV light is being developed in addition to the excimer laser light.

In particular, electron beam lithography is positioned as a next-generation or next-generation pattern formation technique, and a high sensitivity and high resolution positive resist is desired. In particular, high sensitivity is a very important issue due to shortening of wafer processing time. However, in the case of positive resists for electron beams, if the high sensitivity is pursued, not only the resolution is lowered but also the line edge roughness is deteriorated to satisfy these characteristics simultaneously. The development of resists is strongly desired. Here, the line edge roughness means that the edges of the pattern and substrate interface of the resist fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist, so that the edges appear uneven when viewed from above. This unevenness is transferred by an etching process using the resist as a mask, thereby deteriorating electrical characteristics, thereby lowering the yield. In particular, in the ultrafine region of 0.25 µm or less, line edge roughness is a very important improvement problem. High sensitivity, high resolution, good pattern shape, and good line edge roughness are in a trade-off relationship, and how to simultaneously satisfy this is very important.

Similarly, in lithography using X-rays or EUV light, it is important to simultaneously satisfy high sensitivity, high resolution, good pattern shape, and good line edge roughness, and these solutions are required.

In addition, when EUV light is used as a light source, since the wavelength of the light belongs to the extreme ultraviolet region and has a high energy, unlike the conventional light source, the compound in the resist film is destroyed by fragmentation and is exposed as a low molecular weight component during exposure. The problem of outgas that volatilizes and pollutes the environment in the exposure machine becomes remarkable.

As one method of solving such a problem, use of resin which has a photoacid generator in a polymer main chain or a side chain is examined (patent documents 1-8).

For example, Patent Document 1 discloses a photoacid generator-containing resin having an iodonium cation.

Further, Patent Documents 2 to 8 disclose resins having a photoacid generator and a group in which the solubility in an alkaline developer is increased by the acid decomposition in the same molecule.

Japanese Patent Laid-Open No. 9-325497 Japanese Patent Laid-Open No. 10-221852 Japanese Patent Laid-Open No. 2006-178317 Japanese Patent Publication No. 2007-197718 International Publication No. 06/121096 US Patent Application Publication No. 2006/121390 Japanese Patent Publication No. 2009-93137 Japanese Patent Publication No. 2010-85971

However, the photoacid generator-containing resin having the iodonium cation of Patent Document 1 is not a chemically or thermally stable resin structure, and the stability over time of the resist composition obtained using such a resin is insufficient. In addition, since the technique of patent document 1 is a mixed system of resin which has a photo-acid generator, and the dissolution prevention compound which the solubility to alkaline developing solution increases by acid decomposition, favorable pattern shape and line edge roughness are attributable to the heterogeneous mixing property of these materials. It was difficult to get nice.

In addition, Patent Documents 2 to 6 disclose resins having a photoacid generator and a group in which the solubility in an alkaline developer is increased by acid decomposition in the same molecule, but are particularly sufficient for sensitivity to electron beams, X-rays, or EUV light. It was hard to do.

As in the techniques described in Patent Literatures 1 to 8, when the acid generating site corresponding to the acid generator is contained in the resin, the miscibility of the acid generator and the resin is insufficient, or the acid generated from the acid generator by exposure. The problem that the resolution is impaired due to diffusion to an unintended area (unexposed part or the like) tends to be reduced. In addition, since there is no acid generator of low molecular weight, even if it is irradiated with EUV light, the generation of the outgas derived from a low molecular weight component will become more reduced. However, in addition to requiring new improvements in resolution and outgas characteristics in electron beams, X-rays or EUV optical lithography, in addition to the sensitivity, line edge roughness, pattern shape and stability over time, and storage stability as a solution. Even better performance is actually required.

Accordingly, an object of the present invention is to satisfy high sensitivity, high resolution, good pattern shape, and good line edge roughness at the same time in high dimensions, especially in electron beam, X-ray or EUV light lithography, as well as outgas performance and exposure stability at the time of exposure. This is sufficient to provide the actinic-ray-sensitive or radiation-sensitive resin composition excellent in the storage stability as a solution, and the resist film and pattern formation method using the same.

The said subject was discovered to be achieved by the following structures.

(1) A repeating unit (A) having an ionic structure moiety that is decomposed by irradiation with active light or radiation to generate acid anions in the side chain of the resin, and a repeating unit (C) represented by the following general formula (I): An actinic ray-sensitive or radiation-sensitive resin composition containing a resin (P) having, wherein the cation of the ionic structure moiety is a diaryliodonium cation represented by the following general formula (A1): Resin composition.

In General Formula (A1), Ar ₁ represents a (p + 1) valent aromatic ring group, and Ar ₂ represents a (q + 1) valent aromatic ring group.

L ₁ and L ₂ each independently represent a single bond or an oxygen atom.

R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom or an alkyl group. At least two of R ₁₁ , R _12, and R ₁₃ may combine to form a ring. In addition, at least two of R ₂₁ , R _22, and R ₂₃ may combine to form a ring.

p and q each represent an integer of 0 to 9 and satisfy p + q ≧ 2.

In the case of p≥2, the groups represented by a plurality of (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ − may be the same or different.

In the case of q≥2, the groups represented by a plurality of (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL ₂ − may be the same or different.

However, in the general formula (A1), when represented by the following general formula (A1-1), L ₁ and L ₂ are the same as each other, and R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R _{23 are} all Is not the same thing.

In Formula (I), R ₁₁ ′, R ₁₂ ′ and R ₁₃ ′ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₃ ′ may be bonded to Ar ₁ ′ to form a ring, and R ₁₃ ′ in that case represents an alkylene group.

X ₁ represents a single bond or a divalent linking group.

Ar ₁ ′ represents a (n + 1) valent aromatic ring group, and when combined with R ₁₃ ′ to form a ring, (n + 2) valent aromatic ring group.

n represents the integer of 1-4.

(2) The actinic ray-sensitive or radiation-sensitive resin composition according to (1), wherein in the general formula (A1), p is an integer of 1 or more, and q is an integer of 1 or more.

(3) In (2), in the general formula (A1), p groups represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ − and q groups (R ₂₁ ) (R ₂₂ ) ( The groups represented by R ₂₃ ) CL ₂ − are not all the same group, but the actinic ray-sensitive or radiation-sensitive resin composition.

(4) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (3), wherein p and q are integers different from each other in General Formula (A1).

(5) The group represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ -in any of Formulas (A1) and (R ₂₁ ) (R) in any one of (1) to (4). ₂₂ ) An actinic ray-sensitive or radiation-sensitive resin composition in which groups represented by (R ₂₃ ) CL ₂ -each independently represent an alkyl group having 1 to 3 carbon atoms.

(6) The group represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ -in any of Formula (A1) and (R ₂₁ ) (R) in any one of (1) to (5). ₂₂ ) An actinic ray-sensitive or radiation-sensitive resin composition in which at least one of two or more groups selected from the group consisting of groups represented by (R ₂₃ ) CL ₂ -is positioned at the ortho position with respect to the iodonium group on the aromatic ring.

(7) The actinic ray sensitive or radiation sensitive resin composition in any one of (1)-(6) which satisfy | fills p + q≥3 in the said General formula (A1).

(8) The actinic ray sensitive or radiation sensitive resin composition in any one of (1)-(7) which satisfy | fills p + q≥4 in the said General formula (A1).

(9) The actinic ray-sensitive or radiation-sensitive ray according to any one of (1) to (8), wherein the resin (P) further has a repeating unit (C) which is decomposed by the action of an acid to generate an alkali-soluble group. Resin composition.

(10) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (9), wherein the repeating unit (B) is a repeating unit represented by the following General Formula (V) or (VI).

In formula (V), R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₅₂ may be bonded to L ₅ to form a ring, in which case R ₅₂ represents an alkylene group.

L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.

R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may be bonded to each other to form a ring. However, R ₅₅ and R ₅₆ do not simultaneously represent a hydrogen atom.

In General Formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring, in which case R ₆₂ represents an alkylene group.

Ar ₆ represents a (n + 1) valent aromatic ring group, and when combined with R ₆₂ to form a ring, (n + 2) valent aromatic ring group.

Y represents a group which is released by the action of a hydrogen atom or an acid, and when a plurality of Y are present, a plurality of Y may be the same or different. Provided that at least one of Y represents a group that is released by the action of an acid.

n represents the integer of 1-4.

(11) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (10), which is for electron beam, X-ray, or EUV light.

The resist film formed using the actinic-ray-sensitive or radiation-sensitive composition in any one of (12) (1)-(11).

It has a process of exposing and developing the resist film of (13) (12), The pattern formation method characterized by the above-mentioned.

The manufacturing method of an electronic device containing the pattern formation method as described in (14) (13).

The electronic device manufactured by the manufacturing method of the electronic device as described in (15) (14).

It is preferable that this invention is also the following structure.

(16) The actinic ray-sensitive or radiation-sensitive resin composition according to any one of (1) to (11), wherein L ₁ and L ₂ in the general formula (A1) represent an oxygen atom.

(17) In any one of (1)-(11) and (16), the sum total of the Hammett values with respect to the iodonium group of all the substituents in Ar <_1> and Ar <_2> in the said General formula (A1) is -0.5 The actinic ray sensitive or radiation sensitive resin composition which is the following.

(18) The actinic ray-sensitive or radiation-sensitive radiation according to (17), wherein the sum of the Hammet values for the iodonium groups of all substituents in the aromatic rings of Ar ₁ and Ar ₂ in General Formula (A1) is -0.8 or less. Resin composition.

(19) (18), The actinic ray-sensitive or radiation-sensitive radiation in which the sum of Hammet values for the iodonium groups of all substituents in the aromatic rings of Ar ₁ and Ar ₂ in General Formula (A1) is -1.0 or less; Resin composition.

(Effects of the Invention)

According to the present invention, particularly in electron beam, X-ray or EUV lithography, high sensitivity, high resolution, good pattern shape, and good line edge roughness are simultaneously satisfied in high dimensions, and the outgas performance during exposure and stability over time are sufficiently good. The actinic ray sensitive or radiation sensitive resin composition excellent in the storage stability as a solution, the resist film and the pattern formation method using the same can be provided.

Hereinafter, the present invention will be described in detail.

In addition, in description of group (atom group) in this specification, the description which is not describing substitution and unsubstitution includes what has a substituent with the thing which does not have a substituent. For example, an "alkyl group" includes not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

"Active light" or "radiation" in the present specification means, for example, a bright spectrum of mercury lamp, far ultraviolet rays represented by excimer laser, extreme ultraviolet light (EUV light), X-ray, soft X-ray, electron beam and the like. In addition, in this invention, light means actinic light or a radiation.

In addition, unless otherwise indicated, "exposure" in this specification is not only exposure to ultraviolet rays, X-rays, EUV light, etc. represented by a mercury lamp, an excimer laser, but also drawing by particle beams, such as an electron beam and an ion beam. Include in exposure.

The actinic ray sensitive or radiation sensitive resin composition of this invention contains resin (P) demonstrated below.

According to the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, high sensitivity, high resolution, good pattern shape, and good line edge roughness are satisfied simultaneously in high dimensions, and satisfactorily satisfactory outgas performance and time stability at the time of exposure. The storage stability as a solution can be made excellent.

By using the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, the structure of the diaryliodonium cation in the ionic structure site is particularly easy to exhibit good sensitivity to electron beams, X-rays or EUV light (in other words, High acidity, good pattern shape, good line edge roughness, and outgas performance during exposure, particularly in the formation of fine patterns obtained by electron beams, X-rays or EUV light. It is guessed that it contributed to satisfying simultaneously in high dimension.

In addition, the acid generator having an iodonium cation is difficult to use due to insufficient stability over time even if sufficient sensitivity is obtained, but as represented by the general formula (A1), (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) The molecular weight of two or more groups selected from the group represented by CL ₁ -and the group represented by (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL ₂ -is introduced onto the aryl ring of the diaryliodonium cation. This increases the outgas performance at the time of exposure, and the decomposition with water, nucleophiles, etc. is difficult to occur over time, and it is estimated that stability with time is improved.

As described above, the diaryl iodonium cation represented by the general formula (A1) is represented by the general formula (A1-1), and L ₁ and L ₂ are the same as each other, and R ₁₁ and R ₁₂ are the same. The same cation as that of all of R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ is excluded, whereby the actinic ray-sensitive or radiation-sensitive resin composition of the present invention is considered to be excellent in storage stability as a solution.

The reason is not completely clear, but in the compound represented by the general formula (A1-1) excluded above, the (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ − in the aryl ring on the diaryl iodonium cation The groups represented by and the groups represented by (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL ₂ -are groups which tend to increase the symmetry of the iodonium cation molecule, and these groups are also the symmetry of the iodonium cation molecule. It is thought that it is couple | bonded with the aryl ring in the position which increases more. As a result, the compound represented by the general formula (A1-1) exemplified above has a very high symmetry as a molecule and is likely to generate a nodule structure in the solvent, so that the solid content in the resist composition is not dissolved in the solvent or solidified once dissolved. Therefore, it is thought that the solubility to a solvent will interfere and the storage stability as a solution will be impaired. On the other hand, when the diaryl iodonium cation of the present invention is used, the compound having high symmetry is excluded as the molecule as described above, so that the symmetry of the molecule is low, the solvent solubility of the solid content is increased, and as a result, it is estimated that the storage stability is excellent.

The actinic ray sensitive or radiation sensitive resin composition according to the present invention is, for example, a positive composition, and typically a positive resist composition. Hereinafter, the structure of this composition is demonstrated.

[1] resins (P)

Resin (P) contained in the actinic ray-sensitive or radiation-sensitive resin composition comprises a repeating unit (A) having an ionic structure moiety which is decomposed by irradiation of active light or radiation to generate acid anions in the side chain of the resin. Have And the cation of this ionic structure site | part is the diaryl iodonium cation represented by general formula (A1) demonstrated later in detail.

[Repeat unit (A)]

The repeating unit (A) is a repeating unit that is decomposed by irradiation of actinic rays or radiation to generate acid anions in the side chain of the resin, and in one embodiment contains an aromatic ring in the side chain except at least the counter cation of the acid anion. It is preferable that it is a repeating unit.

It is preferable that a repeating unit (A) is a repeating unit more specifically represented by general formula (I) or general formula (II).

In general formula (I), R <_11> , R <_12> , R <_13> represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group, or an alkoxycarbonyl group each independently.

The alkyl group is a linear or branched alkyl group which may have a substituent, and preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group or 2-ethyl which may have a substituent. C20 or less alkyl groups, such as a hexyl group, an octyl group, and a dodecyl group, are mentioned, More preferably, an alkyl group of 8 or less carbon atoms, Especially preferably, an alkyl group of 3 or less carbon atoms is mentioned.

As an alkyl group contained in the alkoxycarbonyl group, the same thing as the alkyl group in said R <_11> , R <_12> and R <_13> is preferable.

As monovalent aliphatic hydrocarbon ring group, the monocyclic or polycyclic aliphatic hydrocarbon ring group which may have a substituent is mentioned. Preferably, a monocyclic monovalent aliphatic hydrocarbon ring group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent is mentioned.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, with fluorine atom being particularly preferred.

Examples of preferable substituent in each of the groups hydroxy, halogen atom (F, Cl, Br, I), an alkyl group, a methoxy group listed in a nitro group, a cyano group, an amide group, a sulfonamide group, R ₁₁ ~R _13, ethoxy groups Alkoxy groups such as hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups, acyl groups such as formyl groups, acetyl groups and benzoyl groups, ace Acyloxy groups, such as a oxy group and a butyloxy group, and a carboxy group are mentioned. In particular, a hydroxyl group and a halogen atom are preferable.

As R ₁₁ , R ₁₂ and R ₁₃ in formula (I), a hydrogen atom, an alkyl group, and a halogen atom are more preferable, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ), and a hydroxymethyl group (-CH ₂ -OH), chloromethyl group (-CH ₂ -Cl), fluorine atom (-F) is particularly preferred.

X ₁₁ , X ₁₂ and X ₁₃ are each independently a single bond, -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing nonaromatic Heterocyclic group or group which combined these is shown.

In -NR-, the alkyl group represented by R is a linear or branched alkyl group which may have a substituent, and the specific example similar to the alkyl group in said R <_11> , R <_12> , R <_13> is mentioned. As R, a hydrogen atom, a methyl group and an ethyl group are particularly preferable.

In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means preferably a 3 to 8 membered non-aromatic heterocyclic group having at least one nitrogen atom, and specific examples thereof include a divalent linking group having the following structure. .

When X ₁₁ is a single bond, R ₁₂ may form a ring with Ar _1, and R ₁₂ in that case represents an alkylene group. As X <_{11>, a} single bond, -COO-, -CONR- (R is a hydrogen atom or an alkyl group) is more preferable, A single bond and -COO- is especially preferable.

A single bond as _{X 12, -O-, -CO-, -SO} 2 -, -NR- more preferred group is a combination of (R is a hydrogen atom or an alkyl group), and these, and a single bond, -OCO-, -OSO ₂ -Is particularly preferred.

A single bond as _{X 13, -O-, -CO-, -SO} 2 -, -NR- more preferred group is a combination of (R is a hydrogen atom or an alkyl group), and these, and a single bond, -OCO-, -OSO ₂ -Is particularly preferred.

L ₁₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group combining two or more thereof. Two or more groups to be combined in the combined group may be the same or different, and as the linking group, -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group) and a divalent nitrogen-containing ratio You may be connected through the aromatic heterocyclic group or the group which combined these.

The alkylene group in L ₁₁ may be linear or branched, and for example, a preferable alkyl group having 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc. It can be mentioned as. More preferably, a C1-C6 alkylene group is preferable, and a C1-C4 alkylene group is especially preferable.

As an alkenylene group, the group which has a double bond in the arbitrary position of the alkylene group demonstrated by said L <_11> is mentioned.

