JP5264665B2 - Actinic ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an actinic ray-sensitive or radiation-sensitive resin composition which is excellent in sensitivity, roughness characteristics, the resolution and dry etching resistance of an isolated pattern and enables a pattern of good configuration to be formed, and to provide a pattern forming method using the actinic ray-sensitive or radiation-sensitive resin composition. <P>SOLUTION: The actinic ray-sensitive or radiation-sensitive resin composition includes a resin having a repeating unit (A) represented by general formula (I) and a repeating unit (B) which generates an acid upon irradiation with actinic rays or radiation. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to an actinic ray-sensitive or radiation-sensitive resin composition and a pattern forming method using the same. More specifically, the present invention relates to an ultra-microlithographic process applicable to a manufacturing process of a VLSI and a high-capacity microchip, a process for producing a mold for nanoimprinting, a manufacturing process of a high-density information recording medium, and other photofabrication. The present invention relates to a composition suitably used in a process, and a pattern forming method using the composition.

  Here, “active light” or “radiation” means, for example, an emission line spectrum of a mercury lamp, far ultraviolet rays represented by an excimer laser, extreme ultraviolet rays (EUV) rays, X rays or electron rays (EB). Yes. In the present invention, “light” means actinic rays or radiation.

  In addition, “exposure” means not only light irradiation with a mercury lamp, far ultraviolet rays, X-rays, EUV light, etc., but also drawing with particle beams such as electron beams and ion beams, unless otherwise specified. .

  Conventionally, in the manufacturing process of semiconductor devices such as IC and LSI, fine processing by lithography using a photoresist composition has been performed. In recent years, with the high integration of integrated circuits, the formation of ultrafine patterns in the submicron region and the quarter micron region has been required. Along with this, there is a tendency to shorten the exposure wavelength from g-line to i-line and further to KrF excimer laser light. Furthermore, at present, in addition to excimer laser light, lithography using electron beams, X-rays, EUV light, and the like is also being developed.

  Due to the recent demand for the formation of ultrafine patterns in the submicron region and the quarter micron region accompanying the high integration of integrated circuits, it is necessary to reduce the thickness. However, a decrease in dry etching resistance has become a problem due to the thinning of the film, and the current situation is that it is not fully satisfactory.

  In addition, due to the formation of ultra-fine patterns, the adhesion to the substrate has decreased, and the resolution of isolated patterns has become a problem. Improvement of the resolution of isolated patterns is desired, but it is fully satisfactory. Not done.

  Furthermore, in particular, electron beam lithography is positioned as a next-generation or next-generation pattern formation technique, and a positive resist with high sensitivity and high resolution is desired. In particular, high sensitivity is an extremely important issue for shortening the wafer processing time. However, in positive resists for electron beams, when trying to increase sensitivity, not only the resolution is lowered, but also the line edge. Roughness deteriorates, and development of a resist that satisfies these characteristics at the same time is strongly desired. Here, the line edge roughness means that when the pattern is viewed from directly above because the resist pattern and the edge of the substrate interface vary irregularly in the direction perpendicular to the line direction due to the characteristics of the resist. Say that the edge looks uneven. The unevenness is transferred by an etching process using a resist as a mask, and the electrical characteristics are deteriorated, so that the yield is lowered. Particularly in the ultrafine region of 0.25 μm or less, the line edge roughness is an extremely important improvement issue. High sensitivity, good pattern shape, and good line edge roughness are in a trade-off relationship, and it is very important how to satisfy them simultaneously.

  Similarly, in lithography using X-rays and EUV light, it is also important to satisfy simultaneously high sensitivity, good pattern shape, good line edge roughness, isolated pattern resolution and dry etching resistance. These solutions are necessary.

  As one method for solving these problems, use of a resin having a naphthalene skeleton has been studied. (For example, see Patent Documents 1 to 3). However, the combination of currently known techniques cannot sufficiently satisfy high sensitivity, good pattern shape, good line edge roughness and dry etching resistance at the same time in electron beam, X-ray or EUV light lithography. It is.

  Moreover, use of the resin which has a photo-acid generator in a polymer principal chain or a side chain is examined (for example, refer patent documents 4-10 and nonpatent literature 1). However, in the study in Patent Document 4, since it is a mixed system of a resin having a photoacid generator and a dissolution inhibiting compound whose solubility in an alkaline developer is increased by acid decomposition, the non-uniform mixing of these materials is reduced. As a result, it is difficult to obtain a good pattern shape and line edge roughness.

  On the other hand, Patent Documents 5 to 9 disclose resins having a photoacid-generating group and a group whose solubility in an alkaline developer is increased by acid decomposition in the same molecule, but electron beam, X-ray or EUV light is disclosed. It was difficult to say that the sensitivity to was sufficient.

  Patent Document 10 and Non-Patent Document 1 describe ternary copolymers of hydroxystyrene, an adamantyl group-containing acrylate, and a photoacid generator-containing acrylate. Patent Document 11 contains a resin containing a repeating unit that is sensitive to high energy rays or heat and generates sulfonic acid at a fluorine-containing terminal of a side chain in order to improve high resolution, density dependency, and exposure margin. A resist is disclosed.

  However, the combination of currently known techniques cannot sufficiently satisfy high sensitivity, high resolution, good pattern shape, good line edge roughness, etc. at the same time in electron beam, X-ray or EUV light lithography. Is the current situation.

JP 2008-169346 A International Publication No. 2007-064553 JP 2008-50568 A JP-A-9-325497 JP-A-10-221852 JP 2006-178317 A JP 2007-197718 A International Publication No. 06/121096 Pamphlet US Patent Application Publication No. 2006/121390 US Patent Application Publication No. 2007/117043 JP 2008-133448 A

Proc. Of SPIE Vol.6923, 692312, 2008

  An object of the present invention is to provide an actinic ray-sensitive or radiation-sensitive resin composition excellent in sensitivity, roughness characteristics, resolution of isolated patterns and dry etching resistance, and capable of forming a pattern having a good shape, and It is to provide a pattern forming method used.

  For example, the present invention is as follows. Here, the “weight average molecular weight” means a polystyrene equivalent value measured by gel permeation chromatography (GPC).

[1] Actinic ray sensitivity or sensitivity comprising a resin comprising a repeating unit (A) represented by the following general formula (I) and a repeating unit (B) that generates an acid upon irradiation with actinic rays or radiation. Radiation resin composition.

In formula (I),
R _a is a hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, An alkylcarbonyloxy group or an aralkyl group is represented.
Y _a represents a divalent linking group.
Ar represents a structural unit including a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or are connected to each other through a single bond.
Y _b represents a single bond or a divalent linking group.
A ₃ represents a group capable of leaving by the action of an acid.
S ₂ represents a substituent (excluding a hydrogen atom), and when r ≧ 2, the plurality of S ₂ may be the same as or different from each other.
p represents an integer of 1 to 5.
q represents the integer of 1-5.
r represents an integer of 0 to 4 that satisfies the relationship of p + r ≦ 5.

[2] The composition according to [1], wherein R _a is a hydrogen atom or a methyl group, p = 1, and q = 1.

[3] The composition according to [2], wherein the repeating unit (A) is represented by the following general formula (III).

In formula (III),
R _a represents a hydrogen atom or a methyl group.
Y _a represents a divalent linking group.
Ar represents a structural unit including a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or are connected to each other through a single bond.
Y _b represents a single bond or a divalent linking group.
A ₃ represents a group capable of leaving by the action of an acid.
S ₂ represents a substituent (excluding a hydrogen atom), and when r ≧ 2, the plurality of S ₂ may be the same as or different from each other.
r represents an integer of 0 to 4.

  [4] The composition according to [3], wherein r = 0.

[5] The composition according to any one of [1] to [4], wherein Y _a represents —O—, —CH ₂ O—, —COO—, or —COOCH ₂ —.

[6] The composition according to [5], wherein Y _b represents a single bond, —CH ₂ O— or —COOCH ₂ —.

  [7] The composition according to any one of [1] to [6], wherein Ar represents a structural unit including a naphthalene or anthracene ring, or a biphenyl or terphenyl structure.

[8] At least a part of the repeating unit (B) is represented by at least one selected from the group consisting of the following general formulas (B1), (B2) and (B3): [1] to [7] The composition in any one.

Where
A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₆ represents a cyano group, a carboxy group, —CO—OR ₂₅ or —CO—N (R ₂₆ ) (R ₂₇ ). R ₂₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ may be bonded to each other to form a ring together with the nitrogen atom. R ₂₆ and R ₂₇ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.
X _{1 to} X ₃ are each independently a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R ₃₃ ) —, or a combination thereof. Represents a divalent linking group. R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.

  [9] The composition according to [8], wherein A is a structural moiety having a sulfonium salt structure or an iodonium salt structure.

  [10] The composition according to [8] or [9], wherein A is a structural moiety that is converted to an acid anion by irradiation with actinic rays or radiation.

[11] The resin further includes at least one of a repeating unit represented by the following general formula (A1) and a repeating unit represented by the general formula (A2). The composition as described.

In general formula (A1),
m represents an integer of 0 to 4.
n represents an integer of 1 to 5 that satisfies the relationship m + n ≦ 5.
S ₁ represents a substituent (excluding a hydrogen atom), and when m ≧ 2, the plurality of S ₁ may be the same as or different from each other.
A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid. When n ≧ 2, the plurality of A ₁ may be the same as or different from each other.
In general formula (A2),
X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, alkyl Represents a carbonyloxy group or an aralkyl group.
A ₂ represents a group capable of leaving by the action of an acid.

  [12] The composition according to any one of [1] to [11], wherein the resin has a weight average molecular weight in the range of 1,000 to 200,000.

  [13] The composition according to any one of [1] to [12], wherein the resin has a weight average molecular weight in the range of 1000 to 100,000.

  [14] The composition according to any one of [1] to [13], wherein the resin has a weight average molecular weight in the range of 1000 to 50000.

  [15] The composition according to any one of [1] to [14], wherein the resin has a weight average molecular weight in the range of 1000 to 25000.

  [16] The composition according to any one of [1] to [15], further comprising a basic compound.

  [17] The basic compound has a proton acceptor functional group and is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor, or change from proton acceptor to acidic. The composition according to [16], which is a compound that generates a compound.

  [18] The composition according to any one of [1] to [17], further comprising a surfactant.

  [19] The composition according to any one of [1] to [18], further comprising a solvent.

  [20] The composition according to [19], wherein the solvent contains propylene glycol monomethyl ether acetate.

  [21] The composition according to [20], wherein the solvent further contains propylene glycol monomethyl ether.

  [22] The composition according to [1] to [21], which is exposed to KrF excimer laser, electron beam, X-ray or EUV light.

  [23] A pattern including forming a film using the composition according to any one of [1] to [22], exposing the film, and developing the exposed film Forming method.

  According to the present invention, an actinic ray-sensitive or radiation-sensitive resin composition excellent in sensitivity, roughness characteristics, resolution of isolated patterns and dry etching resistance, and capable of forming a pattern having a good shape, and the use thereof It is possible to provide a conventional pattern forming method.

Hereinafter, embodiments of the present invention will be described in detail.
Here, the groups and atomic groups that do not explicitly indicate substitution or non-substitution include both those that do not have a substituent and those that have a substituent. For example, an “alkyl group” that does not clearly indicate substitution or unsubstituted is not only an alkyl group that does not have a substituent (unsubstituted alkyl group) but also an alkyl group that has a substituent (substituted alkyl group) Is also included.