The divalent aliphatic hydrocarbon ring group may be either monocyclic or polycyclic, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, a diamantanylene group, or the like. Preferable examples include a C3-C17 divalent aliphatic hydrocarbon ring group. More preferable is a C5-12 divalent aliphatic hydrocarbon ring group, and a C6-10 divalent aliphatic hydrocarbon ring group is particularly preferable.

As a divalent aromatic ring group, the arylene group which may have a C6-C14 substituent, such as a phenylene group, a tolylene group, a naphthylene group, for example, or thiophene, furan, pyrrole, benzothiophene, benzo And divalent aromatic ring groups containing heterocycles such as furan, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazole and thiazole.

In addition, there may be mentioned the same embodiment, respectively in the above-described X ₁₁ as the -NR- and bivalent nitrogen-containing non-aromatic heterocyclic group, as preferred examples.

As L _{11, a} single bond, an alkylene group, or a divalent aliphatic hydrocarbon ring group is more preferable, and a single bond or an alkylene group is particularly preferable.

L ₁₂ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a combination of two or more thereof, and some or all of the hydrogen atoms in the group are fluorine atoms or alkyl fluoride groups. It is substituted by the substituent chosen from nitro group, or cyano group. Two or more groups to be combined in the combined group may be the same or different, and as the linking group, -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group) and a divalent nitrogen-containing ratio You may be connected through the aromatic heterocyclic group or the group which combined these.

As L ₁₂ , an alkylene group in which part or all of hydrogen atoms are substituted with a fluorine atom or an fluorinated alkyl group (more preferably a perfluoroalkyl group), a divalent aromatic ring group, and a group combining these are more preferable, and at least some or all of them are Especially preferred are alkylene groups substituted with fluorine atoms. As L ₁₂ , an alkylene group having 30 to 100% of the number of hydrogen atoms substituted with a fluorine atom is most preferred.

The alkylene group in L ₁₂ may be linear or branched, and for example, a preferred alkyl group having 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc. It can be mentioned as. More preferably, a C1-C6 alkylene group is preferable, and a C1-C4 alkylene group is especially preferable.

As an alkenylene group, the group which has a double bond in the arbitrary position of the said alkylene group is mentioned.

The divalent aliphatic hydrocarbon ring group may be either monocyclic or polycyclic, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, a diamantanylene group, or the like. Preferable examples include a C3-C17 divalent aliphatic hydrocarbon ring group.

Examples of the divalent aromatic ring group include the same groups as the specific examples listed in the divalent aromatic ring group as the linking group in L ₁₁ described above.

Moreover, the same specific example as each in X <_11> mentioned above is mentioned as -NR- and bivalent nitrogen containing non-aromatic heterocyclic group of the coupling group in L <_12> , A preferable example is also the same.

Although the preferable specific example of L <_12> is shown below, it is not specifically limited to these.

Ar ₁ represents a group in which a divalent aromatic ring group or a divalent aromatic ring group and an alkylene group are combined.

The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, tolylene group, naphthylene group, or for example, thiophene, furan, pyrrole, benzothiophene, A bivalent aromatic ring group containing hetero rings, such as benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazole, thiazole, is mentioned as a preferable example.

Preferable substituents in the above groups include an alkoxy group such as an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group and a butoxy group, and a phenyl group listed in R ₁₁ to R ₁₃ . Aryl group is mentioned.

As a group which combined a divalent aromatic ring group and an alkylene group, C1-C8 alkyl, such as the divalent aromatic ring group mentioned above, for example, methylene group, ethylene group, a propylene group, butylene group, hexylene group, octylene group, etc. An aralkylene group which combined the rene group (linear or branched) may be mentioned as a preferable example.

As Ar _{1, a} C 6-18 arylene group which may have a substituent is more preferable, and a phenylene group substituted with a phenylene group, a naphthylene group, a biphenylene group, or a phenyl group is particularly preferable.

Z <_1> represents the site | part which becomes a sulfonic acid group, an imid acid group, or a methic acid group by irradiation of actinic light or a radiation. As the site | part represented by Z <_1> , the structure represented by the following general formula (ZI)-(ZIII) is especially preferable.

In General Formulas (ZII) and (ZIII), Z ₁ , Z ₂ , Z ₃ , Z ₄ and Z ₅ each independently represent -CO- or -SO _2- , and more preferably -SO _2- .

Rz ₁ , Rz ₂ and Rz ₃ each independently represent an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, and an aralkyl group. These groups are more preferably in a form in which some or all of the hydrogen atoms are replaced with a fluorine atom or a fluoroalkyl group (more preferably a perfluoroalkyl group), particularly in a form in which 30 to 100% of the hydrogen atoms are replaced with fluorine atoms desirable.

As said alkyl group, linear or branched form may be sufficient, for example, a C1-C8 alkyl group, such as a methyl group, an ethyl group, a propyl group, a butyl group, a hexyl group, an octyl group, is mentioned as a preferable example. The alkyl group having 1 to 6 carbon atoms is more preferable, and the alkyl group having 1 to 4 carbon atoms is particularly preferable.

As monovalent aliphatic hydrocarbon ring group, C3-C10 monovalent aliphatic hydrocarbon ring groups, such as a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group, are preferable, for example, A C3-C6 monovalent aliphatic hydrocarbon ring group is more preferable. .

As an aryl group, a C6-C18 aryl group is preferable, A C6-C10 aryl group is more preferable, A phenyl group is especially preferable.

As an aralkyl group, the aralkyl group which the C1-C8 alkylene group and the said aryl group couple | bonded is mentioned as a preferable example. The aralkyl group which the C1-C6 alkylene group and the said aryl group couple | bonded is more preferable, and the aralkyl group which the C1-C4 alkylene group and the said aryl group couple | bonded is especially preferable.

Rz ₁ , Rz ₂ and Rz ₃ are more preferably an alkyl group in which part or all of the hydrogen atoms are replaced with fluorine atoms or fluoroalkyl groups (more preferably perfluoroalkyl groups), and 30 to 100% of the number of hydrogen atoms Especially preferred are alkyl groups substituted with fluorine atoms.

In said general formula (ZI)-(ZIII), A <^+> represents the diaryl iodonium cation represented by the following general formula (A1).

In General Formula (A1), Ar ₁ represents a (p + 1) valent aromatic ring group, and Ar ₂ represents a (q + 1) valent aromatic ring group.

L ₁ and L ₂ each independently represent a single bond or an oxygen atom.

R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom or an alkyl group. At least two of R ₁₁ , R _12, and R ₁₃ may combine to form a ring. In addition, at least two of R ₂₁ , R _22, and R ₂₃ may combine to form a ring.

p and q each represent an integer of 0 to 9 and satisfy p + q ≧ 2.

In the case of p≥2, the groups represented by a plurality of (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ − may be the same or different.

In the case of q≥2, the groups represented by a plurality of (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL ₂ − may be the same or different.

However, when the general formula (A1) is represented by the following general formula (A1-1), L ₁ and L ₂ are the same as each other, and R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ are all Is not the same thing.

Although the aromatic ring in the aromatic ring group as Ar ₁ and the aromatic ring group as Ar ₂ is not specifically limited, It is preferable that it is a C6-C14 aromatic ring, It is preferable that it is a phenyl ring, a naphthalene ring, or an anthracene ring, and it is more preferable that it is a phenyl ring. Do.

As described above, L ₁ and L ₂ each independently represent a single bond or an oxygen atom, and in the case of a single bond, in particular, the outgas performance and sensitivity can be further improved, and in the case of an oxygen atom, especially outgas performance and stability over time Can be further improved.

The alkyl group in R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ is preferably an alkyl group having 1 to 20 carbon atoms, more preferably an alkyl group of 1-10, and even more preferably an alkyl group of 1-5. Do.

The groups represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) C- and the groups represented by (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) C- are each methyl group, ethyl group, propyl group, isopropyl group, n It is preferable that it is a C20 or less alkyl group, such as a butyl group, a sec-butyl group, a hexyl group, 2-ethylhexyl group, an octyl group, and a dodecyl group, It is more preferable that it is a C1-C8 alkyl group, and it is C1-C8 It is more preferable that it is an alkyl group of 3.

In particular, the groups represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ -and the groups represented by (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL ₂ -are each an alkyl group having 1 to 3 carbon atoms. Preferred (ie, L ₁ and L ₂ are single bonds in this case).

At least one of R ₁₁ , R ₁₂ and R ₁₃ and at least one of R ₂₁ , R ₂₂ and R ₂₃ are each preferably a hydrogen atom.

As a ring which at least 2 of R <_11> , R <_12> and R <_{13> may} combine and form, and the ring which at least 2 of R <_21> , R <_22> and R <_23> may combine and form, it may be mono-cyclic or polycyclic.

The monocyclic hydrocarbon ring having 3 to 7 carbon atoms is preferable, and the hydrocarbon ring having 5 or 6 carbon atoms is preferable. Examples of the monocyclic ring include a cyclopentane ring and a cyclohexane ring. As a polycyclic ring, a C4-20 hydrocarbon ring is preferable, and a C7-15 hydrocarbon ring is more preferable. Examples of the polycyclic ring include norbornane ring, tetracyclodecane ring, tetracyclododecane ring, and adamantane ring.

It is preferable that p and q respectively represent the integer of 0-5.

In the general formula (A1), any one of (i) p and q may be 2 or more, and the other may be 0, (ii) p may be an integer of 1 or more, and q may be an integer of 1 or more, but (ii ) p is an integer of 1 or more, and it is preferable that q is an integer of 1 or more. That is, each of the two aryl rings of the diaryliodonium cation is represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL _1- , or (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL _2- It is preferable to have a group represented by this, and it can especially improve outgas performance and time-lapse stability by this. In this case, p groups represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ -and q groups represented by (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL ₂ -are not the same group. More preferred.

In addition, in said general formula (A1), it is preferable that p and q are mutually different integers, and it can especially improve outgas performance and stability with time by this.

R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ are each represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL _1- , and (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) The group represented by CL ₂ -may be substituted with an alkenyl group, alkynyl group, aryl group, hydroxyl group, alkoxy group, thiol group, thioalkoxy group, amino group, halogen atom or the like in a range that does not lose electron donating. In addition, these substituents may be further substituted by these substituents, and if possible, may combine and form the ring.

At least two groups selected from the group consisting of a group represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ -and a group represented by (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL _2- It is preferable that one is located in the para position or the ortho position with respect to the iodonium group on an aromatic ring, It is more preferable that at least two of the said 2 or more groups are located in the para position or the ortho position, It is more preferable that all the groups are located in the para position or the ortho position.

In the above general formula (A1), a group represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ −, and a group represented by (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL ₂ − At least one of the two or more groups selected from the group consisting of is preferably positioned at the ortho position relative to the iodonium group on the aromatic ring.

Further, A ⁺ is a group represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ − on an aromatic ring by satisfying p + q ≧ ² in the general formula (A1), or (R ₂₁ ) Although having a total of two or more groups represented by (R ₂₂ ) (R ₂₃ ) CL ₂ −, it is particularly desirable to satisfy p + q ≧ 3 in terms of more reliably compatible outgas performance and aging stability. It is more preferable to satisfy p + q ≧ 4.

Im p≥1 and addition of p _{(R 11) (R 12)} (R 13) CL 1 - with respect to at least one of the groups represented by the dog it is preferred that L ₁ represents an oxygen atom. In addition, in said general formula (A1), it is more preferable that L <_1> and L <_2> represent an oxygen atom.

The diaryl iodonium cation represented by the general formula (A1) preferably has a sum of the Hammet values of all substituents for the iodonium group in the two aromatic rings (ie, Ar ₁ and Ar ₂ ), preferably -0.25. Or less, more preferably -0.5 or less, still more preferably -0.8 or less, and particularly preferably -1.0 or less. Total substituent groups for the iodonium field points to all of the substituents bonded to the aromatic ring (i.e., Ar ₁ and Ar ₂₎ of the diaryl iodonium cation. However, the iodonium group is excluded. In addition, the Hammet value of a substituent is based on the iodonium group in each diaryl iodonium skeleton.

Here, the Hammett value is described. Hammet's rule is an empirical rule proposed by L. P. Hammett in 1935 to quantitatively discuss the effect of substituents on the reaction or equilibrium of benzene derivatives, but this is widely accepted today. Substituent constants obtained by Hammet's law have σp and σm values, which can be found in most common Bible texts.For example, see JA Dean, 12th edition of Lang's Handbook of Chemistry, 1979 (Mc. Graw-Hill) and `` The Field of Chemistry '', 122, 96-103, 1979 (Nankodo), Naoki Inamoto, Chemistry Seminar 10 Hammet Rule -Structure and Reactivity- (1983, Maruzen) Issuance).

The Hammet value in the present invention is published by Naoki Inamoto, Chemistry Seminar 10 Hammet Rule -Structure and Reactivity- (Published by Maruzen, 1983), and Japan Chemical Society, Chemical Handbook Basic Edition Revised 5th Edition (2004, The numerical value described in Maruzen Corporation) is used.

Hammett values are normally used for m and p positions. The Hammet value used in the present invention is an electronic effect, and the value of the o position is calculated as the same value as the value of the p position.

The diaryl iodonium cation may be substituted with an electron withdrawing group on the aryl ring, but it is preferable that the sum of the Hammet values of all the substituents for the iodonium group is 0 or less. However, the value of the alkoxy group -OCH _3, an alkyl group uses a value of -CH _3.

Moreover, in the aromatic ring in Ar <_1> and Ar <_2> , it is represented by (R <_11> (R <_12> ) (R <_13> ) CL <_1-> in the range which the sum total of the Hammet values of all the substituents with respect to an iodonium group becomes zero or less. group, and _{(R 21) (R 22)} (R 23) CL 2 - group represented by may further have another substituent. Examples of such additional substituents include alkoxycarbonyl groups such as hydroxyl groups, halogen atoms (fluorine, chlorine, bromine, iodine), nitro groups, cyano groups, amide groups, sulfonamide groups, methoxycarbonyl groups, and ethoxycarbonyl groups, formyl groups and acetyl groups. And aryl groups such as acyloxy groups such as acyl groups such as benzoyl groups, acetoxy groups, and butyloxy groups, carboxyl groups, and phenyl groups.

Herein, when p≥1 and q≥1 and L ₁ and L ₂ are single bonds, only one of Ar ₁ and Ar ₂ has the above additional substituent, or Ar ₁ and Ar ₂ are different from each other. It is preferable to have the said additional substituent. Thereby, solid content in an actinic-ray-sensitive or radiation-sensitive resin composition becomes easy to melt | dissolve by a solvent, and it can make storage stability as a solution of an actinic-ray-sensitive or radiation-sensitive resin composition more excellent.

Although the preferable specific example of A <^+> in general formula (ZI)-(ZIII) is given below, it is not limited to these. In addition, in some of the following exemplary compounds, a hydrocarbon chain is described by the simplified structural formula which abbreviate | omits the symbol of carbon (C) and hydrogen (H). In addition, the sum total of the Hammet value of all the substituents with respect to the iodonium group of exemplary compound: (Z-1)-(Z-61) is shown in Table 1.

Specific examples of the polymerizable monomers in which the cation is released by actinic light or radiation irradiation to produce sulfonic acid, imide acid or methic acid with respect to the polymerizable monomer corresponding to the repeating unit of the general formula (I) are illustrated below. .

Next, general formula (II) is demonstrated.

In general formula (II), R <_21> , R <_22> , R <_23> represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group, or an alkoxycarbonyl group each independently.

The alkyl group is a linear or branched alkyl group which may have a substituent, and preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group or 2-ethyl which may have a substituent. C20 or less alkyl groups, such as a hexyl group, an octyl group, and a dodecyl group, are mentioned, More preferably, an alkyl group of 8 or less carbon atoms, Especially preferably, an alkyl group of 3 or less carbon atoms is mentioned.

As an alkyl group contained in the alkoxycarbonyl group, the same thing as the alkyl group in said R <_21> , R <_22> and R <_23> is preferable.

As monovalent aliphatic hydrocarbon ring group, the monocyclic or polycyclic aliphatic hydrocarbon ring group which may have a substituent is mentioned. Preferably, a monocyclic monovalent aliphatic hydrocarbon ring group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent is mentioned.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, with fluorine atom being particularly preferred.

Preferred substituents which each group may have include hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamide group, alkyl group listed in R ₂₁ to R ₂₃ , methoxy group, ethoxy Alkoxy groups such as alkoxy groups such as time periods, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups, acyl groups such as formyl groups, acetyl groups and benzoyl groups, Acyloxy groups, such as an acetoxy group and a butyloxy group, and a carboxy group are mentioned. In particular, a hydroxyl group and a halogen atom are preferable.

Formula (II) of R _21, R ₂₂ and R ₂₃ as hydrogen atom, an alkyl group, more preferably a halogen atom and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl (-CF _3), a hydroxymethyl group (-CH according to ₂ -OH), chloromethyl group (-CH ₂ -Cl), fluorine atom (-F) is particularly preferred.

X ₂₁ represents —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof.

As an alkyl group represented by R in -NR-, it is a linear or branched alkyl group which may have a substituent, and the specific example like the alkyl group in said R <_21> , R <_22> , R <_23> is mentioned. As R, a hydrogen atom, a methyl group and an ethyl group are particularly preferable.

In addition, the divalent nitrogen-containing non-aromatic heterocyclic group means preferably a 3-8 membered non-aromatic heterocyclic group having at least one nitrogen atom, and specifically, X ₁₁ to in general formula (I) described above there may be mentioned a structure example according to X _13.

As X _21, -O-, -CO-, -NR- (R is a hydrogen atom or an alkyl group), or a combination thereof is more preferable, and -COO-, -CONR- (R is a hydrogen atom or an alkyl group) is particularly preferable. Do.