(resin)
The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention includes a repeating unit (A) represented by the following general formula (I) and a repeating unit (B) that generates an acid upon irradiation with an actinic ray or radiation. And a resin with As will be described later, the repeating unit (A) includes a group capable of decomposing by the action of an acid to generate an alkali-soluble group (hereinafter also referred to as an acid-decomposable group).

The repeating unit (A) is represented by the following general formula (I).

In formula (I), R _a is a hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group Represents an alkyloxycarbonyl group, an alkylcarbonyloxy group or an aralkyl group.
Y _a represents a divalent linking group.
Ar represents a structural unit including a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or are connected to each other through a single bond.
Y _b represents a single bond or a divalent linking group.
A ₃ represents a group capable of leaving by the action of an acid.
S ₂ represents a substituent (excluding a hydrogen atom), and when r ≧ 2, the plurality of S ₂ may be the same as or different from each other.
p represents an integer of 1 to 5.
q represents the integer of 1-5.
r represents an integer of 0 to 4 that satisfies the relationship of p + r ≦ 5.

R _a is a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, a carboxy group, as described above. Represents an alkyloxycarbonyl group, an alkylcarbonyloxy group or an aralkyl group;

The alkyl group may be a linear alkyl group or a branched alkyl group.
As a linear alkyl group, a C1-C30 thing is preferable and a C1-C20 thing is more preferable. Examples of such linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, and n- A heptyl group, n-octyl group, n-nonyl group, and n-decanyl group are mentioned.

  As a branched alkyl group, a C3-C30 thing is preferable and a C3-C20 thing is more preferable. Examples of such branched alkyl groups include i-propyl, i-butyl, t-butyl, i-pentyl, t-pentyl, i-hexyl, t-hexyl, and i-heptyl. Group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group and t-decanoyl group.

  As an alkoxy group, a C1-C8 thing is preferable. Examples of such an alkoxy group include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, a pentyloxy group, and a hexyloxy group.

  Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is particularly preferable.

  As an acyl group, a C2-C8 thing is preferable. Examples of such an acyl group include a formyl group, an acetyl group, a propanoyl group, a butanoyl group, a pivaloyl group, and a benzoyl group.

  As the acyloxy group, those having 2 to 8 carbon atoms are preferable. Examples of such an acyloxy group include an acetoxy group, a propionyloxy group, a butyryloxy group, a valeryloxy group, a pivaloyloxy group, a hexanoyloxy group, an octanoyloxy group, and a benzoyloxy group.

  The cycloalkyl group may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

  As the monocyclic cycloalkyl group, those having 3 to 8 carbon atoms are preferable. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group.

  Examples of the polycyclic cycloalkyl group include groups having a bicyclo, tricyclo or tetracyclo structure. The polycyclic cycloalkyl group preferably has 6 to 20 carbon atoms. Examples of such a cycloalkyl group include an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclododecyl group, and androstanyl group.

Examples of these cycloalkyl groups include those represented by the following formula.

  As an aryl group, a C6-C14 thing is preferable. Examples of such an aryl group include a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group, and an anthryl group.

  As the alkyloxycarbonyl group, those having 2 to 8 carbon atoms are preferable. Examples of such an alkyloxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group.

  As the alkylcarbonyloxy group, those having 2 to 8 carbon atoms are preferable. Examples of such an alkylcarbonyloxy group include a methylcarbonyloxy group and an ethylcarbonyloxy group.

  As the aralkyl group, those having 7 to 16 carbon atoms are preferable. Examples of such an aralkyl group include a benzyl group.

  Each of these alkyl group, alkoxy group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, alkyloxycarbonyl group, alkylcarbonyloxy group and aralkyl group may further have a substituent. Good.

  Examples of the substituent include a hydroxyl group; a halogen atom such as fluorine, chlorine, bromine and iodine atoms; a nitro group; a cyano group; an amide group; a sulfonamide group; a methyl group, an ethyl group, a propyl group, an isopropyl group, n- Alkyl groups such as butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; Examples include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; acyl groups such as formyl group, acetyl group and benzoyl group; acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group.

Y _a represents a divalent linking group as described above.
By interposing the Y _a between the benzene ring and the Ar constituting the polystyrene backbone, for example, by weakening the strength of the [pi-[pi interaction in the vicinity of the main chain, to reduce the hydrophobicity of the resin, It becomes possible to improve the developability of the composition.

Examples of the linking group include an alkylene group, a cycloalkylene group, an arylene group, a carbonyl group, a sulfide group, a sulfone group, —COO—, —CH ₂ O—, —COOCH ₂ —, —CONH—, and —SO ₂ NH. _{-, - CF 2 -, -} CF 2 CF 2 -, - OCF 2 O -, - CF 2 OCF 2 -, - SS -, - CH 2 SO 2 CH 2 -, - CH 2 COCH 2 -, - COCF 2 CO -, - COCO -, - OCOO -, - OSO 2 O -, - O -, - S -, - NH -, - N (R) -, acyl group, an alkylsulfonyl group, -CH = CH -, - C≡C—, aminocarbonylamino group, aminosulfonylamino group, and combinations of two or more thereof may be mentioned. Here, R represents a monovalent substituent. These linking groups may further have a substituent.

When Y _a has an asymmetric structure, Ar may be bonded to any side of the linking group exemplified above. For example, when Y _a is —COO—, the structure represented by “Y _a —Ar” may be “—COO—Ar” or “Ar—COO—”.

Y _a is preferably —O—, —CH ₂ O—, —COO— or —COOCH ₂ —, and particularly preferably —CH ₂ O—, —COO— or —COOCH ₂ —. If such a configuration is adopted, the sensitivity can be further improved.

Number of atoms contained in Y _a (excluding hydrogen atoms) is preferably 1 to 15, more preferably 1 to 10, more preferably 1 to 8, 2 to 8 Is particularly preferred. If this number of atoms is excessively increased, the distance between the main chain of the resin and the acid-decomposable group described later may be excessively increased, and the roughness characteristics of the composition may be deteriorated. If the number of atoms is excessively small, the flexibility (flexibility) of the side chain is decreased, and the sensitivity of the composition may be decreased.

The “minimum linking atom number” of Y _a is preferably 1 to 10, more preferably 1 to 5, still more preferably 2 to 4, and particularly preferably 2 or 3. When this “minimum number of linked atoms” is excessively increased, the distance between the resin main chain and an acid-decomposable group described later may be excessively increased, and the roughness characteristics of the composition may be deteriorated. If this “minimum number of linking atoms” is too small, the flexibility of the side chain may be reduced, and the sensitivity of the composition may be lowered.

The “minimum number of connected atoms” of Y _a is a number determined as follows. That is, first, among the atoms constituting Y _a , consider a sequence of atoms connecting atoms bonded to a benzene ring directly bonded to the main chain of the resin and atoms bonded to Ar. . Next, the number of atoms contained in each of these columns is obtained. The minimum number of these atoms is _defined as “the minimum number of connected atoms” of Ya.

For example, when Y _a is —O—, the minimum number of linked atoms is 1. When Y _a is —CH ₂ O—, the minimum number of linked atoms is 2. When Y _a is —COO—, the minimum number of linked atoms is 2. When Y _a is —COOCH ₂ —, the minimum number of linked atoms is 3. When Y _a is a 2-methyl-butylene group, the minimum number of linking atoms is 4. When Y _a is a cyclohexylene group, the minimum number of linking atoms is 4. Note that when Y _a is a linear alkylene group, the minimum linking atom number of Y _a is equal to the number of carbon atoms.

As described above, Ar represents a structural unit including a plurality of aromatic rings. The plurality of aromatic rings may be condensed to form a polycyclic structure, or may be connected to each other through a single bond. Each of these aromatic rings may contain a hetero atom.
By using a structural unit containing a plurality of aromatic rings as Ar, for example, improvement in dry etching resistance and improvement in sensitivity due to an increase in the amount of secondary electrons generated can be achieved.

  Examples of the aromatic ring that Ar may include include a benzene ring, a thiophene ring, a pyrrole ring, a furan ring, an imidazole ring, a pyridine ring, and a pyrazole ring. Here, the “benzene ring” refers to a ring composed of 6 carbon atoms, which contains the largest number of non-integrated double bonds (most numerous conjugated double bonds) in the ring. .

  Examples of the polycyclic structure that can be formed by condensing a plurality of aromatic rings include naphthalene ring, anthracene ring, phenanthrene ring, pyrene ring, triphenylene ring, tetracene ring, pentacene ring, chrysene ring, tetraphen ring, and picene. And a ring, pentaphen ring, perylene ring, helicene ring, coronene ring, indole ring, benzimidazole ring, carbazole ring and phenothiazine ring. Among these, an indole ring, a pyrene ring, a phenanthrene ring, an anthracene ring and a naphthalene ring are more preferable, and an anthracene ring and a naphthalene ring are particularly preferable.

  Examples of the structure in which a plurality of aromatic rings are connected to each other through a single bond include a biphenyl structure, a terphenyl structure, and a viologen structure. Among these, a biphenyl structure and a terphenyl structure are particularly preferable.

  The number of aromatic rings contained in Ar is preferably 2 to 5, more preferably 2 to 4, and most preferably 2 or 3. When the number of aromatic rings is excessively large, the hydrophobicity of the resin becomes excessively high, the pattern releasability is lowered, and the pattern shape may be deteriorated. Here, the “number of aromatic rings” is the number of benzene rings or the corresponding monocyclic heteroaryl rings. For example, it is 2 for naphthalene, biphenyl and bipyridine residues and 3 for anthracene, carbazole and phenothiazine residues.

In addition, the aromatic ring contained in Ar may further have a substituent other than — (Y _b COOA ₃ ) _q . Examples of the substituent include a hydroxyl group; a halogen atom such as fluorine, chlorine, bromine and iodine atoms; a nitro group; a cyano group; an amide group; a sulfonamide group; a methyl group, an ethyl group, a propyl group, an isopropyl group, n- Alkyl groups such as butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; Examples include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; acyl groups such as formyl group, acetyl group and benzoyl group; acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group.

Y _b represents a single bond or a divalent linking group as described above. Examples of the divalent linking group, for example, linking groups as described for the earlier Y _a.
Y _b is preferably a single bond, —CH ₂ O— or —COOCH ₂ —.

Number of atoms contained in Y _b (excluding hydrogen atom) is preferably 0 to 15, more preferably 0-10, more preferably 0-8. If this number of atoms is excessively increased, the distance between the main chain of the resin and the acid-decomposable group described later may be excessively increased, and the roughness characteristics of the composition may be deteriorated.

The “minimum linking atom number” of Y _b is preferably 0 to 10, more preferably 0 to 5, and still more preferably 0 to 3. When this “minimum number of linked atoms” is excessively increased, the distance between the resin main chain and an acid-decomposable group described later may be excessively increased, and the roughness characteristics of the composition may be deteriorated. Incidentally, "minimum number of connecting atoms" of Y _b is a number determined in the same manner as described for Y _a.

As described above, A ₃ is a group capable of leaving by the action of an acid.
When an acid is allowed to act on the resin containing the repeating unit represented by the general formula (I), at least a part of A ₃ is eliminated to generate a carboxy group which is an alkali-soluble group. That is, this repeating unit has a group represented by “—COOA ₃ ” as an acid-decomposable group.

A ₃ is preferably a hydrocarbon group. As the hydrocarbon group is preferably those having 1 to 30 carbon atoms, more preferably carbon atoms is of 4 to 25. In particular, A ₃ is preferably a t-butyl group, a t-amyl group, or a hydrocarbon group containing an alicyclic structure (for example, an alicyclic group or an alkyl group substituted by an alicyclic group).

  The alicyclic structure may be monocyclic or polycyclic. Specifically, examples of the alicyclic structure include monocyclo, bicyclo, tricyclo, and tetracyclo structures. The carbon number of the alicyclic structure is typically 5 or more, preferably 6 to 30, and particularly preferably 7 to 25. In addition, the hydrocarbon group containing an alicyclic structure may further have a substituent.

  Specific examples of this alicyclic structure include the same as those described above for the cycloalkyl group of Ra.

  Preferred alicyclic structures include, for example, adamantyl group, noradamantyl group, decalin residue, tricyclodecanyl group, tetracyclododecanyl group, norbornyl group, cedrol group, cyclohexyl group, cycloheptyl group, cyclooctyl group, cyclodecanyl group Group and cyclododecanyl group. More preferably, an adamantyl group, a decalin residue, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, a cyclodecanyl group, and a cyclododecanyl group are exemplified. Here, the alicyclic structure is represented as a monovalent alicyclic group.

  Examples of the substituent that these alicyclic structures may have include an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxy group, and an alkoxycarbonyl group.

The alkyl group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably a methyl group, an ethyl group, a propyl group and an isopropyl group.
As an alkoxy group, C1-C4 alkyl groups, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, are mentioned, for example.

  These alkyl groups and alkoxy groups may further have a substituent. As this substituent, a hydroxyl group, a halogen atom, and an alkoxy group are mentioned, for example.

A ₃ is particularly preferably a group represented by any one of the following formulas (pI) ~ formula (pV).

In general formulas (pI) to (pV),
R ₁₁ represents a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group or a sec-butyl group, and Z is an atom necessary for forming a cycloalkyl group together with a carbon atom. Represents a group.
R ₁₂ to R ₁₆ each independently represents a linear or branched alkyl group, or a cycloalkyl group having 1 to 4 carbon atoms. However, at least one of R _{12 to} R ₁₄ represents a cycloalkyl group. Moreover, any of R ₁₅ and R ₁₆ represents a cycloalkyl group.
R _{17 to} R ₂₁ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{17 to} R ₂₁ represents a cycloalkyl group. Also, one of R ₁₉ and R ₂₁ represents a linear or branched alkyl or cycloalkyl group having 1 to 4 carbon atoms.
R _{22 to} R ₂₅ each independently represents a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. However, at least one of R _{22 to} R ₂₅ represents a cycloalkyl group. R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

Examples of the alkyl group of R _{12 to} R ₂₅ include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and a t-butyl group.
These alkyl groups may further have a substituent. Examples of the substituent include an alkoxy group having 1 to 4 carbon atoms, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), an acyl group, an acyloxy group, a cyano group, a hydroxyl group, a carboxy group, and an alkoxycarbonyl group. And a nitro group.

Examples of the cycloalkyl group formed by Z and a carbon atom and the cycloalkyl groups of R _{12 to} R ₂₅ include the same groups as those described above for the cycloalkyl group of Ra.

Specific examples of A ₃ include the following groups.

S ₂ independently represents a substituent (excluding a hydrogen atom) when r ≧ 2. Kind of substituent represented by S ₂ is not particularly limited. Examples of the substituent include an alkyl group, cycloalkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, aralkyl group, aralkyloxy group, hydroxy group, halogen atom, cyano group, nitro group, Examples include a sulfonylamino group, an alkylthio group, an arylthio group, and an aralkylthio group.

  The alkyl group may be linear or branched. Examples of the alkyl group and cycloalkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, cyclopentyl group, hexyl group, cyclohexyl group, octyl group and C1-C20 things, such as a dodecyl group, are preferable.

  Examples of the aryl group include those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group, and anthryl group.

  Examples of the aralkyl group include a benzyl group.

  These groups may further have a substituent. Examples of the substituent include alkyl group, cycloalkyl group, alkoxy group, hydroxyl group, halogen atom, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, thiophenecarbonyloxy Groups, thiophenemethylcarbonyloxy groups, and heterocyclic residues such as pyrrolidone residues. The number of carbon atoms of this substituent is preferably 12 or less.

  Examples of the substituted alkyl group, cycloalkyl group, aryl group and aralkyl group include a cyclohexylethyl group, an alkylcarbonyloxymethyl group, an alkylcarbonyloxyethyl group, a cycloalkylcarbonyloxymethyl group, and a cycloalkylcarbonyloxyethyl group. Arylcarbonyloxyethyl group, aralkylcarbonyloxyethyl group, alkyloxymethyl group, cycloalkyloxymethyl group, aryloxymethyl group, aralkyloxymethyl group, alkyloxyethyl group, cycloalkyloxyethyl group, aryloxyethyl group, Aralkyloxyethyl group, alkylthiomethyl group, cycloalkylthiomethyl group, arylthiomethyl group, aralkylthiomethyl group, alkylthioethyl group, cycloal Ruchioechiru group, and arylthio ethyl and aralkylthio ethyl.

Examples of the alkylcarbonyloxyethyl group and the cycloalkylcarbonyloxyethyl group include a cyclohexylcarbonyloxyethyl group, a t-butylcyclohexylcarbonyloxyethyl group, and an n-butylcyclohexylcarbonyloxyethyl group. Examples of the aryloxyethyl group include a phenyloxyethyl group and a cyclohexylphenyloxyethyl group. These groups may further have a substituent.
Examples of the aralkylcarbonyloxyethyl group include a benzylcarbonyloxyethyl group. These groups may further have a substituent.

  p is an integer of 1 to 5 as described above. p is preferably 1 or 2, particularly preferably 1.

  q is an integer of 1 to 5 as described above. q is preferably 1 or 2, particularly preferably 1.

  As described above, r is an integer of 1 to 4 that satisfies the relationship of p + r ≦ 5. r is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In the repeating unit (A), R _a is preferably _a hydrogen atom or a methyl group, p = 1, and q = 1. That is, the repeating unit (A) preferably has a structure represented by the following general formula (II).

In formula (II), R _a represents a hydrogen atom or a methyl group. Y _a , Ar, Y _b , A _3, and S ₂ have the same meaning as described above for the general formula (I). r represents an integer of 0 to 4.

In the repeating unit (A), the group represented by “—Y _a —Ar—Y _b —COOA ₃ ” is preferably substituted at the para-position of the benzene ring directly bonded to the main chain of the resin. . In particular, R _a is a hydrogen atom or a methyl group, p = 1, q = 1, and a group represented by “—Y _a —Ar—Y _b —COOA ₃ ” is present in the main chain. Substitution at the para-position of the directly bonded benzene ring is preferred. That is, the repeating unit (A) preferably has a structure represented by the following general formula (III).

In formula (III), R _a represents a hydrogen atom or a methyl group. Y _a , Ar, Y _b , A _3, and S ₂ have the same meaning as described above for the general formula (I). r represents an integer of 0 to 4.

In the repeating unit (A), it is preferable that r = 0 as described above. In particular, R _a is a hydrogen atom or a methyl group, p = 1, q = 1, and a group represented by “—Y _a —Ar—Y _b —COOA ₃ ” is directly bonded to the main chain. It is preferably substituted at the para position of the bonded benzene ring and r = 0. That is, the repeating unit (A) preferably has a structure represented by the following general formula (IV).

In formula (IV), R _a represents a hydrogen atom or a methyl group. Y _a , Ar, Y _b and A ₃ have the same meanings as described above for the general formula (I).

Specific examples of the repeating unit (A) are shown below, but the scope of the present invention is not limited thereto.

  As described above, the composition according to the present invention includes a repeating unit (B) that generates an acid upon irradiation with actinic rays or radiation.

At least a part of the repeating unit (B) is preferably a repeating unit represented by any one of the following general formulas (B1), (B2) and (B3). Among these, the repeating unit represented by the following general formula (B1) or (B3) is more preferable, and the repeating unit represented by the following general formula (B1) is particularly preferable.

In the formula, A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₆ represents a cyano group, a carboxy group, —CO—OR ₂₅ or —CO—N (R ₂₆ ) (R ₂₇ ). R ₂₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ may be bonded to each other to form a ring together with the nitrogen atom. R ₂₆ and R ₂₇ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.
X _{1 to} X ₃ are each independently a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R ₃₃ ) —, or a combination thereof. Represents a divalent linking group. R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.

As the alkyl group for R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ , those having 20 or less carbon atoms are preferable, and those having 8 or less carbon atoms are more preferable. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group. These alkyl groups may further have a substituent.

The cycloalkyl groups of R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ may be monocyclic or polycyclic. As this cycloalkyl group, a C3-C8 thing is preferable. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group.

Examples of the halogen atom for R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Of these, a fluorine atom is particularly preferable.

As the alkyl group contained in the alkoxycarbonyl group of R _04, R ₀₅ and R ₀₇ to R _09, for example, those previously mentioned as the alkyl group of R _04, R ₀₅ and R ₀₇ to R ₀₉ are preferred.

As the alkyl group for R _{25 to} R ₂₇ and R ₃₃ , for example, those previously mentioned as the alkyl groups for R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ are preferable.
As the cycloalkyl group for R _{25 to} R ₂₇ and R ₃₃ , for example, those listed above as the cycloalkyl groups for R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ are preferable.

The alkenyl group of R ₂₅ to R ₂₇ and R _33, preferably having a carbon number of 2-6. Examples of such an alkenyl group include a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, and a hexenyl group.

The cycloalkenyl group for R _{25 to} R ₂₇ and R ₃₃ is preferably one having 3 to 6 carbon atoms. Examples of such a cycloalkenyl group include a cyclohexenyl group.

The aryl group of R _{25 to} R ₂₇ and R ₃₃ may be a monocyclic aromatic group or a polycyclic aromatic group. As this aryl group, a C6-C14 thing is preferable. This aryl group may further have a substituent. In addition, aryl groups may be bonded to each other to form a multicycle. Examples of the aryl group of R _{25 to} R ₂₇ and R ₃₃ include a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, and a naphthyl group.

R _{25 to} R ₂₇ and R ₃₃ are preferably aralkyl groups having 7 to 15 carbon atoms. This aralkyl group may further have a substituent. Examples of the aralkyl group of R _{25 to} R ₂₇ and R ₃₃ include a benzyl group, a phenethyl group, and a cumyl group.

The ring formed by combining R ₂₆ and R ₂₇ together with the nitrogen atom is preferably a 5- to 8-membered ring, and specific examples include pyrrolidine, piperidine, and piperazine.

The arylene group X ₁ to X _3, preferably having a carbon number of 6-14. Examples of such an arylene group include a phenylene group, a tolylene group, and a naphthylene group. These arylene groups may further have a substituent.