L ₂₁ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group or a group of two or more thereof combined. Two or more groups to be combined in the combined group may be the same or different, and as the linking group, -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group) and a divalent nitrogen-containing ratio The aromatic heterocyclic group, the divalent aromatic ring group, or a combination thereof may be connected.

As an alkylene group in L <_21> , linear or branched form may be sufficient, for example, C1-C8, such as a methylene group, ethylene group, a propylene group, butylene group, a hexylene group, an octylene group, is mentioned as a preferable example. Can be. More preferably, a C1-C6 alkylene group is preferable, and a C1-C4 alkylene group is especially preferable.

As an alkenylene group, the group which has a double bond in the arbitrary position of the alkylene group demonstrated by said L <_21> is mentioned.

The divalent aliphatic hydrocarbon ring group may be either monocyclic or polycyclic, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, a diamantanylene group, or the like. Preferable examples include a C3-C17 divalent aliphatic hydrocarbon ring group. More preferable is a C5-12 divalent aliphatic hydrocarbon ring group, and a C6-10 divalent aliphatic hydrocarbon ring group is particularly preferable.

As a bivalent aromatic ring group as a coupling group, the arylene group which may have a C6-C14 substituent, such as a phenylene group, a tolylene group, a naphthylene group, for example, or thiophene, furan, pyrrole, benzothiophene And divalent aromatic ring groups containing hetero rings such as benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazole and thiazole.

In addition, there may be mentioned a specific example, such as each of the -NR- and bivalent nitrogen-containing non-aromatic heterocyclic group as the above X _21, as preferred examples.

L _{21 is an} alkylene group, a divalent aliphatic hydrocarbon ring group, or a group combining an alkylene group and a divalent aliphatic hydrocarbon ring group via -OCO-, -O-, or -CONH- (for example, -alkylene group-O-alkyl Benzene group, -alkylene group-OCO-alkylene group-, -divalent aliphatic hydrocarbon ring group-O-alkylene group-, -alkylene group-CONH-alkylene group-, etc. are especially preferable.

X ₂₂ , X ₂₃ are each independently a single bond, -O-, -S-, -CO-, -SO2-, -NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing nonaromatic heterocyclic group, or The group which combined these is shown.

Examples of -NR- and a divalent nitrogen-containing non-aromatic heterocyclic group for X ₂₂ and X ₂₃ include the same specific examples as in X ₂₁ described above, and preferred examples thereof are also the same.

As X _{22, a} single bond, -S-, -O-, -CO-, -SO _2- , and a combination thereof are more preferable, and a single bond, -S-, -OCO-, -OSO ₂ -is particularly preferable. Do.

X ₂₃ as -O-, -CO-, -SO ₂ -, and a combination of these groups, and more preferably, -OSO ₂ - is particularly preferred.

Ar <_2> represents group which combined a bivalent aromatic ring group or a bivalent aromatic ring group and an alkylene group.

The divalent aromatic ring group may have a substituent, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, tolylene group, naphthylene group, or for example, thiophene, furan, pyrrole, benzothiophene, A bivalent aromatic ring group containing hetero rings, such as benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazole, thiazole, is mentioned as a preferable example.

Preferable substituents in each of the above groups include an alkyl group, a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an alkoxy group such as a hydroxypropoxy group and a butoxy group, and a phenyl group listed in R ₂₁ to R ₂₃ . Aryl group is mentioned.

As a group which combined a divalent aromatic ring group and an alkylene group, C1-C8 alkyl, such as the divalent aromatic ring group mentioned above, for example, methylene group, ethylene group, a propylene group, butylene group, hexylene group, octylene group, etc. An aralkylene group which combined the rene group (linear or branched) may be mentioned as a preferable example.

As Ar <_2> , the arylene group which combined the C6-C18 arylene group which may have a substituent, the C6-C18 arylene group, and the C1-C4 alkylene is more preferable, A phenylene group, a naphthylene group, biphenyl A phenylene group substituted with a ethylene group and a phenyl group is particularly preferable.

L ₂₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group combining two or more thereof, in which some or all of the hydrogen atoms are fluorine, alkyl fluoride, or nitro groups Or a substituent selected from a cyano group. Two or more groups to be combined in the combined group may be the same or different, and as the linking group, -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group) and a divalent nitrogen-containing ratio You may be connected through the aromatic heterocyclic group or the group which combined these.

As L ₂₂ , an alkylene group in which part or all of hydrogen atoms are substituted with a fluorine atom or an fluorinated alkyl group (more preferably a perfluoroalkyl group), a divalent aromatic ring group, and a combination thereof are more preferable, and at least some or all of them are Especially preferred are alkylene groups substituted with fluorine atoms and divalent aromatic ring groups. As L ₂₂ , an alkylene group in which 30 to 100% of the number of hydrogen atoms is substituted with a fluorine atom, and a divalent aromatic ring group are most preferable.

The alkylene group for L ₂₂ may be linear or branched. Examples of preferred alkylene groups of 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group It can be mentioned as. More preferably, a C1-C6 alkylene group is preferable, and a C1-C4 alkylene group is especially preferable.

As an alkenylene group, the group which has a double bond in the arbitrary position of the said alkylene group is mentioned.

The divalent aliphatic hydrocarbon ring group may be either monocyclic or polycyclic, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, a diamantanylene group, or the like. Preferable examples include a C3-C17 divalent aliphatic hydrocarbon ring group.

Examples of the divalent aromatic ring group include the same groups as the specific examples listed in the divalent aromatic ring group as the linking group for L ₂₁ described above.

Moreover, the same specific example as each in X <_21> mentioned above is mentioned as -NR- and bivalent nitrogen containing non-aromatic heterocyclic group of the coupling group in L <_22> , and a preferable example is also the same.

As a preferable specific example of L <_22> , the structure illustrated in L <_12> in General formula (I) mentioned above is mentioned.

Z <_2> represents the site | part which turns into a sulfonic acid group, an imid acid group, or a methic acid group by irradiation of actinic light or a radiation. Z ₂ is suitable even for the above description relates to a Z ₁ and agreed in the formula _{(I), Z 1 Z 2} . In addition, there may be mentioned groups such as the embodiments listed in the Z ₁ As for the specific example.

Specific examples of the polymerizable monomer in which the cation is desorbed by actinic light or radiation irradiation to produce sulfonic acid, imide acid or methic acid with respect to the polymerizable monomer corresponding to the repeating unit of general formula (II) are shown below. .

Moreover, the repeating unit (A) may be a repeating unit which contains an aromatic ring in the said side chain except the counter cation of the said acid anion represented by general formula (I) or general formula (II) in another form.

Specific examples of the polymer monomer in which the cation is released by irradiation of actinic light or radiation with respect to the polymerizable monomer corresponding to this repeating unit (A) to produce sulfonic acid, imide acid or methic acid are shown below.

As a repeating unit (A), what is represented by general formula (III) is also preferable.

In General Formula (III), R ₃₁ , R ₃₂ and R ₃₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group.

The alkyl group is a linear or branched alkyl group which may have a substituent, and preferably a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group or 2-ethyl which may have a substituent. C20 or less alkyl groups, such as a hexyl group, an octyl group, and a dodecyl group, are mentioned, More preferably, an alkyl group of 8 or less carbon atoms, Especially preferably, an alkyl group of 3 or less carbon atoms is mentioned.

As an alkyl group contained in the alkoxycarbonyl group, the same thing as the alkyl group in said R <_31> , R <_32> and R <_33> is preferable.

As monovalent aliphatic hydrocarbon ring group, the monocyclic or polycyclic aliphatic hydrocarbon ring group which may have a substituent is mentioned. Preferably, a monocyclic monovalent aliphatic hydrocarbon ring group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent is mentioned.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, with fluorine atom being particularly preferred.

Preferred substituents which each group may have include hydroxyl group, halogen atom (fluorine, chlorine, bromine, iodine), nitro group, cyano group, amide group, sulfonamide group, alkyl group listed in R ₂₁ to R ₂₃ , methoxy group, ethoxy Alkoxy groups such as alkoxy groups such as time periods, hydroxyethoxy groups, propoxy groups, hydroxypropoxy groups, butoxy groups, alkoxycarbonyl groups such as methoxycarbonyl groups and ethoxycarbonyl groups, acyl groups such as formyl groups, acetyl groups and benzoyl groups, Acyloxy groups, such as an acetoxy group and a butyryloxy group, and a carboxy group are mentioned. In particular, a hydroxyl group and a halogen atom are preferable.

As R ₃₁ , R ₃₂ and R ₃₃ in formula (III), a hydrogen atom, an alkyl group and a halogen atom are more preferable, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ) and a hydroxymethyl group (-CH ₂ -OH), chloromethyl group (-CH ₂ -Cl), fluorine atom (-F) is particularly preferred.

X ₃₁ and X ₃₂ are each independently a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing nonaromatic heterocyclic group, Or group combining these.

As an alkyl group represented by R in -NR-, it is a linear or branched alkyl group which may have a substituent, and the specific example like the alkyl group in said R <_31> , R <_32> , R <_33> is mentioned. As R, a hydrogen atom, a methyl group and an ethyl group are particularly preferable.

In addition, the divalent nitrogen-containing nonaromatic heterocyclic group preferably has a 3 to 8 membered non-aromatic heterocyclic group having at least one nitrogen atom, and specifically, X ₁₁ to X in General Formula (I) described above. _The structure illustrated in ₁₃ is mentioned.

As X <_{31>, a} single bond, -O-, -CO-, -NR- (R is a hydrogen atom or an alkyl group), or group which combined these is more preferable, -COO-, -CONR- (R is a hydrogen atom or an alkyl group) This is particularly preferred.

As X _{32, a} single bond, -O-, -CO-, -SO _2- , a divalent nitrogen-containing nonaromatic heterocyclic group, and a group in combination thereof are more preferable, and a single bond, -OCO-, -OSO _2- , 2 Particularly preferred are groups in which a volatile nitrogen-containing nonaromatic heterocyclic group and -SO ₂ -are combined.

L ₃₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group or a group of two or more thereof combined. Two or more groups to be combined in the combined group may be the same or different, and as the linking group, -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group) and a divalent nitrogen-containing ratio You may be connected through the aromatic heterocyclic group or the group which combined these.

The alkylene group for L ₃₁ may be linear or branched. For example, examples of the alkylene group having 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group are given as preferable examples. Can be. More preferably, a C1-C6 alkylene group is preferable, and a C1-C4 alkylene group is especially preferable.

As an alkenylene group, the group which has a double bond in arbitrary positions of the alkylene group demonstrated by said L <_31> is mentioned.

The divalent aliphatic hydrocarbon ring group may be either monocyclic or polycyclic, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, a diamantanylene group, or the like. Preferable examples include a C3-C17 divalent aliphatic hydrocarbon ring group. More preferable is a C5-12 divalent aliphatic hydrocarbon ring group, and a C6-10 divalent aliphatic hydrocarbon ring group is particularly preferable.

In addition, there may be mentioned a specific example, such as each of the -NR- and bivalent nitrogen-containing non-aromatic heterocycle which X ₃₁ described above as the ventilation, as preferred examples.

L _{31 is a} single bond, an alkylene group, a divalent aliphatic hydrocarbon ring group, or a group combining an alkylene group or a divalent aliphatic hydrocarbon ring group via -OCO-, -O-, or -CONH- (for example, -alkylene group- O-alkylene group-, -alkylene group-OCO-alkylene group-, -divalent aliphatic hydrocarbon ring group-O-alkylene group-, -alkylene group-CONH-alkylene group-, etc. are especially preferable.

L ₃₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a combination of two or more thereof, in which some or all of the hydrogen atoms are selected from a fluorine atom, an alkyl fluoride group, a nitro group, or a cyano group It is substituted by the substituent selected. Two or more groups combined in the combined group may be the same or different, and as a linking group, -O-, -S-, -CO-, -SO2-, -NR- (R is a hydrogen atom or an alkyl group) and a divalent nitrogen-containing nonaromatic You may be connected through the heterocyclic group or the group which combined them.

As L _32, an alkylene group in which part or all of hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably perfluoroalkyl group) is more preferable, and an alkylene group in which part or all of hydrogen atoms are substituted with fluorine atoms is particularly preferred. desirable. As L ₃₂ , an alkylene group having 30 to 100% of the number of hydrogen atoms substituted with a fluorine atom is most preferred.

The alkylene group for L ₃₂ may be linear or branched. Examples of preferred alkylene groups of 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group It can be mentioned as. More preferably, a C1-C6 alkylene group is preferable, and a C1-C4 alkylene group is especially preferable.

As an alkenylene group, the group which has a double bond in the arbitrary position of the said alkylene group is mentioned.

The divalent aliphatic hydrocarbon ring group may be either monocyclic or polycyclic, for example, a cyclobutylene group, a cyclopentylene group, a cyclohexylene group, a norbornanylene group, an adamantylene group, a diamantanylene group, or the like. Preferable examples include a C3-C17 divalent aliphatic hydrocarbon ring group.

Examples of -NR- and a divalent nitrogen-containing non-aromatic heterocyclic group of the linking group in L ₃₂ include the same specific examples as in X ₃₁ described above, and preferred examples thereof are also the same.

As a preferable specific example of L <_32> , the structure illustrated in L <_12> in General formula (I) mentioned above is mentioned.

Z <_3> represents the site | part which turns into a sulfonic acid group, an imid acid group, or a methic acid group by irradiation of actinic light or a radiation. Z ₃ is suitable even for the above description relates to a Z ₁ and agreed in the formula _{(I), Z 1 Z 3} . In addition, there may be mentioned groups such as the embodiments listed in the Z ₁ As for the specific example.

Specific examples of the polymer monomers in which the cation is desorbed by actinic light or radiation irradiation to produce sulfonic acid, imide acid or methic acid with respect to the polymerizable monomer corresponding to the repeating unit of formula (III) are shown below.

The polymerizable compound corresponding to the repeating unit (A) can be synthesized by using a general sulfonic acid esterification reaction or sulfonamide reaction. For example, a method of reacting one sulfonyl halide portion of a bissulfonyl halide compound with a amine, an alcohol or the like to form a sulfonamide bond, a sulfonic acid ester bond, and then hydrolyzing the other sulfonyl halide portion, or It can obtain by the method of ring-opening cyclic sulfonic acid anhydride with amine and alcohol. See also US5554664, J. Fluorine Chem. 105 (2000) 129-136, J. Fluorine Chem. The synthesis described in 116 (2002) 45-48 can also be readily synthesized.

The polymerizable compound corresponding to the repeating unit (A) is disclosed in Japanese Patent Application Laid-Open No. 11-501909, or Japan, from a hydroxide, bromide, chloride or the like of lithium, sodium, potassium salt and iodide or sulfonium of the organic acid synthesized above. It can be synthesize | combined easily using the salt exchange method of Unexamined-Japanese-Patent No. 2003-246786, the salt exchange method of Unexamined-Japanese-Patent No. 10-232490, 404039, etc., and the like.

Specific examples of the polymerizable compound (M) corresponding to the repeating unit (A) in the following table are cationic structures ((Z-1) to (Z-61) in the above examples) and anionic structures ((I-1 described above). )-(I-65), (II-1) to (II-27), and (III-1) to (III-40), except for the hydrogen atom of the organic acid.

The content rate of the repeating unit (A) in the resin (P) is preferably in the range of 0.5 to 80 mol%, more preferably in the range of 1 to 60 mol%, more preferably 3 to 40 mol relative to the total repeating units. Range of%.

[Repeating unit (B)]

The resin (P) has a repeating unit (B) (hereinafter sometimes referred to as a "repeating unit having an acid-decomposable group") in addition to the repeating unit (A), which is decomposed by the action of an acid to generate an alkali-soluble group. It is preferable.

As an alkali-soluble group, a phenolic hydroxyl group, a carboxyl group, a fluorinated alcohol group, a sulfonic acid group, a sulfonamide group, a sulfonimide group, (alkylsulfonyl) (alkylcarbonyl) methylene group, (alkylsulfonyl) (alkylcarbonyl) Imide group, bis (alkylcarbonyl) methylene group, bis (alkylcarbonyl) imide group, bis (alkylsulfonyl) methylene group, bis (alkylsulfonyl) imide group, tris (alkylcarbonyl) methylene group, tris ( Alkyl sulfonyl) methylene group etc. are mentioned.

Preferred alkali-soluble groups include phenolic hydroxyl groups, carboxyl groups, fluorinated alcohol groups (preferably hexafluoroisopropanol), and sulfonic acid groups.

A group preferable as an acid-decomposable group is group which substituted the hydrogen atom of these alkali-soluble groups by the group which detach | desorbs with acid.

Examples of the group that are released to the acid include -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), and -C (= 0) -OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₀₁ ) (R ₀₂ ) -C (= O) -OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -CH (R ₃₆ ) (Ar ), And the like.

In the formula, each of R ₃₆ to R ₃₉ independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group. R ₃₆ and R ₃₇ may be bonded to each other to form a ring.

R ₀₁ to R ₀₂ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, a group in which an alkylene group and a monovalent aromatic ring group are combined, or an alkenyl group.

Ar represents a monovalent aromatic ring group.

The alkyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkyl group having 1 to 8 carbon atoms, and for example, methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group, octyl group Etc. can be mentioned.

The monovalent aliphatic hydrocarbon ring group of R ₃₆ to R ₃₉ , R _01, and R ₀₂ may be monocyclic or polycyclic. As monocyclic type, a C3-C8 aliphatic hydrocarbon ring group is preferable, For example, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cyclooctyl group, etc. are mentioned. As a polycyclic type, a C6-C20 aliphatic hydrocarbon ring group is preferable, For example, an adamantyl group, norbornyl group, isoboroyl group, campanyl group, dicyclopentyl group, (alpha)-pinenel group, tricyclo decanyl group, Tetracyclododecyl group, anthrostanyl group, etc. are mentioned. In addition, a part of the carbon atoms in the aliphatic hydrocarbon ring group may be substituted by a hetero atom such as an oxygen atom.