The alkylene group for X _{1 to} X ₃ is preferably an alkylene group having 1 to 8 carbon atoms. Examples of such an alkylene group include a methylene group, an ethylene group, a propylene group, a butylene group, a hexylene group, and an octylene group. These alkylene groups may further have a substituent.

  As the cycloalkylene group, those having 5 to 8 carbon atoms are preferable. Examples of such a cycloalkylene group include a cyclopentylene group and a cyclohexylene group. These cycloalkylene groups may further have a substituent.

Preferred substituents that each group in the general formulas (B1) to (B3) may have include, for example, a hydroxyl group; a halogen atom (fluorine, chlorine, bromine, iodine); a nitro group; a cyano group; an amide group; Groups; alkyl groups previously mentioned as R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ ; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy, and butoxy; methoxycarbonyl and Examples thereof include alkoxycarbonyl groups such as ethoxycarbonyl group; acyl groups such as formyl group, acetyl group and benzoyl group; acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group. These substituents preferably have 8 or less carbon atoms.

  A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid. Specifically, photoinitiator for photocationic polymerization, photoinitiator for photoradical polymerization, photodecolorant for dyes, Examples thereof include a structural portion possessed by a compound that generates an acid by known light used in a photochromic agent and a microresist.

A is more preferably an ionic structural site containing a sulfonium salt or an iodonium salt. More specifically, A is preferably a group represented by the following general formula (ZI) or (ZII).

In general formula (ZI),
R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represents an organic group.
The carbon number of the organic group as R _201, R ₂₀₂ and R ₂₀₃ is generally from 1 to 30, preferably 1 to 20. Two of R _{201 to} R ₂₀₃ may be bonded to form a ring structure, and the ring may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond, or a carbonyl group. Examples of the group formed by combining two of R _{201 to} R ₂₀₃ include alkylene groups such as a butylene group and a pentylene group.

Z ⁻ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation. Z ⁻ is preferably a non-nucleophilic anion. Examples of the non-nucleophilic anion include a sulfonate anion, a carboxylate anion, a sulfonylimide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion.

  The non-nucleophilic anion means an anion having an extremely low ability to cause a nucleophilic reaction. When a non-nucleophilic anion is used, degradation with time due to intramolecular nucleophilic reaction can be suppressed. This makes it possible to improve the temporal stability of the resin and the composition.

Examples of the organic group for R ₂₀₁ , R ₂₀₂ and R ₂₀₃ include the corresponding groups in the groups represented by (ZI-1), (ZI-2) and (ZI-3) described later.

  More preferable examples of the group represented by (ZI) include the (ZI-1) group, (ZI-2) group, (ZI-3) group and (ZI-4) group described below.

The (ZI-1) group is a group having arylsulfonium as a cation, in which at least one of R _{201 to} R ₂₀₃ in the general formula (ZI) is an aryl group.

All of R ₂₀₁ to R ₂₀₃ may be an aryl group or a part of R ₂₀₁ to R ₂₀₃ is an aryl group and the remainder may be an alkyl group or a cycloalkyl group.

  Examples of the (ZI-1) group include groups corresponding to triarylsulfonium, diarylalkylsulfonium, aryldialkylsulfonium, diarylcycloalkylsulfonium, and aryldicycloalkylsulfonium.

  The aryl group in the arylsulfonium is preferably a phenyl group or a naphthyl group, and more preferably a phenyl group. The aryl group may have a heterocyclic structure containing a hetero atom such as an oxygen atom, a nitrogen atom and a sulfur atom. Examples of this heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran and benzothiophene. When arylsulfonium has two or more aryl groups, these aryl groups may be the same as or different from each other.

  The alkyl group or cycloalkyl group which arylsulfonium has as necessary is preferably a linear or branched alkyl group having 1 to 15 carbon atoms or a cycloalkyl group having 3 to 15 carbon atoms. Examples of such an alkyl group or cycloalkyl group include a methyl group, an ethyl group, a propyl group, an n-butyl group, a sec-butyl group, a t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group. .

Aryl group R ₂₀₁ to R _203, an alkyl group or a cycloalkyl group, an alkyl group (for example, 1 to 15 carbon atoms), a cycloalkyl group (for example, 3 to 15 carbon atoms), an aryl group (for example, 6 to 14 carbon atoms) , An alkoxy group (for example, having 1 to 15 carbon atoms), a halogen atom, a hydroxyl group or a phenylthio group may be substituted.

Preferred examples of the substituent include a linear or branched alkyl group having 1 to 12 carbon atoms, a cycloalkyl group having 3 to 12 carbon atoms, and a linear, branched or cyclic alkoxy group having 1 to 12 carbon atoms. It is done. More preferable substituents include, for example, an alkyl group having 1 to 4 carbon atoms and an alkoxy group having 1 to 4 carbon atoms. The substituent may be substituted with any one of the three R _{201 to} R ₂₀₃ , or may be substituted with two or more of these. Further, when R _{201 to} R ₂₀₃ are a phenyl group, these substituents are preferably substituted at the p-position of the phenyl group.

Next, the (ZI-2) group will be described.
The (ZI-2) group is a group in which R _{201 to} R ₂₀₃ in the general formula (ZI) each independently represents an organic group having no aromatic ring. Here, the aromatic ring includes a heterocycle containing a hetero atom.

The organic group having no aromatic ring as R ₂₀₁ to R ₂₀₃ is generally a carbon number of 1 to 30, preferably 1 to 20.

R _{201 to} R ₂₀₃ are each independently preferably an alkyl group, a cycloalkyl group, an allyl group, or a vinyl group, more preferably a linear or branched 2-oxoalkyl group, 2-oxocyclo An alkyl group or an alkoxycarbonylmethyl group, more preferably a linear or branched 2-oxoalkyl group.

The alkyl group and cycloalkyl group of R ₂₀₁ to R _203, preferably a linear or branched alkyl group having 1 to 10 carbon atoms (e.g., methyl group, ethyl group, propyl group, butyl group or a pentyl group), and And a cycloalkyl group having 3 to 10 carbon atoms (for example, a cyclopentyl group, a cyclohexyl group, or a norbornyl group). More preferred examples of the alkyl group include a 2-oxoalkyl group and an alkoxycarbonylmethyl group. As the cycloalkyl group, a 2-oxocycloalkyl group is more preferable.

  The 2-oxoalkyl group may be linear or branched. As the 2-oxoalkyl group, a group having> C═O at the 2-position of the above alkyl group is preferable. As the 2-oxocycloalkyl group, a group having> C═O at the 2-position of the cycloalkyl group is preferably exemplified.

  The alkoxy group in the alkoxycarbonylmethyl group is preferably an alkoxy group having 1 to 5 carbon atoms (for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, or a pentoxy group).

R _{201 to} R ₂₀₃ may be further substituted with, for example, a halogen atom, an alkoxy group (eg, having 1 to 5 carbon atoms), a hydroxyl group, a cyano group, or a nitro group.

Next, the (ZI-3) group will be described.
The (ZI-3) group is a group represented by the following general formula (ZI-3), which is a group having a phenacylsulfonium salt structure.

In General Formula (ZI-3), R _{1c to} R _5c each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, an alkoxy group, or a halogen atom.
R _6c and R _7c each independently represents a hydrogen atom, an alkyl group or a cycloalkyl group.
R _x and R _y each independently represents an alkyl group, a cycloalkyl group, an allyl group or a vinyl group.
Two or more of R _{1c to} R _5c , R _6c and R _7c , and R _x and R _y may be bonded to each other to form a ring structure. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond and / or an amide bond. Examples of the group formed by bonding these to each other include a butylene group and a pentylene group.
Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same as Z ⁻ in the general formula (ZI).

  Specific examples of the structure of the cation moiety of the general formula (ZI-3) include acids exemplified in paragraphs 0047 and 0048 of JP-A No. 2004-233661 and paragraphs 0040 to 0046 of JP-A No. 2003-35948. See the structure of the cation moiety of the generator.

Subsequently, the (ZI-4) group will be described.
The (ZI-4) group is a group represented by the following general formula (ZI-4). This group is effective for suppressing outgas.

In General Formula (ZI-4), R ^{1 to} R ¹³ each independently represents a hydrogen atom or a substituent. At least one of R ^{1 to} R ¹³ is preferably a substituent containing an alcoholic hydroxyl group. Here, “alcoholic hydroxyl group” means a hydroxyl group bonded to a carbon atom of an alkyl group.
Z is a single bond or a divalent linking group.
Zc ⁻ represents a non-nucleophilic anion, and examples thereof include the same as Z ⁻ in the general formula (ZI).

When R ^{1 to} R ¹³ are substituents containing an alcoholic hydroxyl group, R ^{1 to} R ¹³ are preferably groups represented by — (W—Y). Here, Y is an alkyl group substituted with a hydroxyl group, and W is a single bond or a divalent linking group.

Preferable examples of the alkyl group represented by Y include an ethyl group, a propyl group, and an isopropyl group. Y particularly preferably includes a structure represented by —CH ₂ CH ₂ OH.

  The divalent linking group represented by W is not particularly limited, but preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, A divalent group in which an arbitrary hydrogen atom in an alkoxycarbonyl group or a carbamoyl group is replaced by a single bond, and more preferably an arbitrary hydrogen atom in a single bond, an acyloxy group, an alkylsulfonyl group, an acyl group or an alkoxycarbonyl group. It is a divalent group replaced by a single bond.

When R ^{1 to} R ¹³ are substituents containing an alcoholic hydroxyl group, the number of carbon atoms contained is preferably 2 to 10, more preferably 2 to 6, and particularly preferably 2 to 4.

The substituent containing an alcoholic hydroxyl group as R ^{1 to} R ¹³ may have two or more alcoholic hydroxyl groups. The number of the alcoholic hydroxyl group which the substituent containing the alcoholic hydroxyl group as R < ¹ > -R < ¹³ > has is 1-6, Preferably it is 1-3, More preferably, it is 1.

The number of alcoholic hydroxyl groups contained in the (ZI-4) group is ¹ to 10 in total for R ^{1 to} R ¹³ , preferably 1 to 6, and more preferably 1 to 3.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, examples of the substituent as R ^{1 to} R ¹³ include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, and an aryl group. , Heterocyclic group, cyano group, nitro group, carboxy group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group ( Anilino group), ammonio group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, arylthio group, Duplicate Ring thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocyclic azo group, imide group, phosphino group, Phosphinyl group, phosphinyloxy group, phosphinylamino group, phosphono group, silyl group, hydrazino group, ureido group, boronic acid group [—B (OH) ₂ ], phosphato group [—OPO (OH) ₂ ], Examples thereof include a sulfato group (—OSO ₃ H) and other known substituents.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are preferably a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, Cyano group, carboxy group, alkoxy group, aryloxy group, acyloxy group, carbamoyloxy group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino Group, alkylthio group, arylthio group, sulfamoyl group, alkyl and arylsulfonyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, imide group, silyl group or ureido group.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are more preferably a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, a cyano group, an alkoxy group, an acyloxy group, an acylamino group, An aminocarbonylamino group, an alkoxycarbonylamino group, an alkyl and arylsulfonylamino group, an alkylthio group, a sulfamoyl group, an alkyl and arylsulfonyl group, an alkoxycarbonyl group or a carbamoyl group.

When R ^{1 to} R ¹³ do not contain an alcoholic hydroxyl group, R ^{1 to} R ¹³ are particularly preferably a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, or an alkoxy group.