The monovalent aromatic ring group of R ₃₆ to R ₃₉ , R _01, and R ₀₂ and Ar is preferably a monovalent aromatic ring group having 6 to 10 carbon atoms, for example, an aryl group such as phenyl group, naphthyl group, anthryl group, tee And divalent aromatic ring groups including heterocycles such as opene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazole and thiazole. .

R ₃₆ ~R _39, R ₀₁ and the group as a combination of an alkylene group and a monovalent ventilation direction of the R _02, and preferably an aralkyl group having a carbon number of 7 to 12, for an example, a benzyl group, a phenethyl group, a naphthylmethyl group, etc. Can be mentioned.

The alkenyl group of R ₃₆ to R ₃₉ , R ₀₁ and R ₀₂ is preferably an alkenyl group having 2 to 8 carbon atoms, and examples thereof include vinyl group, allyl group, butenyl group, cyclohexenyl group and the like.

The ring formed by combining R ₃₆ and R ₃₇ with each other may be monocyclic or polycyclic. As monocyclic type, a C3-C8 aliphatic hydrocarbon ring structure is preferable, For example, a cyclopropane structure, a cyclobutane structure, a cyclopentane structure, a cyclohexane structure, a cycloheptane structure, a cyclooctane structure, etc. are mentioned. As the polycyclic type, an aliphatic hydrocarbon ring structure having 6 to 20 carbon atoms is preferable, and examples thereof include adamantane structure, norbornane structure, dicyclopentane structure, tricyclodecane structure, and tetracyclododecane structure. . In addition, a part of the carbon atoms in the aliphatic hydrocarbon ring structure may be substituted by heteroatoms such as oxygen atoms.

Each of the groups as R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ , and Ar may have a substituent, and examples of the substituent include an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, an amino group, an amide group, a ureido group, and a urethane. A group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, an acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, etc. are mentioned, C8 of a substituent is preferable.

As a repeating unit (B), the repeating unit represented with the following general formula (V) or (VI) is more preferable.

In General Formula (V), R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₅₂ may be bonded to L ₅ to form a ring (preferably a 5- or 6-membered ring), in which case R ₅₂ represents an alkylene group.

L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.

R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may be bonded to each other to form a ring. However, R ₅₅ and R ₅₆ do not simultaneously represent a hydrogen atom.

In General Formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring (preferably a 5- or 6-membered ring), in which case R ₆₂ represents an alkylene group.

Ar ₆ represents a (n + 1) valent aromatic ring group, and when combined with R ₆₂ to form a ring, (n + 2) valent aromatic ring group.

Y represents a group which is released by the action of a hydrogen atom or an acid, and when a plurality of Y are present, a plurality of Y may be the same or different. Provided that at least one of Y represents a group that is released by the action of an acid.

n represents the integer of 1-4.

General formula (V) is demonstrated in more detail.

As an alkyl group of R <_51> -R <_53> in general formula (V), The methyl group, ethyl group, propyl group, isopropyl group which may preferably have a substituent, n-butyl group, sec-butyl group, hexyl group, 2- C20 or less alkyl groups, such as an ethylhexyl group, an octyl group, and a dodecyl group, are mentioned, More preferably, an alkyl group of 8 or less carbon atoms, Especially preferably, an alkyl group of 3 or less carbon atoms is mentioned.

As an alkyl group contained in the alkoxycarbonyl group, the same thing as the alkyl group in said R <_51> -R <_53> is preferable.

Examples of the monovalent aliphatic hydrocarbon ring group include monovalent aliphatic hydrocarbon ring groups which may be monocyclic or polycyclic. Preferably, a monocyclic monovalent aliphatic hydrocarbon ring group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group which may have a substituent is mentioned.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom, with fluorine atom being particularly preferred.

As a preferable substituent in each said group, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, an amino group, an amide group, a ureido group, a urethane group, a hydroxyl group, a carboxyl group, a halogen atom, an alkoxy group, a thioether group, An acyl group, an acyloxy group, an alkoxycarbonyl group, a cyano group, a nitro group, etc. are mentioned, As for carbon number of a substituent, 8 or less are preferable.

Moreover, when R <_52> represents an alkylene group, Preferably, as an alkylene group, C1-C8 alkylene groups, such as a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, an octylene group, are mentioned. The alkylene group having 1 to 4 carbon atoms is more preferable, and the alkylene group having 1 to 2 carbon atoms is particularly preferable.

As R ₅₁ and R ₅₃ in formula (V), a hydrogen atom, an alkyl group, and a halogen atom are more preferable, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ), and a hydroxymethyl group (-CH ₂ -OH ), Chloromethyl group (-CH ₂ -Cl) and fluorine atom (-F) are particularly preferred. As R _{52, a} hydrogen atom, an alkyl group, a halogen atom, and an alkylene group (which forms a ring with Q) are more preferable, and a hydrogen atom, a methyl group, an ethyl group, a trifluoromethyl group (-CF ₃ ), and a hydroxymethyl group (-CH _2- OH), a chloromethyl group (-CH ₂ -Cl), a fluorine atom (-F), a methylene group (forms a ring with L ₅ ), and an ethylene group (forms a ring with L ₅ ) is particularly preferred.

Examples of the divalent linking group represented by L ₅ include an alkylene group, a divalent aromatic ring group, -COO-L _1- , -OL _1- , -L ₁ -O-, and a group formed by combining two or more thereof. Can be. Here, L <_1> represents the group which combined the alkylene group, the bivalent aliphatic hydrocarbon ring group, the bivalent aromatic ring group, the alkylene group, and the bivalent aromatic ring group, and may be further substituted by substituents, such as a fluorine atom.

L ₅ is preferably a single bond, -COO-L _1- (L ₁ is preferably an alkylene group having 1 to 5 carbon atoms, more preferably methylene or propylene group) or a group represented by a divalent aromatic ring group.

As an alkyl group of R <_54> -R <_56> , a C1-C20 thing is preferable, More preferably, it is a C1-C10 thing, A methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, Particularly preferred are those having 1 to 4 carbon atoms such as t-butyl group.

The monovalent aliphatic hydrocarbon ring group represented by R ₅₅ and R ₅₆ preferably has 3 to 20 carbon atoms, and may be monocyclic such as a cyclopentyl group and a cyclohexyl group, and may be a norbornyl group, adamantyl group, or tetracyclodeca. Polycyclic ones, such as a silyl group and a tetracyclo dodecanyl group, may be sufficient.

Moreover, as a ring formed by combining R <_55> and R <_56> mutually, C3-C20 is preferable, Monocyclic things, such as a cyclopentyl group and a cyclohexyl group, may be sufficient and a norbornyl group, adamantyl group, and tetracyclo Polycyclic ones, such as a decanyl group and a tetracyclo dodecanyl group, may be sufficient. When R ₅₅ and R ₅₆ are bonded to each other to form a ring, R ₅₄ is preferably an alkyl group having 1 to 3 carbon atoms, and more preferably a methyl group or an ethyl group.

As the monovalent aromatic ring group represented by R ₅₅ and R ₅₆ , one having 6 to 20 carbon atoms is preferable, and examples thereof include a phenyl group and a naphthyl group. When either one of R ₅₅ and R ₅₆ is a hydrogen atom, the other is preferably a monovalent aromatic ring group.

As a synthesis | combining method of the monomer corresponded to the repeating unit represented by general formula (V), it is possible to apply the synthesis | combining method of a general polymeric group containing ester, and it is not specifically limited.

Although the specific example of the repeating unit represented by general formula (V) below is shown, this invention is not limited to this.

General formula (VI) is demonstrated in detail.

As the alkyl group of R ₆₁ to R _{63 in} the general formula (VI), a methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2- which may preferably have a substituent And an alkyl group having 20 or less carbon atoms, such as an ethylhexyl group, an octyl group and a dodecyl group, and more preferably an alkyl group having 8 or less carbon atoms.

As an alkyl group contained in the alkoxycarbonyl group, the same thing as the alkyl group in said R <_61> -R <_63> is preferable.

As monovalent aliphatic hydrocarbon ring group, monocyclic or polycyclic may be sufficient, Preferably, C3-C8 monocyclic monovalent aliphatic hydrocarbon ring groups, such as the cyclopropyl group, cyclopentyl group, and cyclohexyl group which may have a substituent are mentioned. Can be.

As a halogen atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom are mentioned, A fluorine atom is more preferable.

When R ₆₂ represents an alkylene group, an alkylene group preferably has 1 to 8 carbon atoms such as methylene group, ethylene group, propylene group, butylene group, hexylene group and octylene group which may have a substituent.

Ar ₆ represents an (n + 1) valent aromatic ring group. When n is 1, the divalent aromatic ring group is, for example, an arylene group having 6 to 18 carbon atoms such as a phenylene group, tolylene group, naphthylene group, or thiophene, furan, pyrrole, benzoti A bivalent aromatic ring group containing heterocycles, such as offen, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazole, thiazole, is mentioned as a preferable example.

As a specific example of the (n + 1) valent aromatic ring group in case n is an integer of 2 or more, the group formed by dividing (n-1) arbitrary hydrogen atoms from said specific example of a bivalent aromatic ring group is mentioned preferably. The (n + 1) valent aromatic ring group may further have a substituent.

As a substituent which the alkyl group, monovalent aliphatic hydrocarbon ring group, alkoxycarbonyl group, alkylene group, and (n + 1) valent aromatic ring group which were mentioned above may have, each represented by R <_51> -R <_53> in General formula (V) mentioned above Specific examples, such as a substituent which a group may have, are mentioned.

It is preferable that it is 1 or 2, and, as for n, it is more preferable.

each of n Y independently represents a group which is released by the action of a hydrogen atom or an acid. Provided that at least one of n represents a group that is released by the action of an acid.

Examples of the group Y desorbed by the action of an acid include the groups exemplified above, that is, -C (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (= O) -OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ), -C (R ₀₁ ) (R ₀₂ ) (OR ₃₉ ), -C (R ₀₁ ) (R ₀₂ ) -C (= O) -OC (R ₃₆ ) (R ₃₇ ) (R ₃₈ ),- CH (R ₃₆ ) (Ar) etc. are mentioned. In these formulas, R ₃₆ to R ₃₉ , R _01, and R ₀₂ are synonymous with the groups described above.

As group Y detached by the action of an acid, the structure represented by the following general formula (VI-A) is more preferable.

Herein, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a monovalent aromatic ring group, or a group combining an alkylene group and a monovalent aromatic ring group.

M represents a single bond or a divalent linking group.

Q represents an alkyl group, the monovalent aliphatic hydrocarbon ring group which may contain the hetero atom, the monovalent aromatic ring group which may contain the hetero atom, an amino group, an ammonium group, a mercapto group, a cyano group, or an aldehyde group.

At least two of Q, M, and L ₁ may be bonded to form a ring (preferably a 5- or 6-membered ring).

The alkyl groups as L ₁ and L ₂ are, for example, alkyl groups having 1 to 8 carbon atoms, and specific examples thereof include methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group, hexyl group and octyl group.

The monovalent aliphatic hydrocarbon ring group as L ₁ and L ₂ is, for example, an aliphatic hydrocarbon ring group having 3 to 15 carbon atoms, and specific examples thereof include a cyclopentyl group, a cyclohexyl group, a norbornyl group, and an adamantyl group. have.

The monovalent aromatic ring groups as L ₁ and L ₂ are, for example, an aryl group having 6 to 15 carbon atoms, and specific examples thereof include phenyl group, tolyl group, naphthyl group, anthryl group and the like.

The group which combined the alkylene group and monovalent aromatic ring group as L <_1> and L <_2> is C6-C20, for example, and aralkyl groups, such as a benzyl group and a phenethyl group, are mentioned.

The divalent linking group as M is, for example, an alkylene group (for example, methylene group, ethylene group, propylene group, butylene group, hexylene group, octylene group, etc.), a divalent aliphatic hydrocarbon ring group (for example, cyclopentyl Ethylene group, cyclohexylene group, adamantylene group, etc.), alkenylene group (for example, ethylene group, propenylene group, butenylene group, etc.), divalent aromatic ring group (for example, phenylene group, tolylene group, a naphthylene group, etc.), -S-, -O-, -CO-, -SO 2 -, -N (R 0) -, and a divalent linking group combining a plurality of these. R ₀ is a hydrogen atom or an alkyl group (for example, an alkyl group having 1 to 8 carbon atoms, and specifically, methyl, ethyl, propyl, n-butyl, sec-butyl, hexyl, or octyl).

The alkyl group as Q is the same as each group as L ₁ and L ₂ described above.

As a monovalent aliphatic hydrocarbon ring group which may contain the hetero atom as Q, and the aliphatic hydrocarbon ring group which does not contain the hetero atom in the monovalent aromatic ring group which may contain the hetero atom, and the monovalent aromatic ring group which does not contain the hetero atom, The monovalent aliphatic hydrocarbon ring group as above-mentioned L <_1> and L <_2>, a monovalent aromatic ring group, etc. are mentioned, Preferably they are C3-C15.

As a monovalent aliphatic hydrocarbon ring group containing a hetero atom and the monovalent aromatic ring group containing a hetero atom, for example, thiran, cyclothiorane, thiophene, furan, pyrrole, benzothiophene, benzofuran, benzopyrrole, tri Groups having heterocyclic structures such as azine, imidazole, benzimidazole, triazole, thiadiazole, thiazole, pyrrolidone, etc. may be mentioned, but a structure generally called a heterocyclic ring (a ring formed of carbon and heteroatoms, Or a ring formed with a hetero atom).

As a ring which at least 2 of Q, M, and L <_{1> may} combine and form, at least 2 of Q, M, and L <_1> couple | bonds, for example, 5-membered which forms a propylene group and a butylene group, and contains an oxygen atom Or the case of forming a six-membered ring.

Each group represented by L ₁ , L ₂ , M, Q in General Formula (VI-A) may have a substituent, for example, R ₃₆ to R ₃₉ , R ₀₁ , R ₀₂ , and Ar described above. The thing enumerated as this substituent which may have is mentioned, As for carbon number of a substituent, 8 or less is preferable.

As group represented by -M-Q, group which consists of C1-C30 is preferable, and group which consists of C5-C20 is more preferable.

Although the specific example of the repeating unit represented by general formula (VI) is shown below, this invention is not limited to this.

As for the content rate of the repeating unit (B) in resin (P) of this invention, the range of 3-90 mol% is preferable with respect to all the repeating units, The range of 5-80 mol% is more preferable, 7-70 mol The range of% is especially preferable.

Further, the ratio (moles of A / moles of B) of the repeating unit (A) and the repeating unit (B) in the resin is preferably 0.04 to 1.0, more preferably 0.05 to 0.9, and particularly preferably 0.06 to 0.8.

[Repeat unit (C)]

Resin (P) of this invention has a repeating unit (C) which has alkali-soluble group. The repeating unit (C) is preferably an alkali-soluble group having an aromatic ring group, and more preferably a structure represented by the following general formula (I).

Here, R ₁₁ ′, R ₁₂ ′ and R ₁₃ ′ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₃ ′ may be bonded to Ar ₁ ′ to form a ring (preferably a 5- or 6-membered ring), in which case R ₁₃ ′ represents an alkylene group.

X ₁ represents a single bond or a divalent linking group.

Ar ₁ ′ represents a (n + 1) valent aromatic ring group, and when combined with R ₁₃ ′ to form a ring, (n + 2) valent aromatic ring group.

n represents the integer of 1-4.

Specific examples of the alkyl group represented by R ₁₁ ′, R ₁₂ ′, and R ₁₃ ′ in formula (I), monovalent aliphatic hydrocarbon ring groups, halogen atoms, and alkoxycarbonyl groups and the substituents that these groups may have include general formula (V) The specific example similar to each group in is mentioned.

X ₁ represents a single bond or a divalent linking group. As the divalent linking group represented by X ₁ , for example, -COO-, -CONH-, -OCO-, -CO-, -O-, -S-, -SO-, -SO _2- , -NH-, Alkylene group, a cycloalkylene group, and an alkenylene group are mentioned. Among them, -COO-, -CONH-, -OCO-, -CO-, -S-, -SO- or -SO ₂ -are preferable, and -COO-, -CONH-, -SO ₂ -or -SO ₃ -More preferred.

Ar ₁ ′ represents an aromatic ring group having a (n + 1) valence. The divalent aromatic ring group in the case where n is 1, for example, arylene groups having 6 to 18 carbon atoms such as phenylene group, tolylene group, naphthylene group, anthracenylene group, or for example, thiophene, furan, A bivalent aromatic ring group containing hetero rings, such as pyrrole, benzothiophene, benzofuran, benzopyrrole, triazine, imidazole, benzoimidazole, triazole, thiadiazole, thiazole, is mentioned as a preferable example.

As a specific example of the (n + 1) valent aromatic ring group in case n is an integer of 2 or more, the group formed by dividing (n-1) arbitrary hydrogen atoms from said specific example of a bivalent aromatic ring group is mentioned preferably.

The (n + 1) valent aromatic ring group may further have a substituent, and as such further substituents, the alkyl groups, methoxy groups, ethoxy groups, hydroxyethoxy groups, propoxy groups and hydroxypropenes listed in R ₅₁ to R _{53 may be used} . Aryl groups, such as an alkoxy group, such as an alkoxy group and butoxy group, and a phenyl group, are mentioned.

As Ar <_1>', the C6-C18 aromatic ring group which may have a substituent is more preferable, A benzene ring group, a naphthalene ring group, and a biphenylene ring group are especially preferable.

As for the content rate of the repeating unit which has alkali-soluble group represented by General formula (I), 3-90 mol% is preferable with respect to all the repeating units in resin (P), More preferably, it is 5-80 mol%, More preferably, it is 7- 70 mol%.