Two adjacent ones of R ^{1 to} R ¹³ may be bonded to each other to form a ring structure. This ring structure includes aromatic and non-aromatic hydrocarbon rings and heterocycles. These ring structures may be further combined to form a condensed ring.

The (ZI-4) group preferably has a structure in which at least one of R ^{1 to} R ¹³ contains an alcoholic hydroxyl group, and more preferably at least one of R ^{9 to} R ¹³ is alcoholic. It has a structure containing a hydroxyl group.

  Z represents a single bond or a divalent linking group as described above. Examples of the divalent linking group include an alkylene group, an arylene group, a carbonyl group, a sulfonyl group, a carbonyloxy group, a carbonylamino group, a sulfonylamide group, an ether group, a thioether group, an amino group, a disulfide group, an acyl group, Examples thereof include an alkylsulfonyl group, -CH = CH-, an aminocarbonylamino group, and an aminosulfonylamino group.

This divalent linking group may have a substituent. As these substituents, for example, those similar to those listed above for R ^{1 to} R ¹³ can be mentioned.

  Z is preferably a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, a bond having no electron withdrawing property such as —CH═CH—, an aminocarbonylamino group, and an aminosulfonylamino group, or A group, more preferably a single bond, an ether group or a thioether group, and particularly preferably a single bond.

Next, general formula (ZII) will be described.
In formula (ZII), R ₂₀₄ ~R ₂₀₅ each independently represents an aryl group, an alkyl group or a cycloalkyl group.
Aryl group R ₂₀₄ to R _207, an alkyl group, specific examples and preferred embodiments, such as cycloalkyl group are the same as those described for R ₂₀₁ to R ₂₀₃ in the compound of the aforementioned (ZI-1).

Aryl group, alkyl group of R ₂₀₄ to R _207, cycloalkyl groups may have a substituent. Examples of this substituent include the same as those described for R _{201 to} R ₂₀₃ in the aforementioned compound (ZI-1).

Z ⁻ represents an acid anion generated by decomposition upon irradiation with actinic rays or radiation, and is preferably a non-nucleophilic anion, and examples thereof include the same as Z ⁻ in the general formula (ZI).

Preferred examples of A also include groups represented by the following general formula (ZCI) or (ZCII).

In the above general formula (ZCI),
R ₃₀₁ and R ₃₀₂ each independently represents an organic group. The organic group generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. R ₃₀₁ and R ₃₀₂ may be bonded to each other to form a ring structure. This ring structure may contain an oxygen atom, a sulfur atom, an ester bond, an amide bond and / or a carbonyl group in the ring. Examples of the group that R ₃₀₁ and R ₃₀₂ can be bonded to each other include alkylene groups such as a butylene group and a pentylene group.
The organic group of R ₃₀₁ and R _302, for example, aryl groups mentioned as examples of R ₂₀₁ to R ₂₀₃ in formula (ZI), include alkyl groups and cycloalkyl groups.

  M represents an atomic group that forms an acid when a proton is added thereto. More specifically, a structure represented by any one of the general formulas AN1 to AN3 described later can be given. Of these, the structure represented by the general formula AN1 is particularly preferable.

R ₃₀₃ represents an organic group. The organic group as R ₃₀₃ generally has 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms. Specific examples of the organic group for R ₃₀₃ include an aryl group, an alkyl group, a cycloalkyl group, and the like given as specific examples of R ₂₀₄ and R ₂₀₅ in the general formula (ZII).

  Moreover, as a structural site | part which generate | occur | produces an acid by irradiation of actinic light or a radiation, the structural site | part used as the sulfonic acid precursor which the following photoacid generator has can be mentioned, for example. Examples of the photoacid generator include the following compounds (1) to (3).

(1) M.TUNOOKA et al., Polymer Preprints Japan, 35 (8); G. Berner et al., J. Rad. Curing, 13 (4); WJMijs et al., Coating Technol., 55 (697) H. Adachi et al., Polymer Preprints, Japan, 37 (3); European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122, USA Patent Documents Nos. 618,564, 4,371,605, 4,431,774, JP-A-64-18143, JP-A-2-245756, JP-A-4-365048, etc. A compound that generates sulfonic acid by photolysis represented by
(2) Disulfone compounds described in JP-A No. 61-166544.
(3) VNR Pillai, Synthesis, (1), 1 (1980); A. Abad et al, Tetrahedron Lett., (47) 4555 (1971); DHRBarton et al., J. Chem. Soc., (C) 329 (1970); U.S. Pat. No. 3,779,778; and European Patent No. 126,712.

  The repeating unit (B) preferably has a structural site that is converted to an acid anion by irradiation with actinic rays or radiation. For example, A in the general formulas (B1) to (B3) is preferably a structural site that is converted into an acid anion by irradiation with actinic rays or radiation.

  That is, it is more preferable that the repeating unit (B) has a structure in which an acid anion is generated in the side chain of the resin by irradiation with actinic rays or radiation. By adopting such a structure, the diffusion of the generated acid anions is suppressed, and the resolution and roughness characteristics can be further improved.

Formula sites _-X 1 -A in (B1), the general formula (B2) site _-X 2 -A in, and each of the sites _-X 3 -A in formula (B3), the following formula (L1), It is preferably represented by either (L2) or (L3).

_{-X 11 -L 11 -X 12 -Ar 1} -X 13 -L 12 -Z 1 (L1)
_{-Ar 2 -X 21 -L 21 -X 22} -L 22 -Z 2 (L2)
_{-X 31 -L 31 -X 32 -L 32} -Z 3 (L3)
First, the site | part represented by general formula (L1) is demonstrated.

X ₁₁ represents —O—, —S—, —CO—, —SO ₂ —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or these Represents a combined group.

  The alkyl group of R may be linear or branched. Moreover, the alkyl group of R may further have a substituent. The alkyl group preferably has 20 or less carbon atoms, more preferably 8 or less carbon atoms, and still more preferably 3 or less carbon atoms. Examples of such an alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, a hexyl group, a 2-ethylhexyl group, an octyl group, and a dodecyl group. R is particularly preferably a hydrogen atom, a methyl group or an ethyl group.

  The divalent nitrogen-containing non-aromatic heterocyclic group means a 3- to 8-membered non-aromatic heterocyclic group having at least one nitrogen atom.

X ₁₁ is more preferably —O—, —CO—, —NR— (R is a hydrogen atom or an alkyl group), or a combination thereof, and —COO— or —CONR— (R is hydrogen). Particularly preferred is an atom or an alkyl group.

L ₁₁ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, or a group obtained by combining two or more thereof. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

The alkylene group for L ₁₁ may be linear or branched. As this alkylene group, a C1-C8 thing is preferable, a C1-C6 thing is more preferable, and a C1-C4 thing is still more preferable.

As the alkenylene group for L ₁₁ , for example, a group having a double bond at any position of the above alkylene group can be mentioned.

The divalent aliphatic hydrocarbon ring group as L ₁₁ may be monocyclic or polycyclic. The divalent aliphatic hydrocarbon ring group preferably has 5 to 12 carbon atoms, and more preferably 6 to 10 carbon atoms.

  The divalent aromatic ring group as the linking group may be an arylene group or a heteroarylene group. The aromatic ring group preferably has 6 to 14 carbon atoms. This aromatic ring group may further have a substituent.

In addition, —NR— as a linking group and a divalent nitrogen-containing non-aromatic heterocyclic group are the same as, for example, each of X ₁₁ described above.

L ₁₁ is an alkylene group, a divalent aliphatic hydrocarbon ring group, or a combination of an alkylene group and a divalent aliphatic hydrocarbon ring group via —OCO—, —O— or —CONH—. Group (for example, -alkylene group-O-alkylene group-, -alkylene group-OCO-alkylene group- or -valent aliphatic hydrocarbon ring group-O-alkylene group-, -alkylene group-CONH-alkylene group- Is particularly preferred.

Specific examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₁₂ and X ₁₃ are the same as those in X ₁₁ described above, and preferred examples are also the same.

X ₁₂ is more preferably a single bond, —S—, —O—, —CO—, —SO ₂ —, or a combination thereof, and is a single bond, —S—, —OCO—, or —OSO ₂ —. Is particularly preferred.

X ₁₃ is more preferably —O—, —CO—, —SO ₂ —, or a combination thereof, and particularly preferably —OSO ₂ —.

Ar ₁ represents a divalent aromatic ring group. The divalent aromatic ring group may be an arylene group or a heteroarylene group. This divalent aromatic ring group may further have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, and an aryl group.

Ar ₁ is more preferably an arylene group having 6 to 18 carbon atoms which may have a substituent, or an aralkylene group in which an arylene group having 6 to 18 carbon atoms and an alkylene having 1 to 4 carbon atoms are combined. A phenylene group, a naphthylene group, a biphenylene group, or a phenylene group substituted with a phenyl group is particularly preferable.

L ₁₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these, and these groups are a part of a hydrogen atom or All are substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, and a cyano group. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

As L ₁₂ , an alkylene group, a divalent aromatic ring group, or a combination thereof, in which some or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group) A group is more preferable, and an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable. L ₁₂ is particularly preferably an alkylene group or a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms.

The alkylene group for L ₁₂ may be linear or branched. The alkylene group preferably has 1 to 6 carbon atoms, and more preferably 1 to 4 carbon atoms.

Examples of the alkenylene group for L ₁₂ include a group having a double bond at an arbitrary position of the alkylene group.

The divalent aliphatic hydrocarbon ring group represented by L ₁₂ may be monocyclic or polycyclic. The divalent aliphatic hydrocarbon ring group is preferably one having 3 to 17 carbon atoms.

Examples of the divalent aromatic ring group for L ₁₂ include the same groups as those described above as the linking group for L ₁₁ .

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₁₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

Z ₁ represents a site that becomes a sulfonic acid group upon irradiation with actinic rays or radiation, and specifically includes, for example, a structure represented by the above formula (ZI).

Next, the site | part represented by general formula (L2) is demonstrated.
Ar ₂ represents a divalent aromatic ring group. The divalent aromatic ring group may be an arylene group or a heteroarylene group. These divalent aromatic ring groups preferably have 6 to 18 carbon atoms. These divalent aromatic ring groups may further have a substituent.

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

Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₂₁ include the same as those described above for X ₁₁ .

X ₂₁ is more preferably —O—, —S—, —CO—, —SO ₂ —, or a combination thereof, and particularly preferably —O—, —OCO—, or —OSO ₂ —.

X ₂₂ represents a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R represents a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, or And represents a combination of these. Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in X ₂₂ include the same as those described above for X ₁₁ .
X ₂₂ is more preferably —O—, —S—, —CO—, —SO ₂ —, or a combination thereof, and particularly preferably —O—, —OCO—, or —OSO ₂ —.

L ₂₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

Examples of the alkylene group, alkenylene group, and divalent aliphatic hydrocarbon ring group for L ₂₁ include the same groups as those described above for L ₁₁ .

The divalent aromatic ring group of L ₂₁ may be an arylene group or a heteroarylene group. The divalent aromatic ring group preferably has 6 to 14 carbon atoms.

Examples of —NR— and divalent nitrogen-containing non-aromatic heterocyclic group in L ₂₁ include the same as those described above for X ₁₁ .

L ₂₁ includes, for example, a single bond, an alkylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these (for example, -alkylene group-2 divalent aromatic ring group- Or a group in which two or more of these are combined through a linking group such as -OCO-, -COO-, -O-, and -S- For example, -alkylene group-OCO-2 valent aromatic ring group-, -alkylene group-S-2 valent aromatic ring group-, or -alkylene group-O-alkylene group-2 valent aromatic ring group-). Particularly preferred.

L ₂₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these, and these groups are a part of hydrogen atoms or All may be substituted with a substituent selected from a fluorine atom, a fluorinated alkyl group, a nitro group, and a cyano group. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

L ₂₂ is an alkylene group, a divalent aromatic ring group, or a combination thereof, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable.

Specific examples of the alkylene group, the alkenylene group, the group aliphatic hydrocarbon ring group, the divalent aromatic ring group, and a combination of two or more of these represented by L ₂₂ include L ₁₂ in the general formula (VI). The same group as the specific example illustrated previously is mentioned.

Specific examples of the linking group —NR— and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₂₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

Z ₂ represents a site that becomes a sulfonic acid group when irradiated with actinic rays or radiation. Specific examples of Z ₂ are the same as those described above for Z ₁ .

Then, the site | part represented by general formula (L3) is demonstrated.
X ₃₁ and X ₃₂ each independently represent a single bond, —O—, —S—, —CO—, —SO ₂ —, —NR— (R is a hydrogen atom or an alkyl group), divalent nitrogen-containing non- An aromatic heterocyclic group or a group obtained by combining them is represented.
Examples of —NR— and a divalent nitrogen-containing non-aromatic heterocyclic group in each of X ₃₁ and X ₃₂ include the same as those described above for X ₁₁ .

X ₃₁ is preferably a single bond, —O—, —CO—, —NR— (wherein R is a hydrogen atom or an alkyl group), or a combination thereof, and more preferably a single bond, —COO— or —CONR—. (R is a hydrogen atom or an alkyl group) is particularly preferred.

X ₃₂ is more preferably —O—, —S—, —CO—, —SO ₂ —, a divalent nitrogen-containing non-aromatic heterocyclic group, or a combination thereof, —O—, — OCO- or -OSO ₂ - is particularly preferred.

L ₃₁ represents a single bond, an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more thereof. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

Examples of the alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, and divalent aromatic ring group of L ₃₁ include the same as those described above for L ₂₁ .

Specific examples of -NR- and a divalent nitrogen-containing non-aromatic heterocyclic group in L ₃₁ include the same specific examples as those in X ₁₁ described above, and preferred examples are also the same.

L ₃₂ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group, a divalent aromatic ring group, or a group obtained by combining two or more of these. In the combined group, two or more groups to be combined may be the same as each other or different from each other. These groups, -O -, - S -, - CO -, - SO 2 -, - NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing non-aromatic heterocyclic group, a divalent May be connected via a group of aromatic rings or a combination thereof.

L _{32 is} an alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, divalent aromatic ring group, or a combination of two or more thereof, wherein a part or all of the hydrogen atoms are fluorine atoms, It is preferably substituted with a substituent selected from a fluorinated alkyl group, a nitro group, and a cyano group.

L ₃₂ is an alkylene group, a divalent aromatic ring group, or a combination of these, in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluorinated alkyl group (more preferably a perfluoroalkyl group). Are more preferable, and an alkylene group or a divalent aromatic ring group in which part or all of the hydrogen atoms are substituted with fluorine atoms is particularly preferable.

Examples of the L ₃₂ alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, divalent aromatic ring group, and a group obtained by combining two or more of these include L ₁₂ described above. The same thing is mentioned. Specific examples of the —NR— of the linking group and the divalent nitrogen-containing non-aromatic heterocyclic group in L ₃₂ include the same specific examples as in X ₁₁ described above, and preferred examples are also the same.

In addition, when X ₃ is a single bond and L ₃₁ is an aromatic ring group, when R ₃₂ forms a ring with the aromatic ring group of L ₃₁ , the alkylene group represented by R ₃₂ has 1 carbon atom -8 are preferable, those having 1 to 4 carbon atoms are more preferable, and those having 1 to 2 carbon atoms are still more preferable.

Z ₃ represents an onium salt that becomes an imido acid group or a methide acid group upon irradiation with actinic rays or radiation. The onium salt represented by Z ₃ is preferably a sulfonium salt or an iodonium salt, and a structure represented by the following general formula (ZIII) or (ZIV) is preferred.

In general formulas (ZIII) and (ZIV), Z ₁ , Z ₂ , Z ₃ , Z ₄ , and Z ₅ are each independently-
CO— or —SO ₂ — is represented, and more preferably —SO ₂ —.

Rz ₁ , Rz ₂ and Rz ₃ each independently represents an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group. An embodiment in which part or all of the hydrogen atoms are substituted with a fluorine atom or a fluoroalkyl group (more preferably a perfluoroalkyl group) is more preferable.

The alkyl groups of Rz ₁ , Rz ₂ and Rz ₃ may be linear or branched. The alkyl group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and still more preferably 1 to 4 carbon atoms.

The monovalent aliphatic hydrocarbon ring group represented by Rz ₁ , Rz ₂ and Rz ₃ preferably has 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms.

Aryl groups Rz _1, Rz ₂ and Rz ₃ preferably has a carbon number of 6 to 18, more preferably a carbon number of an aryl group having from 6 to 10. As this aryl group, a phenyl group is particularly preferable.

Preferable examples of the aralkyl group represented by Rz ₁ , Rz ₂ and Rz ₃ include those in which an alkylene group having 1 to 8 carbon atoms and the aryl group are bonded. An aralkyl group formed by bonding an alkylene group having 1 to 6 carbon atoms and the aryl group is more preferable, and an aralkyl group formed by bonding an alkylene group having 1 to 4 carbon atoms and the aryl group is particularly preferable.

A ⁺ represents a sulfonium cation or an iodonium cation. Preferable examples of A ⁺ include a sulfonium cation in the general formula (ZI) or an iodonium cation structure in the general formula (ZII).

Specific examples of the repeating unit (B) are shown below, but the scope of the present invention is not limited thereto.

It is preferable that the resin further includes at least one of a repeating unit represented by the following general formula (A1) and a repeating unit represented by the following general formula (A2).

In general formula (A1), m represents an integer of 0 to 4. n represents an integer of 1 to 5 that satisfies the relationship m + n ≦ 5. S ₁ represents a substituent (excluding a hydrogen atom), and when m ≧ 2, the plurality of S ₁ may be the same as or different from each other. A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid. When n ≧ 2, the plurality of A ₁ may be the same as or different from each other.

In general formula (A2), X represents a hydrogen atom, an alkyl group, a hydroxyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, an acyl group, an acyloxy group, a cycloalkyl group, a cycloalkyloxy group, an aryl group, or a carboxy group. Represents an alkyloxycarbonyl group, an alkylcarbonyloxy group or an aralkyl group. A ₂ represents a group capable of leaving by the action of an acid.

First, the repeating unit represented by formula (A1) will be described.
As described above, m is an integer from 0 to 4. m is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.
As described above, n is an integer of 1 to 5 that satisfies the relationship m + n ≦ 5. n is preferably 1 or 2, particularly preferably 1.

S ₁ represents a substituent (excluding a hydrogen atom) as described above. As the substituent, for example, those previously in the general formula (I) has been described S ₂ similar to the.

As described above, A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid. When A ₁ is a group capable of leaving by the action of an acid, the repeating unit represented by the general formula (A1) is a repeating unit containing an acid-decomposable group. When A ₁ is a hydrogen atom, this repeating unit is a repeating unit not containing an acid-decomposable group.

Examples of the group capable of leaving by the action of an acid include tertiary alkyl groups such as t-butyl group and t-amyl group, t-butoxycarbonyl group, t-butoxycarbonylmethyl group, and formula -C (L ₁ ) (L ₂ ) —O—Z ² represents an acetal group.

Hereinafter, the acetal group represented by the formula —C (L ₁ ) (L ₂ ) —O—Z ² will be described. In the formula, L ₁ and L ₂ each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group, or an aralkyl group. Z ² represents an alkyl group, a cycloalkyl group, or an aralkyl group. Z ² and L ₁ may be bonded to each other to form a 5-membered or 6-membered ring.

The alkyl group may be a linear alkyl group or a branched alkyl group.
As a linear alkyl group, a C1-C30 thing is preferable and a C1-C20 thing is more preferable. Examples of such linear alkyl groups include methyl, ethyl, n-propyl, n-butyl, sec-butyl, t-butyl, n-pentyl, n-hexyl, and n- A heptyl group, n-octyl group, n-nonyl group, and n-decanyl group are mentioned.

  As a branched alkyl group, a C3-C30 thing is preferable and a C3-C20 thing is more preferable. Examples of such branched alkyl groups include i-propyl, i-butyl, t-butyl, i-pentyl, t-pentyl, i-hexyl, t-hexyl, and i-heptyl. Group, t-heptyl group, i-octyl group, t-octyl group, i-nonyl group and t-decanoyl group.

  These alkyl groups may further have a substituent. Examples of the substituent include a hydroxyl group; a halogen atom such as fluorine, chlorine, bromine and iodine atoms; a nitro group; a cyano group; an amide group; a sulfonamide group; a methyl group, an ethyl group, a propyl group, an isopropyl group, n- Alkyl groups such as butyl, sec-butyl, hexyl, 2-ethylhexyl, octyl and dodecyl; alkoxy groups such as methoxy, ethoxy, hydroxyethoxy, propoxy, hydroxypropoxy and butoxy; Examples include alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; acyl groups such as formyl group, acetyl group and benzoyl group; acyloxy groups such as acetoxy group and butyryloxy group, and carboxy group.

  As the alkyl group, an ethyl group, an isopropyl group, an isobutyl group, a cyclohexylethyl group, a phenylmethyl group, or a phenylethyl group is particularly preferable.

  The cycloalkyl group may be monocyclic or polycyclic. In the latter case, the cycloalkyl group may be bridged. That is, in this case, the cycloalkyl group may have a bridged structure. A part of carbon atoms in the cycloalkyl group may be substituted with a hetero atom such as an oxygen atom.

  As the monocyclic cycloalkyl group, those having 3 to 8 carbon atoms are preferable. Examples of such a cycloalkyl group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group.

  Examples of the polycyclic cycloalkyl group include groups having a bicyclo, tricyclo or tetracyclo structure. The polycyclic cycloalkyl group preferably has 6 to 20 carbon atoms. Examples of such a cycloalkyl group include an adamantyl group, norbornyl group, isobornyl group, camphanyl group, dicyclopentyl group, α-pinel group, tricyclodecanyl group, tetocyclododecyl group, and androstanyl group.

  Specific examples of the cycloalkyl group include those listed above for Ra in the general formula (I). These cycloalkyl groups may further have a substituent. Examples of the substituent include those described above as the substituent that the alkyl group may have. As the cycloalkyl group, a cyclohexyl group is particularly preferable.

Examples of the aralkyl group in L ₁ , L ₂ and Z ² include those having 7 to 15 carbon atoms such as a benzyl group and a phenethyl group.