Although the specific example of the repeating unit which has alkali-soluble group represented by General formula (I) is shown below, this invention is not limited to this. In formula, a represents the integer of 0-2.

[Repeat unit (D)]

It is preferable that resin (P) also has a repeating unit (D) which has group which decomposes by the action of an alkaline developing solution, and the dissolution rate in an alkaline developing solution increases.

A lactone structure, a phenyl ester structure, etc. are mentioned as group which decomposes by the action of an alkaline developing solution, and the dissolution rate in an alkaline developing solution increases.

As a repeating unit (D), the repeating unit represented with the following general formula (AII) is more preferable.

In general formula (AII)

Rb ₀ represents a hydrogen atom, a halogen atom or an alkyl group (preferably having 1 to 4 carbon atoms) which may have a substituent.

The preferable substituent which the alkyl group of Rb ₀ may have include a hydroxyl group and a halogen atom. Examples of the halogen atom of Rb ₀ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Rb ₀ is preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a trifluoromethyl group, and a hydrogen atom or a methyl group is particularly preferable.

Ab represents a divalent linking group having a single bond, an alkylene group, a monocyclic or polycyclic aliphatic hydrocarbon ring structure, an ether bond, an ester bond, a carbonyl group, or a divalent linking group combining these. Ab is preferably a single bond, a divalent linking group represented by -Ab ₁ -CO _2- .

Ab ₁ is a linear or branched alkylene group, a monocyclic or polycyclic aliphatic hydrocarbon ring group, preferably a methylene group, an ethylene group, a cyclohexylene group, an adamantylene group or a norbornylene group.

V decomposes | dissolves by the action of an alkaline developing solution, and shows the group which the dissolution rate in an alkaline developing solution increases. Preferably it is group which has an ester bond, and the group which has lactone structure is especially preferable.

Although any group can be used as long as it has a lactone structure, Preferably it is a 5-7 member cyclic lactone structure, The ring structure which forms a bicyclo structure and a spiro structure in a 5-7 member cyclic lactone structure is another ring structure. It is preferable that is condensed. It is more preferable to have a repeating unit having a lactone structure represented by any one of the following General Formulas (LC1-1) to (LC1-17). In addition, the lactone structure may be directly bonded to the main chain. Preferred lactone structures are (LC1-1), (LC1-4), (LC1-5), (LC1-6), (LC1-13), (LC1-14) and (LC1-17).

The lactone structure portion may or may not have a substituent (Rb ₂ ). Preferred substituents (Rb ₂ ) include an alkyl group having 1 to 8 carbon atoms, a monovalent aliphatic hydrocarbon ring group having 4 to 7 carbon atoms, an alkoxy group having 1 to 8 carbon atoms, an alkoxycarbonyl group having 1 to 8 carbon atoms, a carboxyl group, a halogen atom, a hydroxyl group and a cyano group And acid-decomposable groups. More preferably, they are a C1-C4 alkyl group, cyano group, and an acid-decomposable group. n ₂ represents an integer of 0 to 4. n substituents (Rb _2), which _second plurality is present as 2 or more, which may be the same or different, or may form a ring by combining with each other the substituent (Rb ₂₎ to present a plurality.

The repeating unit having a lactone group usually has an optical isomer, but any optical isomer may be used. In addition, 1 type of optical isomers may be used individually, or some optical isomers may be mixed and used. When one type of optical isomer is mainly used, the optical purity (ee) thereof is preferably 90% or more, and more preferably 95% or more.

The content rate of the repeating unit (D) in the resin (P) is preferably in the range of 0.5 to 80 mol%, more preferably in the range of 1 to 60 mol%, more preferably 2 to 40 mol, based on the total repeating units. Range of%. One type of repeating unit (D) may be used, and may be used in combination of 2 or more type. By using a specific lactone structure, line edge roughness and development defects are improved.

Although the specific example of the repeating unit (D) in resin (P) is shown below, this invention is not limited to this. In the formula, Rx represents H, CH ₃ , CH ₂ OH, or CF ₃ .

[Other repeating units]

Resin (P) may further have a repeating unit which has a polar group as repeating units other than the above-mentioned repeating unit. Examples of polar group a hydroxyl group, a cyano group, a carboxyl group, a sulfonyl imide group, a bis sulfonyl imide group, the α position, for the alcoholic hydroxyl group (for example, substituted by electron withdrawing groups, hexafluoroisopropanol: -C (CF ₃ ) ₂ OH). When resin (P) has such a repeating unit, board | substrate adhesiveness and developer affinity can be improved by this. The repeating unit having a polar group other than the above-mentioned repeating unit is preferably a repeating unit having a hydroxyl group or a cyano group, more preferably a repeating unit having an alicyclic hydrocarbon structure substituted with a hydroxyl group or a cyano group, and having no acid-decomposable group. More preferred. As an alicyclic hydrocarbon structure in the alicyclic hydrocarbon structure substituted by the hydroxyl group or the cyano group, an adamantyl group, diamantyl group, and norbornane group are preferable. As an alicyclic hydrocarbon structure substituted by the hydroxyl group or the cyano group, the partial structure represented by the following general formula (VIIa)-(VIId) is preferable.

In formulas (VIIa) to (VIIc), R ₂ c to R ₄ c each independently represent a hydrogen atom, a hydroxyl group, or a cyano group. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group or a cyano group. Preferably, one or two of R ₂ c to R ₄ c are hydroxyl groups, and the rest are hydrogen atoms. In general formula (VIIa), More preferably, _two of R < ₂ > c-R <_4> c are hydroxyl groups, and the remainder is a hydrogen atom.

As a repeating unit which has the partial structure represented by general formula (VIIa)-(VIId), the repeating unit represented by the following general formula (AIIa)-(AIId) is mentioned.

In General Formulas (AIIa) to (AIId), R ₁ c represents a hydrogen atom, a methyl group, a trifluoromethyl group, or a hydroxymethyl group.

R ₂ is R ₂ c~R c~R ₄ c ₄ c and agreement in the formula (VIIa) ~ (VIIc).

Although resin (P) does not need to contain even if it contains the repeating unit which has a polar group, when it contains, the content rate is 1-60 mol% with respect to all the repeating units in resin (P), More preferably, it is 5-50 Molar%.

Although the specific example of the repeating unit which has a polar group is given to the following, this invention is not limited to these.

Resin (P) of this invention may also have a repeating unit which has a cyclic hydrocarbon structure which does not have a polar group, and does not show acid decomposability. As such a repeating unit, the repeating unit represented by general formula (VII) is mentioned.

R <_5> in general formula (VII) represents a hydrocarbon group which has at least 1 cyclic hydrocarbon structure, and does not have a polar group (hydroxyl group, cyano group, etc.).

Ra represents a hydrogen atom, an alkyl group or a -CH ₂ -O-Ra ₂ group. In the formula, Ra ₂ represents a hydrogen atom, an alkyl group or an acyl group. Ra is preferably a hydrogen atom, a methyl group, a hydroxymethyl group or a trifluoromethyl group, and particularly preferably a hydrogen atom or a methyl group.

The cyclic hydrocarbon structure of R ₅ includes a monocyclic hydrocarbon group and a polycyclic hydrocarbon group. Examples of the monocyclic hydrocarbon group include a C3-C12 cycloalkyl group such as a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group, and a C3-C12 cycloalkenyl group such as a cyclohexenyl group and a phenyl group. Can be mentioned. As a preferable monocyclic hydrocarbon group, it is a C3-C7 monocyclic hydrocarbon group, More preferably, a cyclopentyl group and a cyclohexyl group are mentioned.

The polycyclic hydrocarbon group includes a ring group hydrocarbon group and a temporary exchange hydrocarbon group, and examples of the ring group hydrocarbon group include a bicyclohexyl group, a perhydronaphthalenyl group, a biphenyl group, and a 4-cyclohexylphenyl group. Examples of the cross-linked hydrocarbon ring include, but are not limited to, evacuation, boran, norfinan, norbornane, bicyclooctane ring (bicyclo [2.2.2] octane ring, bicyclo [3.2.1] octane ring, etc.). Tricyclic hydrocarbon rings, such as bicyclic hydrocarbon rings and homobendan, adamantane, tricyclo [5.2.1.0 ^2,6 ] decane, tricyclo [4.3.1.1 ^2,5 ] undecane ring, tetracyclo [4.4.0.1 ^{2 , 5.1 7,10} ] tetracyclic hydrocarbon rings such as dodecane, perhydro-1,4-methano-5,8-methanonaphthalene ring, and the like. In addition, condensed cyclic hydrocarbon rings include, for example, perhydronaphthalene (decalin), perhydroanthracene, perhydrophenanthrene, perhydroacenaphthene, perhydrofluorene, perhydroindene, and perhydrophenant. Condensed rings in which a plurality of 5- to 8-membered cycloalkane rings such as a len ring are condensed are also included.

As a preferable crosslinkable hydrocarbon ring, a norbornyl group, adamantyl group, bicyclooctanyl group, tricyclo [5.2.1.0 ^2,6 ] decanyl group, etc. are mentioned. Norbornyl group and an adamantyl group are mentioned as a more preferable crosslinkable hydrocarbon ring.

These cyclic hydrocarbon groups may have a substituent, and a preferable substituent includes a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, an amino group substituted with a hydrogen atom, and the like. Preferred halogen atoms include bromine, chlorine and fluorine atoms, and preferred alkyl groups include methyl, ethyl, butyl and t-butyl groups. The alkyl group may further have a substituent, and examples of the substituent which may have a substituent include a halogen atom, an alkyl group, a hydroxyl group substituted with a hydrogen atom, and an amino group substituted with a hydrogen atom.

As a substituent which substitutes the said hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aralkyl group, a substituted methyl group, a substituted ethyl group, an alkoxycarbonyl group, an aralkyloxycarbonyl group is mentioned, for example. As a preferable alkyl group, it is a C1-C4 alkyl group, As a preferable substituted methyl group, As a methoxymethyl, methoxythiomethyl, benzyloxymethyl, t-butoxymethyl, 2-methoxyethoxymethyl group, As a preferable substituted ethyl group, 1-ethoxyethyl And 1-methyl-1-methoxyethyl, and preferred acyl groups include aliphatic acyl groups and alkoxycarbonyl groups having 1 to 6 carbon atoms, such as formyl, acetyl, propionyl, butyryl, isobutyryl, valeryl, and pivaloyl groups. C1-C4 alkoxycarbonyl group etc. are mentioned.

The resin (P) may have a cyclic hydrocarbon structure having no polar group and may not contain even if it contains a repeating unit which does not exhibit acid decomposability, but when it contains, the content rate is 1 to 40 moles with respect to all the repeating units in the resin (P). % Is preferable, More preferably, it is 5-20 mol%.

Although the specific example of the repeating unit which has a cyclic hydrocarbon structure which does not have a polar group and does not show acid decomposability is given to the following, this invention is not limited to these. In the formula, Ra represents H, CH ₃ , CH ₂ OH, or CF ₃ .

In addition to the repeating structural unit, the resin (P) of the present invention may have various repeating structural units for the purpose of adjusting dry etching resistance, standard developer aptitude, substrate adhesion, resist profile, and resolution, heat resistance, sensitivity, etc. which are general necessary characteristics of the resist. Can be.

Although a repeating structural unit corresponded to the following monomer as a repeating structural unit is mentioned, It is not limited to these.

Thereby, the performance calculated | required by resin used for the composition of this invention, especially,

(1) solubility in coating solvents,

(2) film forming property (glass transition point),

(3) alkali developability,

(4) film thickness reduction (selection of hydrophilic, alkali-soluble groups),

(5) adhesion to the unexposed portion of the substrate,

(6) dry etching resistance,

Fine adjustment of the back and the like becomes possible.

As such monomers, for example, addition polymerization selected from acrylic acid esters, methacrylic acid esters, acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, styrenes, crotonic acid esters, and the like The compound etc. which have one sex unsaturated bond are mentioned. In addition, maleic anhydride, maleimide, acrylonitrile, methacrylonitrile and maleonitrile are also mentioned.

In addition, it may be copolymerized as long as it is an addition polymerizable unsaturated compound which can be copolymerized with a monomer corresponding to the above various repeating structural units.

Although the preferable specific example of the repeating unit derived from such another polymeric monomer is given to the following, it is not limited to these.

In the resin (P) used in the composition of the present invention, the molar ratio of each repeating structural unit is determined by the dry etching resistance of the resist, the standard developer aptitude, the substrate adhesion, the resist profile, and the resolution, heat resistance, sensitivity, etc. which are general required performances of the resist. It is set appropriately to adjust.

The form of the resin (P) of the present invention may be any of random form, block form, comb form, and star form.

Resin (P) can be synthesize | combined by radical, cation, or anionic polymerization of the unsaturated monomer corresponding to each structure, for example. Moreover, it is also possible to obtain the target resin by performing a polymer reaction after superposing | polymerizing using the unsaturated monomer corresponding to the precursor of each structure.

For example, as a general synthesis method, the batch polymerization method which superposes | polymerizes by melt | dissolving and heating an unsaturated monomer and a polymerization initiator in a solvent, and the dropping polymerization method which adds an unsaturated monomer and a polymerization initiator solution dropwise to a heating solvent over 1 to 10 hours, and adds it. Etc. are mentioned, and the dropping polymerization method is preferable.

As a solvent used for superposition | polymerization, the solvent etc. which can be used when preparing the actinic ray-sensitive or radiation-sensitive resin composition mentioned later are mentioned, for example, More preferably, it is the same as the solvent used for the composition of this invention. It is preferable to superpose | polymerize using a solvent. As a result, generation of particles during storage can be suppressed.

It is preferable that a polymerization reaction is performed in inert gas atmosphere, such as nitrogen and argon. As a polymerization initiator, superposition | polymerization is started using a commercial radical initiator (azo initiator, peroxide, etc.). As a radical initiator, an azo initiator is preferable, and the azo initiator which has an ester bond, a cyano group, and a carboxyl group is preferable. Preferred initiators include azobisisobutylonitrile, azobisdimethylvaleronitrile, dimethyl 2,2'-azobis (2-methylpropionate) and the like. As needed, you may superpose | polymerize in presence of a chain transfer agent (for example, alkyl mercaptan etc.).

The concentration of the solute in the reaction solution is 5 to 70% by mass, preferably 10 to 50% by mass. Reaction temperature is 10 degreeC-150 degreeC normally, Preferably it is 30 degreeC-120 degreeC, More preferably, it is 40-100 degreeC.

The reaction time is usually 1 to 48 hours, preferably 1 to 24 hours, more preferably 1 to 12 hours.

After the reaction is completed, the reaction mixture is allowed to cool to room temperature and purified. Purification is carried out by a liquid extraction method for removing residual monomers and oligomer components by washing with water or combining a suitable solvent, a purification method in a solution state such as ultrafiltration for extracting and removing only those having a specific molecular weight or less, or by dropping a resin solution into a poor solvent. Conventional methods such as a reprecipitation method for removing residual monomer and the like by coagulating the resin in a poor solvent and a purification method in a solid state such as washing the separated resin slurry with a poor solvent can be applied. For example, the resin is precipitated as a solid by contacting a poorly or insoluble solvent (poor solvent) in a volume amount of 10 times or less, preferably 10 to 5 times the volume of the reaction solution.

The solvent (precipitation or reprecipitation solvent) used in the precipitation or reprecipitation operation from the polymer solution may be a poor solvent of the polymer, and may be a hydrocarbon, a halogenated hydrocarbon, a nitro compound, an ether, a ketone, an ester, or a carbonate depending on the type of polymer. , Alcohols, carboxylic acids, water, mixed solvents containing these solvents, and the like, may be appropriately selected. Among these, a solvent containing at least an alcohol (particularly methanol or the like) or water as the precipitation or reprecipitation solvent is preferable.

The amount of precipitation or reprecipitation solvent can be appropriately selected in consideration of efficiency, yield, and the like, but is generally 100-10000 parts by mass, preferably 200-2000 parts by mass, more preferably 300, based on 100 parts by mass of the polymer solution. It is -1000 mass parts.

Although it can select suitably as temperature at the time of precipitation or reprecipitation, considering efficiency and operability, it is about 0-50 degreeC normally, Preferably it is near room temperature (for example, about 20-35 degreeC). Precipitation or reprecipitation operation can be performed by well-known methods, such as a batch type and a continuous type, using common mixing vessels, such as a stirring tank.

Precipitated or reprecipitated polymers are usually supplied to conventional solid-liquid separation, such as filtration and centrifugation, to be dried and used for use. Filtration uses the filter medium of solvent resistance, Preferably it is performed under pressure. Drying is performed at a temperature of about 30 to 100 ° C, preferably about 30 to 50 ° C, under normal pressure or reduced pressure (preferably under reduced pressure).

In addition, once the resin is precipitated and separated, it may be dissolved in a solvent again and brought into contact with a solvent that is poorly soluble or insoluble. That is, after completion of the radical polymerization reaction, the polymer is contacted with a solvent that is poorly soluble or insoluble to precipitate a resin (step a), the resin is separated from the solution (step b), and dissolved in a solvent to prepare a resin solution A. The resin solid is then contacted by contacting the resin solution A with a solvent in which the resin is poorly soluble or insoluble in a volume amount of less than 10 times the volume of the resin solution A (preferably 5 times or less). The method may include depositing (step d) and separating the precipitated resin (step e).

Although the molecular weight of resin (P) by this invention is not specifically limited, It is preferable that the weight average molecular weight is the range of 1000-100000, It is more preferable that it is the range of 1500-60000, It is especially preferable that it is the range of 2000-30000. Do. By setting a weight average molecular weight in the range of 1000-100000, deterioration of heat resistance and dry etching resistance can be prevented, and developability deteriorates or a viscosity becomes high and it can prevent that film forming property deteriorates. Here, the weight average molecular weight of resin represents the polystyrene conversion molecular weight measured by GPC (carrier: THF or N-methyl- 2-pyrrolidone (NMP)).