  These aralkyl groups may further have a substituent. Preferred examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, and an aralkylthio group. Examples of the aralkyl group having a substituent include an alkoxybenzyl group, a hydroxybenzyl group, and a phenylthiophenethyl group. In addition, carbon number of the substituent which these aralkyl groups may have is preferably 12 or less.

Examples of the 5-membered or 6-membered ring that can be formed by bonding Z ² and L ₁ to each other include a tetrahydropyran ring and a tetrahydrofuran ring. Of these, a tetrahydropyran ring is particularly preferred.

Z ² is preferably a linear or branched alkyl group. Thereby, the effect of the present invention becomes more remarkable.

Although the specific example of the repeating unit represented by general formula (A1) below is given, it is not limited to these.

  Next, the repeating unit represented by general formula (A2) is demonstrated. As will be described later, this repeating unit has an acid-decomposable group.

X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyl as described above. An oxycarbonyl group, an alkylcarbonyloxy group or an aralkyl group is represented. These groups or atoms, for example, those previously in formula (I) in the same as described for R _a.

A ₂ represents a group capable of leaving by the action of an acid as described above. That is, the repeating unit represented by (A2) has a group represented by “—COOA ₂ ” as an acid-decomposable group. The A _2, for example, those previously in the general formula (I) has been described A ₃ similar to the.

Specific examples of the monomer corresponding to the repeating unit represented by the general formula (A2) are shown below, but are not limited thereto.

Although the specific example of the structure of the repeating unit represented by general formula (A2) below is given, it is not limited to these.

The repeating unit represented by the general formula (A2) is preferably a repeating unit of t-butyl methacrylate or ethylcyclopentyl methacrylate. The repeating unit represented by the general formula (A2) is also preferably a repeating unit represented by the following general formula (A2 ′).

  In General Formula (A2 ′), AR represents a phenyl group, a naphthyl group, or an anthryl group. Rn represents an alkyl group, a cycloalkyl group, or an aryl group. A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group. AR and Rn may be bonded to each other to form a ring.

  As described above, AR is a phenyl group, a naphthyl group, or an anthryl group. When AR is a naphthyl group or an anthryl group, the bonding position between the carbon atom to which Rn is bonded and AR is not particularly limited. For example, when AR is a naphthyl group, this carbon atom may be bonded to the α-position of the naphthyl group or may be bonded to the β-position. Alternatively, when AR is an anthryl group, this carbon atom may be bonded to the 1-position, the 2-position, or the 9-position of the anthryl group.

Phenyl group, naphthyl group and anthryl group as AR, respectively, may have one or more substituents.
Examples of the substituent include 1 methyl group such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group and dodecyl group. -20 linear or branched alkyl groups, alkoxy groups containing these alkyl groups, cycloalkyl groups such as cyclopentyl and cyclohexyl groups, cycloalkoxy groups containing these cycloalkyl groups, hydroxyl groups, halogen atoms, aryls Heterocycles such as groups, cyano groups, nitro groups, acyl groups, acyloxy groups, acylamino groups, sulfonylamino groups, alkylthio groups, arylthio groups, aralkylthio groups, thiophenecarbonyloxy groups, thiophenemethylcarbonyloxy groups, and pyrrolidone residues Residue. As this substituent, from the viewpoint of the resolving power of the composition, a linear or branched alkyl group having 1 to 5 carbon atoms or an alkoxy group containing these alkyl group moieties is preferable.

  AR is preferably a phenyl group, a paramethylphenyl group, or a paramethoxyphenyl group.

As described above, Rn represents an alkyl group, a cycloalkyl group, or an aryl group.
The alkyl group of Rn may be a straight chain alkyl group or a branched chain alkyl group. The alkyl group is preferably a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a t-butyl group, a pentyl group, a hexyl group, a cyclohexyl group, an octyl group or a dodecyl group. A thing with 1-20 carbon atoms is mentioned.

  Examples of the cycloalkyl group represented by Rn include those having 3 to 15 carbon atoms such as a cyclopentyl group and a cyclohexyl group.

  As the aryl group of Rn, for example, those having 6 to 14 carbon atoms such as phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group and anthryl group are preferable.

  Each of these alkyl group, cycloalkyl group and aryl group may further have a substituent. Examples of the substituent include an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, a sulfonylamino group, an alkylthio group, an arylthio group, an aralkylthio group, a thiophenecarbonyloxy group, and a thiophenemethylcarbonyl group. Examples include oxy groups and heterocyclic residues such as pyrrolidone residues. Among these, an alkoxy group, a hydroxyl group, a halogen atom, a nitro group, an acyl group, an acyloxy group, an acylamino group, and a sulfonylamino group are particularly preferable.

  As described above, A represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group, or an alkyloxycarbonyl group.

  Examples of the alkyl group and cycloalkyl group of A include the same as those described above for Rn. Each of these alkyl groups and cycloalkyl groups may have a substituent. Examples of this substituent include the same as those described above for Rn.

When A is an alkyl group or a cycloalkyl group having a substituent, particularly preferable A includes, for example, a CF ₃ group, an alkyloxycarbonylmethyl group, an alkylcarbonyloxymethyl group, a hydroxymethyl group, and an alkoxymethyl group. .

  Examples of the halogen atom for A include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Among these, a fluorine atom is particularly preferable.

  As the alkyl group moiety contained in the alkyloxycarbonyl group of A, for example, the configuration described above as the alkyl group of A can be employed.

Specific examples of the repeating unit represented by the general formula (A2 ') below, but is not limited thereto.

The resin preferably further contains a repeating unit represented by the following general formula (A4) in addition to the repeating units (A) and (B). By adopting such a configuration, for example, it is possible to further improve the film quality and further suppress the film loss of the unexposed portion.

In General Formula (A4), R ₂ represents a hydrogen atom, a methyl group, a cyano group, a halogen atom, or a perfluoro group having 1 to 4 carbon atoms. R ₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, an aryl group, an alkoxy group or an acyl group. q represents an integer of 0 to 4. W represents a group that is not decomposed by the action of an acid (hereinafter also referred to as an acid stabilizing group).

  Examples of the acid stabilizing group for W include a hydrogen atom, a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, an aryl group, an acyl group, an alkylamide group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group, An aryloxy group, an arylamidomethyl group, and an arylamido group are mentioned. W is preferably an acyl group, an alkylamide group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group or an aryloxy group, more preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group, a cycloalkyloxy group. Group or an aryloxy group.

  As the alkyl group for W, those having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group are preferable.

  As the cycloalkyl group of W, those having 3 to 10 carbon atoms such as cyclopropyl group, cyclobutyl group, cyclohexyl group and adamantyl group are preferable.

  As the alkenyl group for W, those having 2 to 4 carbon atoms such as vinyl group, propenyl group, allyl group and butenyl group are preferable.

  As the aryl group for W, those having 6 to 14 carbon atoms such as a phenyl group, a xylyl group, a toluyl group, a cumenyl group, a naphthyl group and an anthryl group are preferable.

  W can substitute any hydrogen atom contained in the benzene ring in the styrene skeleton as shown in the general formula (A4). The substitution position of W is not particularly limited, but is preferably a meta position or a para position, and particularly preferably a para position.

Hereinafter, specific examples of the repeating unit represented by the general formula (A4) is not limited thereto.

In addition to the repeating units (A) and (B), the resin may further include a repeating unit composed of a (meth) acrylic acid derivative that is not decomposed by the action of an acid. Although the specific example is given to the following, it is not limited to these.

In addition to the repeating units (A) and (B), the resin may further include a repeating unit having an acid-decomposable group represented by the formula —C (═O) —X ₁ —R _0. . Wherein, _{X 1} is an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. R ₀ is a group capable of leaving by the action of an acid, such as a tertiary alkyl group such as a t-butyl group and a t-amyl group, an isoboronyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, 1- 1-alkoxyethyl groups such as isobutoxyethyl group and 1-cyclohexyloxyethyl group, alkoxymethyl groups such as 1-methoxymethyl group and 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group , Trialkylsilyl ester groups, 3-oxocyclohexyl ester groups, 2-methyl-2-adamantyl groups, and mevalonic lactone residues.

  In addition, the said resin may further contain the other repeating unit provided with alkali-soluble groups, such as a phenolic hydroxyl group and a carboxy group, in order to maintain the favorable developability with respect to an alkaline developing solution. Moreover, in order to further improve the film quality, a hydrophobic repeating unit obtained from a monomer such as alkyl acrylate and alkyl methacrylate may be further included.

  The content of the repeating unit containing an acid-decomposable group in the resin is preferably 5 to 95 mol%, more preferably 10 to 60 mol%, based on all repeating units. It is especially preferable to set it as 50 mol%.

  The content of the repeating unit (A) in the resin is preferably 1 to 70 mol%, more preferably 1 to 50 mol%, based on all repeating units, and 1 to 30 mol%. It is particularly preferable to do this.

  The content of the repeating unit (B) in the resin is preferably 0.1 to 80 mol%, more preferably 0.5 to 60 mol%, based on all repeating units. It is especially preferable to set it as 40 mol%.

  When the said resin contains the repeating unit represented by general formula (A1), it is preferable that the content rate shall be 20-90 mol% on the basis of all the repeating units, and shall be 30-80 mol%. It is more preferable that the content be 40 to 70 mol%.

  When the said resin contains the repeating unit represented by general formula (A2), it is preferable that the content rate shall be 1-90 mol% on the basis of all the repeating units, and shall be 5-75 mol%. More preferably, it is particularly preferably 10 to 60 mol%.

  When the said resin contains the repeating unit represented by general formula (A4), it is preferable that the content rate shall be 1-50 mol% on the basis of all the repeating units, and shall be 1-40. More preferably, it is especially preferable to set it as 1-30 mol%.

  The weight average molecular weight (Mw) of the resin is preferably in the range of 1000 to 200000, more preferably in the range of 1000 to 100,000, still more preferably in the range of 1000 to 50000, 1000 It is particularly preferred that it is in the range of ˜25000. If this weight average molecular weight is excessively increased, the dissolution rate of the resin in the alkali and the sensitivity of the composition may decrease.

The degree of dispersion (Mw / Mn) of the resin is preferably 1.0 to 3.0, more preferably 1.0 to 2.5, and 1.0 to 2.0. Further preferred.
A resin having a high degree of dispersion can be synthesized, for example, as follows. That is, by performing radical polymerization using an azo polymerization initiator, for example, a resin having a dispersity of 1.2 to 2.0 can be synthesized. Further, by using the living radical polymerization method, for example, it can be synthesized resin dispersity 1.0 to 1.5.

  The above resins may be used alone or in combination of two or more. The total amount of these resins is usually 10 to 99% by mass, preferably 20 to 99% by mass, and particularly preferably 30 to 99% by mass, based on the total solid content of the composition.

Although the specific example of resin provided with repeating unit (A) and (B) below is shown, it is not limited to these.

<Other ingredients>
The composition according to the present invention may further contain a photoacid generator, a basic compound, a surfactant, a solvent, a dye, a photobase generator, an antioxidant, a solvent, and the like. Hereinafter, these components will be described.

(Photoacid generator)
The composition according to the present invention may further contain a photoacid generator in addition to the resin having the repeating units (A) and (B).