Moreover, dispersion degree (Mw / Mn) becomes like this. Preferably it is 1.00-5.00, More preferably, it is 1.03-3.50, More preferably, it is 1.05-2.50. The smaller the molecular weight distribution is, the better the resolution and the resist shape are, and the sidewalls of the resist pattern are smooth and the roughness is excellent.

Resin (P) of this invention can be used individually by 1 type or in combination of 2 or more types. As for content rate of resin (P), 30-100 mass% is preferable on the basis of the total solid in the actinic-ray-sensitive or radiation-sensitive resin composition of this invention, 50.0-99.95 mass% is more preferable, 70.0-99.90 mass % Is particularly preferred.

Although the more preferable specific example of resin (P) is shown below, this invention is not limited to these.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, a compound which generates an acid by irradiation with a resin, active light or radiation, which is decomposed by the action of an acid as necessary to increase the dissolution rate in an aqueous alkali solution (low molecular weight). Photoacid generators (conventional)), basic compounds, low molecular weight compounds having groups that are released by the action of an acid, surfactants, substances that decompose by the action of an acid to produce acids stronger than carboxylic acids, and the like. Can be.

[2] resins, decomposed by the action of acids, to increase their dissolution rate in aqueous alkali

In addition to the resin (P), the actinic ray sensitive or radiation sensitive resin composition of the present invention may contain a resin that is decomposed by the action of an acid and the dissolution rate in the aqueous alkali solution is increased.

A resin that is decomposed by the action of an acid to increase its dissolution rate in an aqueous alkali solution (hereinafter also referred to as an "acid-decomposable resin") is decomposed by the action of an acid on both the main chain or the side chain of the resin, or both the main chain and the side chain, and is alkali. It is resin which has group (acid-decomposable group) which produces | generates a soluble group. Among these, resin which has an acid-decomposable group in a side chain is more preferable.

The acid-decomposable resin is a group which can be decomposed into an acid in an alkali-soluble resin as disclosed in European Patent No. 254853, Japanese Patent Laid-Open No. 2-25850, Japanese Patent No. 3-223860, Japanese Patent No. 4-251259 and the like. An alkali-soluble resin monomer having a group bonded to react with a precursor or decomposed into an acid can be obtained by copolymerization with various monomers.

As an acid-decomposable group, group which substituted the hydrogen atom of the alkali-soluble group of the left side with the group which detach | desorbs by the effect of an acid in resin which has alkali-soluble groups, such as -COOH group and -OH group, is preferable, for example.

As an acid-decomposable group, specifically, the same group as the acid-decomposable group demonstrated by resin (P) of this invention mentioned above (for example, the acid-decomposable group demonstrated as repeating unit (B) in resin (P)) is a preferable example. Can be mentioned.

Although it does not specifically limit as resin which has the said alkali-soluble group, For example, poly (o-hydroxy styrene), poly (m-hydroxy styrene), poly (p-hydroxy styrene), its copolymer, hydrogenated poly (Hydroxystyrene), poly (hydroxystyrene) having a substituent represented by the following structure, resin having a phenolic hydroxyl group, styrene-hydroxystyrene copolymer, α-methylstyrene-hydroxystyrene copolymer, hydrogenation Alkali-soluble resin which has hydroxy styrene structural units, such as a novolak resin, Alkali-soluble resin containing the repeating unit which has carboxyl groups, such as (meth) acrylic acid and norbornene carboxylic acid, is mentioned.

The alkali dissolution rate of these alkali-soluble resins is preferably measured at 2.38% by mass of tetramethylammonium hydroxide (23 ° C), and preferably 17 nm / sec or more. Especially preferably, it is 33 nm / sec or more.

The content of groups that can be decomposed in an acid has a number (X) of repeating units having a group that can be decomposed into an acid in the resin and a number (Y) of repeating units having an alkali-soluble group that is not protected by a group that is desorbed to an acid. It is represented by X / (X + Y). The content rate is preferably 0.01 to 0.7, more preferably 0.05 to 0.50, still more preferably 0.05 to 0.40.

The preferable range of the molecular weight and dispersion degree of acid-decomposable resin is the same as that of resin (P).

You may use acid-decomposable resin in combination of 2 or more types.

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention may not contain an acid-decomposable resin except for the resin (P), but when it contains, the blending ratio of the acid-decomposable resin except the resin (P) in the composition of the composition 0.1-70 mass% is preferable in solid content, More preferably, it is 0.1-50 mass%, More preferably, it is 0.1-30 mass%.

[3] compounds, which generate acids by irradiation with active light or radiation (low molecular weight photoacid generators)

The actinic ray-sensitive or radiation-sensitive resin composition of the present invention contains a resin (P) having a photo-generating structure, but in addition to the resin (P), a low molecular compound that generates an acid by irradiation with actinic light or radiation (hereinafter referred to) Or "acid generator" or "acid generator".

It is preferable that it is 3000 or less, and, as for the molecular weight of such a low molecular acid generator, it is more preferable that it is 2000 or less. The lower limit of the molecular weight of the low molecular acid generator is usually 200.

Such acid generators include photoinitiators of photocationic polymerization, photoinitiators of photo-radical polymerization, photochromic agents of pigments, photochromic agents, known compounds which generate acids by irradiation of actinic rays or radiation used in micro resists, and the like. Mixtures may be appropriately selected and used.

For example, a diazonium salt, a phosphonium salt, a sulfonium salt, an iodonium salt, an imide sulfonate, an oxime sulfonate, a diazo disulfone, a disulfone, o-nitrobenzyl sulfonate is mentioned. As these specific examples, what is described in [0164]-[0248] of the specification of US patent application publication 2008 / 0241737A1 is mentioned, for example.

In the actinic ray-sensitive or radiation-sensitive resin composition of the present invention, when an acid generator is used in addition to the resin (P) having a photoacid generator structure, the acid generator may be used alone or in combination of two or more thereof. have. As for content in the composition of an acid generator, 0-20 mass% is preferable based on the total solid of the composition of this invention, More preferably, it is 0-10 mass%, More preferably, it is 0-7 mass%. Although an acid generator is not an essential component in this invention, in order to acquire the effect of addition, it is normally used in 0.01 mass% or more.

[4] basic compounds

It is preferable that the actinic light or radioactive composition of this invention contains a basic compound.

It is preferable that a basic compound is a nitrogen containing organic basic compound.

Although the compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(4) is used preferably.

(1) the compound represented by the following general formula (BS-1)

In general formula (BS-1),

R each independently represents a hydrogen atom, an alkyl group (linear or branched), a monovalent aliphatic hydrocarbon ring group (monocyclic or polycyclic), an aryl group, or an aralkyl group. However, not all three Rs are hydrogen atoms.

Although carbon number of the alkyl group as R is not specifically limited, Usually, it is 1-20, Preferably it is 1-12.

Although carbon number of the monovalent aliphatic hydrocarbon ring group as R is not specifically limited, Usually, it is 3-20, Preferably it is 5-15.

Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20, Preferably it is 6-10. Specifically, a phenyl group, a naphthyl group, etc. are mentioned.

Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20, Preferably it is 7-11. Specifically, a benzyl group etc. are mentioned.

In the alkyl group, monovalent aliphatic hydrocarbon ring group, aryl group or aralkyl group as R, the hydrogen atom may be substituted with a substituent. As this substituent, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, an aralkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, etc. are mentioned, for example.

In the compound represented by the general formula (BS-1), only one of the three R's is preferably a hydrogen atom, or all R's are preferably hydrogen atoms.

Specific examples of the compound of formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexylmethylamine , Tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethyl undecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N- Dibutyl aniline, N, N-dihexyl aniline, 2,6-diisopropylaniline, 2,4,6-tri (t-butyl) aniline and the like.

In addition, in general formula (BS-1), the compound whose at least 1 R is an alkyl group substituted by the hydroxyl group is mentioned as one of the preferable forms. Specific examples of the compound include triethanolamine, N, N-dihydroxyethyl aniline, and the like.

Moreover, the alkyl group as R may have an oxygen atom in the alkyl chain, and the oxyalkylene chain may be formed. As the oxyalkylene chain, -CH ₂ CH ₂ O- is preferable. Specific examples include tris (methoxyethoxyethyl) amine, compounds exemplified after columns 3 and 60, and the like in US Pat. No. 6060112.

(2) a compound having a nitrogen-containing heterocyclic structure

The heterocyclic structure may or may not have aromaticity. Moreover, it may have two or more nitrogen atoms, and may contain hetero atoms other than nitrogen. Specifically, compounds having an imidazole structure (2-phenylbenzoimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure (N-hydroxyethyl piperidine, bis ( 1,2,2,6,6-pentamethyl-4-piperidyl) sebacate, etc.), a compound having a pyridine structure (such as 4-dimethylaminopyridine), a compound having an antipyrine structure (antipyrine, hydroxyantipyrine, etc.) ).

Moreover, the compound which has two or more ring structures is also used preferably. Specifically, 1, 5- diazabicyclo [4.3.0] nona-5-ene, 1, 8- diazabicyclo [5.4.0]-undeca-7-ene, etc. are mentioned.

(3) an amine compound having a phenoxy group

An amine compound having a phenoxy group is one having a phenoxy group at a terminal opposite to the nitrogen atom of the alkyl group of the amine compound. The phenoxy group may be a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group or an aryloxy group. You may have it.

More preferably, the compound has at least one oxyalkylene chain between the phenoxy group and the nitrogen atom. The number of oxyalkylene chains in one molecule is preferably 3 to 9, more preferably 4 to 6. Among the oxyalkylene chains, -CH ₂ CH ₂ O- is preferable.

Specific examples thereof include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, but US Patent Application Publication No. 2007 / 0224539A1 The compound (C1-1)-(C3-3) etc. which were illustrated by stage of the above are mentioned.

(4) ammonium salt

Ammonium salts are also suitably used. Preferably hydroxide or carboxylate. More specifically, tetraalkylammonium hydroxide represented by tetrabutylammonium hydroxide is preferable.

(5) Compounds whose basicity is increased by the action of acid

The compound whose basicity increases by the action of an acid can also be used as one kind of basic compound. As this example, what has a structure represented by following General formula (A) is mentioned, for example. The following compounds have low basicity as they are adjacent to N atoms with electron-withdrawing ester bonds. It is thought that substantial basicity is expressed because the site is decarbonized to remove the electron-binding ester binding site.

In general formula (A), Ra represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, or an aralkyl group. When n = 2, two Ras may be the same or different, and two Ras may be bonded to each other to form a divalent heterocyclic hydrocarbon group (preferably having 20 or less carbon atoms) or a derivative thereof.

Each R b independently represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, or an aralkyl group. However, in -C (Rb) (Rb) (Rb), three Rb do not simultaneously represent a hydrogen atom.

At least two Rb's may combine to form an alicyclic hydrocarbon group, an aromatic hydrocarbon group, a heterocyclic hydrocarbon group, or a derivative thereof.

n represents the integer of 0-2, m represents the integer of 1-3, and n + m = 3.

In general formula (A), the alkyl group, monovalent aliphatic hydrocarbon ring group, aryl group, and aralkyl group which Ra and Rb represent, such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, etc. It may be substituted with a functional group, an alkoxy group, or a halogen atom.

Examples of the Ra, Rb alkyl group, monovalent aliphatic hydrocarbon ring group, aryl group or aralkyl group (their alkyl group, aliphatic hydrocarbon ring group, aryl group and aralkyl group may be substituted with the functional group, alkoxy group and halogen atom).

For example, groups derived from linear, branched alkanes such as methane, ethane, propane, butane, pentane, hexane, heptane, octane, nonane, decane, undecane, dodecane, groups derived from alkanes thereof, Groups substituted with, for example, cycloalkyl groups,

Groups derived from cycloalkanes such as cyclobutane, cyclopentane, cyclohexane, cycloheptane, cyclooctane, norbornane, adamantane, and noradamantane, and groups derived from these cycloalkanes, for example, linear or A group substituted with a branched alkyl group,

Groups derived from aromatic compounds such as benzene, naphthalene and anthracene, groups derived from these aromatic compounds, for example, groups substituted with linear or branched alkyl groups,

Groups derived from heterocyclic compounds such as pyrrolidine, piperidine, morpholine, tetrahydrofuran, tetrahydropyran, indole, indolin, quinoline, perhydroquinoline, indazole, benzimidazole, and heterocycles thereof A group derived from a linear or branched alkyl group or a group derived from an aromatic compound, or a group derived from a linear or branched alkane derived from a cycloalkane, for example, a group derived from an aromatic compound The group etc. which the said substituent was substituted by functional groups, such as a hydroxyl group, a cyano group, an amino group, a pyrrolidino group, a piperidino group, a morpholino group, an oxo group, etc. are mentioned.

Moreover, as said bivalent heterocyclic hydrocarbon group (preferably C2-C20) or its derivative (s) which Ra forms and combines with each other, for example, pyrrolidine, piperidine, morpholine, 1,4,5, 6-tetrahydropyrimidine, 1,2,3,4-tetrahydroquinoline, 1,2,3,6-tetrahydropyridine, homopiperazine, 4-azabenzimidazole, benzotriazole, 5-azabenzo Triazole, 1H-1,2,3-triazole, 1,4,7-triazacyclononane, tetrazole, 7-azaindole, indazole, benzimidazole, imidazo [1,2-a] pyridine , (1S, 4S)-(+)-2,5-diazabicyclo [2.2.1] heptane, 1,5,7-triazabicyclo [4.4.0] dec-5-ene, indole, indolin, Groups derived from heterocyclic compounds such as 1,2,3,4-tetrahydroquinoxaline, perhydroquinoline, 1,5,9-triazacyclodecane, and groups derived from these heterocyclic compounds, linear or branched And cycloalkanes derived from alkanes on And groups substituted with groups derived from aromatic compounds, groups derived from aromatic compounds, groups derived from heterocyclic compounds, hydroxyl groups, cyano groups, amino groups, pyrrolidino groups, piperidino groups, morpholino groups, oxo groups, and the like. Can be.

Although the compound which basicity increases by the effect | action of especially preferable acid in this invention is shown concretely, this invention is not limited to this.

The compound represented by general formula (A) can be conveniently synthesized from a commercially available amine by the method described in Protective Groups in Organic Synthesis fourth edition and the like. The most common method is a method obtained by reacting a dicarboxylic acid ester or a haloformic acid ester with a commercial amine. In the formula, X represents a halogen atom. Ra and Rb are synonymous with general formula (A).

In addition, the compound synthesize | combined in the Example of Unexamined-Japanese-Patent No. 2002-363146, the compound of Paragraph 0108 of Unexamined-Japanese-Patent No. 2007-298569, etc. are mentioned as what can be used for the composition of this invention.

A basic compound is used individually or in combination of 2 or more types.

The usage-amount of a basic compound is 0.001-10 mass% normally, based on solid content of a composition, Preferably it is 0.01-5 mass%.

The molar ratio of the acid generator / basic compound is preferably 2.5 to 300. That is, a molar ratio of 2.5 or more is preferable from the point of sensitivity and resolution, and 300 or less is preferable from the point of suppression of the fall of the resolution by the thickness of the pattern over time until post-exposure heat processing. As this molar ratio, More preferably, it is 5.0-200, More preferably, it is 7.0-150.

In addition, the acid generator in the said molar ratio is the quantity of the sum total of the repeating unit (a) contained in resin (P), and acid generators other than resin (P) mentioned above.

[5] low molecular weight compounds having groups decomposed by the action of acids or alkalis

The composition of the present invention may contain a low molecular weight compound having a group that is decomposed by the action of an acid or an alkali (except for compounds whose basicity is increased by the action of the acid described above). It is preferable that the molecular weight of such a low molecular weight compound is 3000 or less. The group decomposed by the action of an acid or an alkali is not particularly limited, but an acetal group, a carbonate group, a carbamate group, a tertiary ester group, a tertiary hydroxyl group, a hemiamino ether group, and a lactone structure are preferable, It is especially preferable that they are a carbamate group and a hemiamine ether group.

When irradiating with an electron beam or EUV light, it is preferable to contain the structure which substituted the phenolic hydroxyl group of the phenolic compound by the acid-decomposer. As a phenolic compound, what contains 1-9 phenol skeletons is preferable, More preferably, it contains 2-6.

Although a specific example is shown below, this invention is not limited to these.

The low molecular weight compound which has a group decomposed | disassembled by the action of the said acid or alkali may use a commercial thing, or the thing synthesize | combined by a well-known method may be used.

[6] surfactants

The composition of this invention may contain surfactant further. When it contains, as surfactant, a fluorine type and / or silicone type surfactant is preferable.

As surfactants corresponding to these, Megapack F176, manufactured by Dainippon Ink & Chemicals Co., Ltd. Fluoride FC430 by the Co., Ltd., polysiloxane polymer KP-341 by the Shin-Etsu Kagaku Kogyo Co., etc. are mentioned.

Moreover, surfactant other than fluorine type and / or silicone type surfactant can also be used. More specifically, polyoxyethylene alkyl ethers, polyoxyethylene alkyl aryl ethers, etc. are mentioned.

In addition, a well-known surfactant can be used suitably. As the surfactant that can be used, for example, the surfactant described later in the specification of US Patent Application Publication No. 2008 / 0248425A1 can be mentioned.

Surfactant may be used independently and may use 2 or more types together.

The amount of the surfactant to be used is preferably 0 to 2% by mass, more preferably 0.0001 to 2% by mass, particularly preferably based on the total solids (the total amount of the solvent except the solvent) of the actinic ray-sensitive or radiation-sensitive resin composition. It is 0.0005-1 mass%.

[7] solvents

The solvent that can be used when preparing the composition is not particularly limited as long as it dissolves each component. Examples thereof include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, lactic acid alkyl ester and cyclic lactone. And linear or cyclic ketones, alkylene carbonates, alkyl carboxylic acid, alkyl alkoxyacetic acid, alkyl pyruvate and the like. As other usable solvents there may be mentioned, for example, the solvents described later in the specification of US Patent Application Publication No. 2008 / 0248425A1.

Examples of the alkylene glycol monoalkyl ether carboxylates include propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, propylene glycol monobutyl ether acetate, and propylene glycol monomethyl ether propionate. , Propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate, and ethylene glycol monoethyl ether acetate are preferable.

Examples of the alkylene glycol monoalkyl ethers include propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and ethylene glycol monoethyl ether. Can be.

As lactic acid alkyl ester, methyl lactate, ethyl lactate, propyl lactic acid, and butyl lactate are mentioned preferably, for example.

As alkyl alkoxy propionate, 3-ethoxy propionate ethyl, 3-methoxy propionate methyl, 3-ethoxy propionate methyl, and 3-methoxy ethylpropionate are mentioned preferably, for example.

Examples of cyclic lactones include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, and γ-valerolactone , γ-caprolactone, γ-octanoic lactone, and α-hydroxy-γ-butyrolactone are preferable.

Examples of the chain or cyclic ketones include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, and 4-methyl-2-penta. Paddy, 2-methyl-3-pentanone, 4,4-dimethyl-2-pentanone, 2,4-dimethyl-3-pentanone, 2,2,4,4-tetramethyl-3-pentanone, 2 -Hexanone, 3-hexanone, 5-methyl-3-hexanone, 2-heptanone, 3-heptanone, 4-heptanone, 2-methyl-3-heptanone, 5-methyl-3-heptanone , 2,6-dimethyl-4-heptanone, 2-octanone, 3-octanone, 2-nonanone, 3-nonanone, 5-nonanone, 2-decanone, 3-decanone, 4-de Canon, 5-hexen-2-one, 3-penten-2-one, cyclopentanone, 2-methylcyclopentanone, 3-methylcyclopentanone, 2,2-dimethylcyclopentanone, 2,4,4 -Trimethylcyclopentanone, cyclohexanone, 3-methylcyclohexanone, 4-methylcyclohexanone, 4-ethylcyclohexanone, 2,2-dimethylcyclohexanone, 2,6-dimethylcyclohexanone, 2 , 2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcycloheptanone, 3-methylcycle There may be mentioned preferably heptanone.

As alkylene carbonate, a propylene carbonate, vinylene carbonate, ethylene carbonate, butylene carbonate is mentioned preferably, for example.

As alkyl carboxylic acid, butyl acetate is mentioned preferably, for example.

As an alkoxy acetic acid alkyl, For example, 2-methoxy ethyl acetate, 2-ethoxy ethyl acetate, 2- (2-ethoxy ethoxy) ethyl acetate, 3-methoxy-3- methylbutyl, Acetic acid-1-methoxy-2-propyl is mentioned preferably.

Examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

Preferable solvents include 2-heptanone, cyclopentanone, γ-butyrolactone, cyclohexanone, butyl acetate, ethyl lactate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, and propylene glycol monomethyl Ether, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid-2- (2-ethoxyethoxy) ethyl, and propylene carbonate. As a particularly preferable solvent, propylene glycol monomethyl ether acetate and propylene glycol monomethyl ether are mentioned.

These solvents may be used alone or in combination of two or more thereof. When mixing 2 or more types, it is preferable to mix the solvent which has a hydroxyl group, and the solvent which does not have a hydroxyl group. The mass ratio of the solvent which has a hydroxyl group and the solvent which does not have a hydroxyl group is 1 / 99-99 / 1, Preferably it is 10 / 90-90 / 10, More preferably, it is 20 / 80-60 / 40.

As a solvent which has a hydroxyl group, alkylene glycol monoalkyl ether is preferable, and as a solvent which does not have a hydroxyl group, alkylene glycol monoalkyl ether carboxylate is preferable.

Although the content rate of the solvent in the composition of this invention can be adjusted suitably according to desired film thickness etc., generally the total solid content concentration of a composition is 0.5-30 mass%, Preferably it is 1.0-20 mass%, More preferably, It is prepared so that it may become 1.5-10 mass%.

[8] substances that decompose by the action of acids and produce acids stronger than carboxylic acids

The composition of the present invention may be decomposed by the action of an acid, and may contain a substance (hereinafter, also referred to as an "acid increasing agent") that produces an acid stronger than a carboxylic acid.

It is preferable that the acid produced | generated from an acid multiplying agent has a big intensity | strength, specifically, 3 or less are preferable as a dissociation constant (kKa) of the acid, More preferably, it is 2 or less. As the acid generated from the acid multiplying agent, sulfonic acid is preferable.

The acid increasing agent is disclosed in International Publication No. 95/29968, International Publication No. 98/24000, Japanese Patent Application Laid-Open No. 8-305262, Japanese Patent Application Laid-Open No. 9-34106, and Japanese Patent Application Laid-Open No. 8-248561. Japanese Patent Application Laid-Open No. 8-503082, US Patent No. 5,445,917, Japanese Patent Publication No. 8-503081, US Patent No. 5,534,393, US Patent No. 5,395,736, US Patent No. 5,741,630, U.S. Patent 5,334,489, U.S. Patent 5,582,956, U.S. Patent 5,578,424, U.S. Patent 5,453,345, U.S. Patent 5,445,917, European 665,960, European 757,628, Europe Patent No. 665,961, US Patent No. 5,667,943, Japanese Patent Application Laid-Open No. 10-1508, Japanese Patent Application Laid-Open No. 10-282642, Japanese Patent Application Laid-open No. 9-512498, and Japanese Patent Publication 20 The acid increasing agent described in 00-62337, Unexamined-Japanese-Patent No. 2005-17730, Unexamined-Japanese-Patent No. 2008-209889, etc. can be used 1 type, or in combination of 2 or more types.

Specifically, the compound represented by following General formula (1)-(6) is preferable.

In the general formulas (1) to (6),

R represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group.

R ₀ represents a group that is released by the action of an acid.

R ₁ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, an aralkyl group, an alkoxy group, or an aryloxy group.

R ₂ represents an alkyl group or an aralkyl group.

R <_3> represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, or an aralkyl group.

R ₄ and R ₅ each independently represent an alkyl group, and R ₄ and R ₅ may be bonded to each other to form a ring.

R ₆ represents a hydrogen atom or an alkyl group.

R ₇ represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, or an aralkyl group.

R ₈ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, or an aralkyl group.

R ₉ represents a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, or an aralkyl group.

R ₉ may be bonded to R ₇ to form a ring.

R ₁₀ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group or an alkenyloxy group.

R ₁₁ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an alkoxy group, an aryl group, an aralkyl group, an aryloxy group or an alkenyl group.

R ₁₀ and R ₁₁ may be bonded to each other to form a ring.

R ₁₂ represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group, an alkenyl group, an alkynyl group, or a cyclic imide group.

In general formula (1)-(6), an alkyl group is a C1-C8 alkyl group, As a monovalent aliphatic hydrocarbon ring group, a C4-C10 monocyclic or polycyclic aliphatic hydrocarbon ring group is mentioned, As an aryl group, C6-C14 aryl group is mentioned, Aralkyl group is a C7-C20 aralkyl group, As an alkoxy group, C1-C8 alkoxy group is mentioned, As an alkenyl group, C2-C6 alkenyl is mentioned A group is mentioned, As an aryloxy group, a C6-C14 aryloxy group is mentioned, As an alkenyloxy group, a C2-C8 alkenyloxy group is mentioned.

Each said substituent may have a substituent further and the following can be illustrated as a substituent, for example. That is, acylamino groups, such as halogen atoms, such as Cl, Br, and F, -CN group, -OH group, a C1-C4 alkyl group, a C3-C8 cycloalkyl group, a C1-C4 alkoxy group, an acetylamino group, Aralkyl groups, such as a benzyl group and a phenethyl group, allyloxyalkyl groups, such as a phenoxyethyl group, a C2-C5 alkoxycarbonyl group, a C2-C5 acyloxy group, etc. are mentioned.

Examples of the ring formed by bonding of R ₄ and R ₅ to each other include a 1,3-dioxolane ring, a 1,3-dioxane ring, and the like.

Cyclopentyl ring, cyclohexyl ring, etc. are mentioned as a ring which R <_7> and R <_9> combine and form each other.

Examples of the ring formed by bonding of R ₁₀ and R ₁₁ to each other include a 3-oxocyclohexenyl ring and a 3-oxoindenyl ring which may contain an oxygen atom in the ring.

Examples of the group detached by the action of R ₀ acid include tertiary alkyl groups such as t-butyl group and t-amyl group, isoboroyl group, 1-ethoxyethyl group, 1-butoxyethyl group and 1- Alkoxymethyl groups, such as 1-alkoxyethyl group, 1-methoxymethyl group, and 1-ethoxymethyl group, such as isobutoxyethyl group and 1-cyclohexyloxyethyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl group, 3- Oxocyclohexyl group, etc. may be mentioned.

The following are mentioned as a preferable thing of said R, R <_0> , R <_1> -R _{< 11>} .

R; methyl group, ethyl group, propyl group, butyl group, octyl group, trifluoromethyl group, nonafluorobutyl group, heptadecafluorooctyl group, 2,2,2-trifluoroethyl group, phenyl group, pentafuluro Phenyl group, methoxyphenyl group, toluyl group, mesityl group, fluorophenyl group, naphthyl group, cyclohexyl group, camphor group.

R _0; t- butyl group, methoxymethyl group, ethoxymethyl group, 1-ethoxy ethyl group, a tetrahydropyranyl group.

R ₁ ; methyl, ethyl, propyl, cyclopropyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, benzyl, phenethyl, methoxy, ethoxy, propoxy, phenoxy, naphthoxy.

R ₂ ; methyl group, ethyl group, propyl group, butyl group, benzyl group.

R ₃ ; methyl group, ethyl group, propyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, naphthylmethyl group.

R ₁ , R ₅ ; a methyl group, an ethyl group, a propyl group, and combine with each other to form an ethylene group and a propylene group.

R ₆ ; a hydrogen atom, a methyl group, an ethyl group.

R ₇ , R ₉ ; hydrogen atom, methyl group, ethyl group, propyl group, butyl group, pentyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, phenyl group, naphthyl group, benzyl group, phenethyl group, combine with each other cyclophene What formed the thyme ring and the cyclohexyl ring.

R ₈ ; a methyl group, an ethyl group, isopropyl group, t-butyl group, neopentyl group, cyclohexyl group, phenyl group, benzyl group.

R ₁₀ ; methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, cyclopropyl group, cyclopentyl group, cyclohexyl group, methoxy group, ethoxy group, phenyl group, naphthyl group, benzyl group, phenoxy group, A naphthoxy group, a vinyloxy group, a methylvinyloxy group, which combine with each other to form the 3-oxocyclohexenyl ring and 3-oxoindenyl ring which may contain an oxygen atom.

R ₁₁ ; methyl, ethyl, propyl, isopropyl, butyl, isobutyl, cyclopropyl, cyclopentyl, cyclohexyl, methoxy, ethoxy, phenyl, naphthyl, benzyl, phenoxy, A naphthoxy group, a vinyl group, an allyl group, which combine with each other to form the 3-oxocyclohexenyl ring and 3-oxoindenyl ring which may contain an oxygen atom.

In general formula (6), when R <_12> represents an alkyl group, the C1- _C12 linear and C3- _C12 branched alkyl group is more preferable.

When R ₁₂ represents a monovalent aliphatic hydrocarbon ring group, a monocyclic or polycyclic monovalent aliphatic hydrocarbon ring group having 5 to 10 carbon atoms is more preferable.

When R ₁₂ represents a substituted alkyl group or a substituted aliphatic hydrocarbon ring group, monovalent non-metallic atom groups other than hydrogen are used as the substituent, and as a preferred example, a halogen atom (-F, -Br, -Cl, -I), an alkoxy group, Aryloxy group, alkylthio group, arylthio group, N-alkylamino group, N, N-dialkylamino group, acyloxy group, N-alkylcarbamoyloxy group, N-arylcarbamoyloxy group, acylamino group, formyl group , Acyl group, carboxyl group, alkoxycarbonyl group, aryloxycarbonyl group, carbamoyl group, N-alkylcarbamoyl group, N, N-dialkylcarbamoyl group, N-arylcarbamoyl group, N-alkyl-N-arylcarbamo Diary, sulfo group, sulfonate group, sulfamoyl group, N-alkylsulfamoyl group, N, N-dialkylsulfamoyl group, N-arylsulfamoyl group, N-alkyl-N-arylsulfamoyl group, phosphono Group, phosphonate group, dialkyl phosphono group, diaryl phosphono group, monoalkyl phosphono group, alkyl phosphonane And the like group, a monoaryl phosphono group, an aryl phosphonate group, a phosphono oxy group, a phosphonate oxy group, an aryl group, an alkenyl group.

When R <_12> represents an aryl group, the thing in which 1 to 3 benzene rings formed the condensed ring as the aryl group, and the thing in which the benzene ring and the 5-membered unsaturated ring formed the condensed ring are mentioned, As a specific example, a phenyl group, a naphthyl group, and anthryl A group, a phenanthryl group, an indenyl group, an acenaphthenyl group, a fluorenyl group, etc. are mentioned, Among these, a phenyl group and a naphthyl group are more preferable. In addition, the aryl group includes a heterocyclic (hetero) aryl group in addition to the carbocyclic aryl group. Examples of the heterocyclic aryl group include those having 3 to 20 carbon atoms and 1 to 5 heteroatoms such as a pyridyl group, a furyl group, and a quinolyl group, a benzofuryl group, a thioxanthone group, and a carbazole group having been condensed with a benzene ring. Can be.

When R <_12> represents a substituted aryl group, what has a monovalent nonmetallic atom group except hydrogen as a substituent on the ring-forming carbon atom of the above-mentioned aryl group is used. As an example of a preferable substituent, what was shown as a substituent in the above-mentioned alkyl group and cycloalkyl group is mentioned.

When R ₁₂ represents an alkenyl group, a substituted alkenyl group [-C (R ₁₄ ) = C (R ₁₅ ) (R ₁₆ )], an alkynyl group, or a substituted alkynyl group [-C≡C (R ₁₇ )]; ₁₄ ~R ₁₇ may be used as the non-metallic atomic group monovalent. Examples of preferred R ₁₄ to R ₁₇ include a hydrogen atom, a halogen atom, an alkyl group, a substituted alkyl group, an aryl group and a substituted aryl group. As these specific examples, what was shown by the above-mentioned example is mentioned. As a more preferable substituent of R <_14> -R <_17> , a hydrogen atom, a halogen atom, and a C1-C10 linear, branched, cyclic alkyl group is mentioned.

When R ₁₂ represents a cyclic imide group, examples of the cyclic imide include those having 4 to 20 carbon atoms such as succinic acid imide, phthalic acid imide, cyclohexanedicarboxylic acid imide and norbornenedicarboxylic acid imide. Can be.

As a specific example of the compound represented by General Formula (1)-(6), the compound (1-1)-(1-11), (exemplified after Unexamined-Japanese-Patent No. 2008-209889, for example) ( 2-1) to (2-6), (3-1) to (3-6), (4-1) to (4-7), (5-1) to (5-4), (6- 1) to (6-20).

[9] other components

In addition to the components described above, the composition of the present invention may suitably contain dyes, plasticizers, photosensitizers, light absorbers, and the like described in the onium carboxylate salt, Proceeding of SPIE, 2724, 355 (1996) and the like.

[10] pattern formation methods

The present invention relates to a resist film formed by using the composition of the present invention described above.

Moreover, the pattern formation method of this invention has the process of exposing and developing the said resist film.

The composition of this invention dissolves the said component in a solvent, for example, filter-filters, and apply | coats to a support body, and is used.

As a filter, the thing of polytetrafluoroethylene, polyethylene, and nylon of pore size 0.1 micrometer or less, More preferably, 0.05 micrometer or less, More preferably, 0.03 micrometer or less is preferable.

Although the film thickness of a film | membrane is not specifically limited, 0.01-0.2 micrometer is preferable and 0.02-0.1 micrometer is more preferable.

As a method of apply | coating on a board | substrate, spin coating is preferable and the rotation speed of 1000-3000 rpm is preferable.

The composition is applied by a suitable coating method such as a spinner on a substrate (eg, silicon / silicon dioxide coating) used in the manufacture of integrated circuit devices, photomasks, imprint molds and the like. Then, it dries and a resist film is formed.

The film is irradiated with actinic light or radiation through a predetermined mask, and preferably baked (heated), developed and rinsed. Thus, a good pattern can be obtained. In addition, drawing (straight drawing) which does not pass through a mask is common in irradiation of an electron beam.

In addition, the mold structure for imprint may be produced using the composition of the present invention, and the details thereof include, for example, the basis of nanoimprint and the technology development and application development-substrate technology of nanoimprint and the latest technology development-editing: Reference may be made to Hirai Yoshihiko Frontier Shot Plate (issued in June 2006), Japanese Patent No. 4029085, Japanese Patent Application Laid-Open No. 2008-162101, and the like.

Although it does not specifically limit as an active light or a radiation, For example, a KrF excimer laser, an ArF excimer laser, an electron beam, an X-ray, or EUV light is preferable, and an electron beam, X-ray, or EUV light is especially preferable.

In the developing step, an alkaline developer is usually used. As the alkaline developer in the developing step, quaternary ammonium salts usually represented by tetramethylammonium hydroxide are used. In addition, inorganic alkalis (for example, sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, etc.) Primary to tertiary amines (e.g. ethylamine, n-propylamine, diethylamine, di-n-butylamine, triethylamine, methyldiethylamine, etc.), alcoholamines (e.g. dimethylethanolamine , Triethanolamine, etc.), and cyclic amine (for example, pyrrole, piperidine etc.), alkali aqueous solution, etc. can also be used.

Moreover, you may add an appropriate amount of alcohols and surfactant to the said alkaline developing solution.

The alkali concentration of alkaline developing solution is 0.1-20 mass% normally.

The pH of alkaline developing solution is 10.0-15.0 normally.

Pure water is preferable as the rinse liquid, and an appropriate amount of a surfactant may be added and used.

In addition, you may apply an antireflection film on a board | substrate before forming a resist film. As the antireflection film, both an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon, amorphous silicon, and an organic film type made of a light absorber and a polymer material can be used. As the organic anti-reflection film, commercially available organic anti-reflection films such as DUV30 series manufactured by Bruwa Science, DUV-40 series, and AR-2, AR-3, AR-5 manufactured by Cypress, etc. may be used.

Moreover, this invention relates also to the manufacturing method of the electronic device containing the pattern formation method of this invention mentioned above, and the electronic device (for example, semiconductor device) manufactured by this manufacturing method.

The electronic device of the present invention is preferably mounted in electrical and electronic equipment (home appliances, OA media related equipment, optical equipment and communication equipment, etc.).

(Example)

Hereinafter, although an Example demonstrates this invention further in detail, the content of this invention is not limited by this.

Synthesis Example 1 (Synthesis of M-I-57)

100.00 parts by mass of p-acetoxy styrene was dissolved in 400 parts by mass of ethyl acetate, cooled to 0 ° C, 47.60 parts by mass of sodium methoxide (28% methanol solution) was added dropwise over 30 minutes, and stirred at room temperature for 5 hours. Ethyl acetate was added, the organic layer was washed three times with distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 131.70 parts by mass of p-hydroxystyrene (54% ethyl acetate solution).

18.52 parts by mass of p-hydroxystyrene (54% ethyl acetate solution) was dissolved in 56.00 parts by mass of ethyl acetate, and 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride 31.58 mass parts was added and it cooled to 0 degreeC. The solution which melt | dissolved 12.63 mass parts of triethylamine in 25.00 mass parts of ethyl acetate was dripped over 30 minutes, and it stirred for 4 hours in the state which is 0 degreeC. Ethyl acetate was added, the organic layer was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 32.90 parts by mass of compound A.

35.00 mass parts of compound A was melt | dissolved in 315 mass parts of methanol, it cooled at 0 degreeC, 245 mass parts of 1N sodium hydroxide aqueous solution was added, and it stirred at room temperature for 2 hours. The solvent was distilled off, ethyl acetate was added, the organic layer was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off to obtain 34.46 parts by mass of compound B.

28.25 mass parts of compound B was dissolved in 254.25 mass parts of methanol, 36.36 mass parts of 4-octyloxy and 2 ', 4', 6'- trimethoxyphenyl iodonium chloride were added, and it stirred at room temperature for 3 hours. The solvent was distilled off, distilled water was added, and extracted three times with chloroform. After wash | cleaning the obtained organic layer three times with distilled water, the solvent was distilled off and 44.27 mass parts of target compounds (M-I-57) were obtained.

Synthesis Example 2 (Synthesis of M-II-21)

13.9 parts by mass of N- (4-hydroxyphenylethyl) methacrylamide and 21.4 parts by mass of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride (tetrahydrofuran ( THF) was dissolved in 160 parts by mass and 160 parts by mass of triethylamine was added thereto. After stirring at 50 ° C for 2 hours, 11.1 parts by mass of trifluoromethanesulfonamide was added, and the mixture was stirred at 80 ° C for 4 hours. Ethyl acetate was added, the organic layer was washed sequentially with dilute hydrochloric acid and water, and the organic layer was dried over sodium sulfate.

After the solvent was concentrated, the brown oil of the residue was dissolved in 400 parts by mass of methanol, 20 parts by mass of solid sodium bicarbonate was added thereto, and the mixture was stirred at 50 ° C for 4 hours. Ethyl acetate was added, the organic layer was washed sequentially with saturated brine and water, and the organic layer was dried over sodium sulfate to give N- (trifluoromethanesulfonyl) -1,1,2,2,3,3- brown oil. 24.5 parts by mass of hexafluoro-3-((4- (2- (methacrylamide) ethyl) phenoxy) sulfonyl) -1-propanesulfonamide sodium salt was obtained. 24.4 mass parts of this brown oil was melt | dissolved in 200 mass parts of methanol, 20.0 mass parts of 4-octyloxy and 2 ', 4', 6'- trimethoxyphenyl iodonium chloride were added, and it stirred at room temperature for 3 hours. 400 mass parts of chloroforms were added, the organic layer was wash | cleaned with water, the solvent was concentrated, and 27.4 mass parts of brown transparent oily compounds (M-II-21) were obtained.

Other monomers (MI-2, MI-6, MI-24, MI-28, MI-74, MI-79, MI-81, MI-82, MI-86, MI-88, MI-90, MI-127 , MI-160, MI-175, MI-179, MI-183, M-II-50, M-III-2, M-III-39 and M-III-53) were similarly synthesized.

Synthesis Example 3 (Synthesis of Resin P-1)

8.10 mass parts of 1-methoxy-2-propanol were heated at 80 degreeC under nitrogen stream. While stirring this liquid, 5.28 mass parts of monomers (MI-57) represented by general formula (I), 6.12 mass parts of monomers of the following structural formula A, 6.01 mass part of monomers of the following structural formula B, and 1-methoxy- 2-propanol 32.5 Mass part, 2,2'- azobisisobutyric acid dimethyl [V-601, Wako Pure Chemical Industries Ltd. make] 1.61 mass part of the mixed solution was dripped over 2 hours. After completion of the dropwise addition, the mixture was further stirred at 80 ° C for 4 hours. After cooling the reaction solution, 13.5 parts by mass of the resin (P-1) of the present invention was obtained by reprecipitation and vacuum drying with a large amount of hexane / ethyl acetate.

The weight average molecular weight (Mw: polystyrene conversion) calculated | required from GPC (carrier: N-methyl- 2-pyrrolidone (NMP)) of obtained resin was Mw = 6700, and dispersion degree Mw / Mn = 1.61.

Hereinafter, resin P-2-P-28 were synthesize | combined similarly. The structure, composition ratio (molar ratio), weight average molecular weight, and dispersion degree of each synthesize | combined resin are shown in the following figure.

Hereinafter, the other resin and the photo-acid generator used for the Example and the comparative example are shown.

Resist Evaluation

The components shown in the following table are dissolved in a solvent, and a solution having a solid content concentration of 4% by mass is prepared for each of them, and this is filtered through a polytetrafluoroethylene filter having a pore size of 0.10 占 퐉 to actinic ray-sensitive or radiation-sensitive resin. The composition was prepared. The actinic ray sensitive or radiation sensitive resin composition was evaluated by the following method, and the results are shown in the following table.

The ratio in the case of using more than one about each component in the following table | surface is a mass ratio.

(Exposure Condition 1: EB Exposure) Examples 1 to 34 and Comparative Examples 1 to 5

The prepared radiation-sensitive resin composition was uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater, and heated and dried on a hot plate at 120 ° C. for 90 seconds to form a radiation-sensitive film having a thickness of 100 nm. I was. The radiation-sensitive film was irradiated with an electron beam using an electron beam irradiation device (HL750 manufactured by Hitachi Seisakusho, acceleration voltage 50 keV). Immediately after irradiation it was heated on a hotplate at 110 ° C. for 90 seconds. Furthermore, it developed at 23 degreeC for 60 second using the tetramethylammonium hydroxide aqueous solution of concentration 2.38 mass%, rinsed with pure water for 30 second, and spin-dried to obtain a resist pattern.

(Exposure Condition 2: EUV Exposure) Examples 35 to 44 and Comparative Example 6

The prepared radiation-sensitive resin composition was uniformly coated on a hexamethyldisilazane-treated silicon substrate using a spin coater, and heated and dried on a hot plate at 120 ° C. for 90 seconds to form a radiation-sensitive film having a thickness of 100 nm. I was. The radiation-sensitive film was irradiated with an EUV exposure apparatus and heated on a hot plate at 110 ° C. for 90 seconds immediately after irradiation. Furthermore, it developed at 23 degreeC for 60 second using the tetramethylammonium hydroxide aqueous solution of 2.38 mass% in concentration, and rinsed with pure water for 30 second, and spin-dried to obtain a resist pattern.

(Sensitivity evaluation)

The cross-sectional shape of the obtained pattern was observed using a scanning electron microscope (S-9220 manufactured by Hitachi Seisakusho). The minimum irradiation energy at the time of resolving a 100 nm line (line: space = 1: 1) was made into the sensitivity.

(Resolution evaluation)

The limit resolution power (separation resolution of a line and a space) in the irradiation amount which shows the said sensitivity was made into the resolution power.

(Pattern Shape Evaluation)

The cross-sectional shape of the 100 nm line pattern in the irradiation amount which shows the said sensitivity was observed using the scanning electron microscope (S-4300 by Hitachi Seisakusho), and three-step evaluation of a rectangle, a slightly taper, and a taper was performed.

(LER evaluation)

The distance from the reference line which should have an edge using a scanning electron microscope (S-9220 manufactured by Hitachi Seisakusho) for any 30 points in the longitudinal direction of 50 μm of the 100 nm line pattern in the irradiation dose indicating the sensitivity. It measured and calculated | required standard deviation, and computed 3 (sigma).

(Out gas performance: film thickness fluctuation rate by exposure)

The electron beam was irradiated at a dose of 2.0 times the irradiation amount to impart the sensitivity, the film thickness after exposure and before the post-heating was measured, and the variation rate from the film thickness at the unexposed time was obtained using the following formula.

Film thickness variation rate (%) = [(film thickness at unexposed-film thickness after exposure) / film thickness at unexposed] * 100

(Time stability)

After storing a resist composition for 1 month at room temperature, based on the said exposure condition 1 about Examples 1-34 and Comparative Examples 1-5, based on the said exposure condition 2 about Examples 35-44 and Comparative Example 6, The degree of sensitivity fluctuation before and after forming a resist pattern and storing for one month was evaluated according to the following criteria.

○: A sensitivity change of <1 μC / cm 2 was observed.

A sensitivity fluctuation of Δ: 1 μC / cm 2 or more and 3 μC / cm 2 or less was observed.

×: Sensitivity fluctuation of> 3 µC / cm 2 was observed.

(Solvent solubility)

After dissolving the component shown in the following table | surface in the organic solvent shown in the following table | surface, it was left to stand at 25 degreeC for 10 hours, and it evaluated, visually checking the presence or absence of precipitation of the obtained solution, and cloudiness.

(Circle): There is no precipitation and cloudy.

(Triangle | delta): There was no precipitation but it became cloudy.

X: Precipitation occurred.

These measurement results are shown in the following table.

[Basic Compound]

TBAH: tetrabutylammonium hydroxide

TOA: tri (n-octyl) amine

TPI: Triphenylimidazole

〔Surfactants〕

W-1: Megapack F176 (product made by Dainippon Ink & Chemicals Co., Ltd.) (fluorine system)

W-2: Mega pack R08 (product made by Dainippon Ink & Chemicals Co., Ltd.) (fluorine and silicon type)

W-3: Polysiloxane polymer KP-341 (made by Shin-Etsu Kagaku Kogyo Co., Ltd.) (silicone system)

W-4: PF6320 (product made by OMNOVA company) (fluorine system)

〔solvent〕

S1: Propylene glycol monomethyl ether acetate (PGMEA; 1-methoxy-2-acetoxy propane)

S2: Propylene glycol monomethyl ether (PGME; 1-methoxy-2-propanol)

S3: ethyl lactate

S4: 2-heptanone

S5: cyclohexanone

S6: γ-butyrolactone

S7: propylene carbonate

From the results shown in the above table, the actinic ray sensitive or radiation sensitive resin composition of the present invention simultaneously satisfies high sensitivity, high resolution, good pattern shape, good line edge roughness, low out gas performance, and stability over time in EB exposure. It is obvious.

In addition, it is apparent that the actinic ray sensitive or radiation sensitive resin composition of the present invention simultaneously satisfies high sensitivity, good pattern shape and stability over time even in EUV exposure.

Moreover, it is clear that the actinic ray sensitive or radiation sensitive resin composition of this invention has high solvent solubility of solid content, and is excellent in the storage stability as a solution (resist liquid).

Claims (15)

Resin having a repeating unit (A) having an ionic structure moiety that is decomposed by irradiation of active light or radiation to generate acid anions in the side chain of the resin, and a repeating unit (C) represented by the following general formula (I) An actinic ray-sensitive or radiation-sensitive resin composition containing P), wherein the cation of the ionic structure moiety is a diaryliodonium cation represented by the following general formula (A1). Radioactive resin composition.

[In General Formula (A1), Ar ₁ represents a (p + 1) valent aromatic ring group, and Ar ₂ represents a (q + 1) valent aromatic ring group.
L ₁ and L ₂ each independently represent a single bond or an oxygen atom.
R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R ₂₃ each independently represent a hydrogen atom or an alkyl group. Two or more of R ₁₁ , R _12, and R ₁₃ may combine to form a ring. In addition, two or more of R ₂₁ , R _22, and R ₂₃ may combine to form a ring.
p and q each represent an integer of 0 to 9 and satisfy p + q ≧ 2.
In the case of p≥2, the groups represented by a plurality of (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ − may be the same or different.
In the case of q≥2, the groups represented by a plurality of (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL ₂ − may be the same or different.
However, in the general formula (A1), when represented by the following general formula (A1-1), L ₁ and L ₂ are the same as each other, and R ₁₁ , R ₁₂ , R ₁₃ , R ₂₁ , R ₂₂ and R _{23 are} all Is not the same thing]

[In General Formula (I), R ₁₁ ′, R ₁₂ ′ and R ₁₃ ′ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₁₃ ′ may be bonded to Ar ₁ ′ to form a ring, and R ₁₃ ′ in that case represents an alkylene group.
X ₁ represents a single bond or a divalent linking group.
Ar ₁ ′ represents a (n + 1) valent aromatic ring group, and when combined with R ₁₃ ′ to form a ring, (n + 2) valent aromatic ring group.
n represents an integer of 1 to 4] The method of claim 1,
In said general formula (A1), p is an integer of 1 or more, and q is an integer of 1 or more, The actinic-ray-sensitive or radiation-sensitive resin composition characterized by the above-mentioned. The method of claim 2,
In the general formula (A1), p groups represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ − and q groups represented by (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL ₂ − The groups are not all the same group, wherein the actinic ray-sensitive or radiation-sensitive resin composition. The method according to any one of claims 1 to 3,
In General Formula (A1), p and q are integers different from each other. The method according to any one of claims 1 to 3,
In the general formula (A1), a group represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ -and a group represented by (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL ₂ -are each independently. An actinic ray sensitive or radiation sensitive resin composition characterized by showing an alkyl group having 1 to 3 carbon atoms. The method according to any one of claims 1 to 3,
In the formula (A1), in the group consisting of a group represented by (R ₁₁ ) (R ₁₂ ) (R ₁₃ ) CL ₁ -and a group represented by (R ₂₁ ) (R ₂₂ ) (R ₂₃ ) CL _2- At least one of the two or more groups selected is an actinic ray-sensitive or radiation-sensitive resin composition, characterized in that located in the ortho position with respect to the iodonium group on the aromatic ring. The method according to any one of claims 1 to 3,
P + q≥3 in the said General formula (A1), The actinic-ray-sensitive or radiation-sensitive resin composition characterized by the above-mentioned. The method according to any one of claims 1 to 3,
P + q≥4 in the said General formula (A1), The actinic-ray-sensitive or radiation-sensitive resin composition characterized by the above-mentioned. The method according to any one of claims 1 to 3,
Said resin (P) further has a repeating unit (C) which decomposes by the action of an acid, and generates an alkali-soluble group. The method according to any one of claims 1 to 3,
The said repeating unit (B) is an actinic-ray-sensitive or radiation-sensitive resin composition characterized by the repeating unit represented by the following general formula (V) or (VI).

[In formula (V), R ₅₁ , R ₅₂ and R ₅₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₅₂ may be bonded to L ₅ to form a ring, in which case R ₅₂ represents an alkylene group.
L ₅ represents a single bond or a divalent linking group, and in the case of forming a ring with R ₅₂ , represents a trivalent linking group.
R ₅₄ represents an alkyl group, and R ₅₅ and R ₅₆ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group or a monovalent aromatic ring group. R ₅₅ and R ₅₆ may be bonded to each other to form a ring. However, R ₅₅ and R ₅₆ do not simultaneously represent a hydrogen atom.
In General Formula (VI), R ₆₁ , R ₆₂ and R ₆₃ each independently represent a hydrogen atom, an alkyl group, a monovalent aliphatic hydrocarbon ring group, a halogen atom, a cyano group or an alkoxycarbonyl group. R ₆₂ may be bonded to Ar ₆ to form a ring, in which case R ₆₂ represents an alkylene group.
Ar ₆ represents a (n + 1) valent aromatic ring group, and when combined with R ₆₂ to form a ring, (n + 2) valent aromatic ring group.
Y represents a group which is released by the action of a hydrogen atom or an acid, and when a plurality of Y are present, a plurality of Y may be the same or different. Provided that at least one of Y represents a group that is released by the action of an acid.
n represents an integer of 1 to 4] The method according to any one of claims 1 to 3,
An actinic ray-sensitive or radiation-sensitive resin composition, which is for electron beam, X-ray or EUV light. It is formed using the actinic-ray-sensitive or radiation-sensitive composition in any one of Claims 1-3, The resist film characterized by the above-mentioned. It has a process of exposing and developing the resist film of Claim 12, The pattern formation method characterized by the above-mentioned. The manufacturing method of the electronic device containing the pattern formation method of Claim 13. It is manufactured by the manufacturing method of the electronic device of Claim 14, The electronic device characterized by the above-mentioned.