  The photoacid generator is a compound that generates an acid upon irradiation with actinic rays or radiation. Examples of the photoacid generator include photo-initiators of photo-cationic polymerization, photo-initiators of photo-radical polymerization, photo-decoloring agents, photo-discoloring agents, and acid by irradiation with actinic rays or radiation used in micro-resist. A known compound that generates a salt, and a mixture thereof can be appropriately selected and used. Examples of these include onium salts such as sulfonium salts and iodonium salts, and diazodisulfone compounds such as bis (alkylsulfonyldiazomethane).

Preferable examples of the photoacid generator include compounds represented by the following general formulas (ZI), (ZII) and (ZIII).

In the general formulas (ZI) and (ZII), R ₂₀₁ , R ₂₀₂ , R ₂₀₃ , R ₂₀₄ and R ₂₀₅ each independently represents an organic group. Specifically, these organic groups are the same as those mentioned in the description of the structural site that is decomposed by irradiation with actinic rays or radiation to generate an acid anion.

X ⁻ represents a non-nucleophilic anion. Examples of X ⁻ include a sulfonate anion, a bis (alkylsulfonyl) amide anion, a tris (alkylsulfonyl) methide anion, BF ₄ ⁻ , PF ₆ ^—, and SbF ₆ ^— . X ⁻ is preferably an organic anion containing a carbon atom. As a preferable organic anion, the organic anion shown to following AN1-AN3 is mentioned, for example.

In the formula _AN1~AN3, Rc 1 ~Rc ₃ independently represents an organic group. Examples of the organic group include those having 1 to 30 carbon atoms, preferably an alkyl group, an aryl group, or a group in which a plurality of these groups are linked through a linking group. Examples of this linking group include a single bond, —O—, —CO ₂ —, —S—, —SO ₃ —, and —SO ₂ N (Rd ₁ ) —. Here, Rd ₁ represents a hydrogen atom or an alkyl group, and may form a ring structure with a bonded alkyl group or aryl group.

The organic group of Rc _{1 to} Rc ₃ may be an alkyl group substituted at the 1-position with a fluorine atom or a fluoroalkyl group, or a phenyl group substituted with a fluorine atom or a fluoroalkyl group. By containing a fluorine atom or a fluoroalkyl group, it becomes possible to increase the acidity of the acid generated by light irradiation. Thereby, the sensitivity of the actinic ray-sensitive or radiation-sensitive resin composition can be improved. Rc _{1 to} Rc ₃ may be bonded to other alkyl groups and aryl groups to form a ring structure.

As the photoacid generator, a compound having a plurality of structures represented by the general formula (ZI) may be used. For example, the general formula at least one of R ₂₀₁ to R ₂₀₃ of a compound represented by (ZI), at least one coupling structure of R ₂₀₁ to R ₂₀₃ of another compound represented by formula (ZI) It may be a compound.

Hereinafter, Formula (ZIII) will be described.
In general formulas (ZII) and (ZIII), R _{206 to} R ₂₀₇ each independently represents an aryl group, an alkyl group, or a cycloalkyl group. These aryl group, alkyl group and cycloalkyl group may have a substituent.

In addition, X < ^- > in general formula (ZIII) is synonymous with X < ^- > in general formula (ZI).

Other preferred examples of the photoacid generator include compounds represented by the following general formula (ZIV), (ZV) or (ZVI).

In general formulas (ZIV) to (ZVI),
Ar ₃ and Ar ₄ each independently represents a substituted or unsubstituted aryl group.
R ₂₀₈ represents an alkyl group, a cycloalkyl group, or an aryl group independently in the general formulas (ZV) and (ZVI). These alkyl group, cycloalkyl group and aryl group may be substituted or unsubstituted.
These groups are preferably substituted with a fluorine atom. In this way, it is possible to increase the strength of the acid generated by the photoacid generator.

R ₂₀₉ and R ₂₁₀ each independently represents an alkyl group, a cycloalkyl group, an aryl group, or an electron withdrawing group. These alkyl group, cycloalkyl group, aryl group and electron withdrawing group may be substituted or unsubstituted.
Preferable R ₂₀₉ includes a substituted or unsubstituted aryl group.
Preferable R ₂₁₀ includes an electron withdrawing group. As this electron withdrawing group, Preferably, a cyano group and a fluoroalkyl group are mentioned.

  A represents an alkylene group, an alkenylene group or an arylene group. These alkylene group, alkenylene group and arylene group may have a substituent.

A compound having a plurality of structures represented by the general formula (ZVI) is also preferable as the photoacid generator. Such compounds, for example, binding to _{R 209} or _{R 210} of the compound represented by the general formula (ZVI), and the _{R 209} or _{R 210} of another compound represented by the general formula (ZVI) together And a compound having the above structure.

  As the photoacid generator, compounds represented by the general formulas (ZI) to (ZIII) are more preferable, and a compound represented by the general formula (ZI) is more preferable.

Specific examples of the photoacid generator are shown below, but are not limited thereto.

The composition according to the present invention may further contain a compound that generates a carboxylic acid upon irradiation with actinic rays or radiation as a photoacid generator. Examples of such compounds include the following.

  The molecular weight of these photoacid generators is, for example, in the range of 100-1500, and typically in the range of 200-1000.

  In addition, a photo-acid generator may be used individually by 1 type, and may be used in combination of 2 or more type. In the latter case, it is preferable to combine two types of compounds that generate two kinds of organic acids whose total number of atoms excluding hydrogen atoms is 2 or more.

  When the composition according to the present invention further contains a photoacid generator, the content thereof is preferably 0.1 to 40% by mass, more preferably 0.5, based on the total solid content of the composition. It is -30 mass%, More preferably, it is 1-20 mass%.

(Basic compound)
The composition according to the present invention may further contain a basic compound. The basic compound is preferably a compound having a stronger basicity than phenol. Moreover, this basic compound is preferably an organic basic compound, and more preferably a nitrogen-containing basic compound.

  Although the nitrogen-containing basic compound which can be used is not specifically limited, For example, the compound classified into the following (1)-(5) can be used.

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

In general formula (BS-1),
Each R independently represents a hydrogen atom or an organic group. However, at least one of the three Rs is an organic group. This organic group is a linear or branched alkyl group, a monocyclic or polycyclic cycloalkyl group, an aryl group, or an aralkyl group.

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 cycloalkyl 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. Specific examples include a phenyl group and a naphthyl group.
Although carbon number of the aralkyl group as R is not specifically limited, Usually, it is 7-20, Preferably it is 7-11. Specific examples include a benzyl group.

  In the alkyl group, cycloalkyl group, aryl group and aralkyl group as R, a hydrogen atom may be substituted with a substituent. Examples of the substituent include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxy group, a carboxy group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, and an alkyloxycarbonyl group.

  In the compound represented by the general formula (BS-1), it is preferable that at least two of R are organic groups.

  Specific examples of the compound represented by the general formula (BS-1) include tri-n-butylamine, tri-n-pentylamine, tri-n-octylamine, tri-n-decylamine, triisodecylamine, dicyclohexyl. Methylamine, tetradecylamine, pentadecylamine, hexadecylamine, octadecylamine, didecylamine, methyloctadecylamine, dimethylundecylamine, N, N-dimethyldodecylamine, methyldioctadecylamine, N, N-dibutylaniline, N , N-dihexylaniline, 2,6-diisopropylaniline, and 2,4,6-tri (t-butyl) aniline.

  Moreover, as a preferable basic compound represented by the general formula (BS-1), a compound in which at least one R is an alkyl group substituted with a hydroxy group can be given. Specific examples include triethanolamine and N, N-dihydroxyethylaniline.

In addition, the alkyl group as R may have an oxygen atom in the alkyl chain. That is, an oxyalkylene chain may be formed. As the oxyalkylene chain, —CH ₂ CH ₂ O— is preferable. Specifically, for example, tris (methoxyethoxyethyl) amine and compounds exemplified in the 60th and subsequent lines of column 3 of US6040112 can be mentioned.

(2) Compound having nitrogen-containing heterocyclic structure This nitrogen-containing heterocyclic ring may have aromaticity or may not have aromaticity. Moreover, you may have two or more nitrogen atoms. Furthermore, you may contain hetero atoms other than nitrogen. Specifically, for example, compounds having an imidazole structure (2-phenylbenzimidazole, 2,4,5-triphenylimidazole, etc.), compounds having a piperidine structure [N-hydroxyethylpiperidine and bis (1,2,2) , 6,6-pentamethyl-4-piperidyl) sebacate], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (such as antipyrine and hydroxyantipyrine).

  A compound having two or more ring structures is also preferably used. Specific examples include 1,5-diazabicyclo [4.3.0] non-5-ene and 1,8-diazabicyclo [5.4.0] -undec-7-ene.

(3) Amine compound having a phenoxy group An amine compound having a phenoxy group is a compound having a phenoxy group at the terminal opposite to the N atom of the alkyl group contained in the amine compound. The phenoxy group is, for example, a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxy group, a carboxylic acid ester group, a sulfonic acid ester group, an aryl group, an aralkyl group, an acyloxy group, and an aryloxy group. You may have.

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

  Specific examples include 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine and paragraph [0066] of US2007 / 0224539A1. ] (C1-1) to (C3-3) exemplified in the above.

  The amine compound having a phenoxy group is prepared by reacting, for example, a primary or secondary amine having a phenoxy group with a haloalkyl ether, and adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. And then extracted with an organic solvent such as ethyl acetate and chloroform. In addition, the amine compound having a phenoxy group reacts by heating a primary or secondary amine and a haloalkyl ether having a phenoxy group at the terminal, to form a strong base such as sodium hydroxide, potassium hydroxide or tetraalkylammonium. It can also be obtained by adding an aqueous solution and then extracting with an organic solvent such as ethyl acetate and chloroform.

(4) Ammonium salt As the basic compound, an ammonium salt can also be used as appropriate.
Examples of the anion of the ammonium salt include halides, sulfonates, borates, and phosphates. Of these, halides and sulfonates are particularly preferred.

As the halide, chloride, bromide and iodide are particularly preferable.
As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. Examples of the organic sulfonate include alkyl sulfonates having 1 to 20 carbon atoms and aryl sulfonates.

  The alkyl group contained in the alkyl sulfonate may have a substituent. Examples of the substituent include a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group. Specific examples of the alkyl sulfonate include methane sulfonate, ethane sulfonate, butane sulfonate, hexane sulfonate, octane sulfonate, benzyl sulfonate, trifluoromethane sulfonate, pentafluoroethane sulfonate, and nonafluorobutane sulfonate.

  Examples of the aryl group contained in the aryl sulfonate include a phenyl group, a naphthyl group, and an anthryl group. These aryl groups may have a substituent. As this substituent, a C1-C6 linear or branched alkyl group and a C3-C6 cycloalkyl group are preferable, for example. Specifically, for example, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferable. Examples of the other substituent include an alkoxy group having 1 to 6 carbon atoms, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group.

  The ammonium salt may be hydroxide or carboxylate. In this case, the ammonium salt is a tetraalkylammonium hydroxide having 1 to 8 carbon atoms (tetramethylammonium hydroxide, tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide, etc.). It is particularly preferred.

  Preferred basic compounds include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, piperazine, aminomorpholine and aminoalkylmorpholine. . These may further have a substituent. Preferred substituents include, for example, amino group, aminoalkyl group, alkylamino group, aminoaryl group, arylamino group, alkyl group, alkoxy group, acyl group, acyloxy group, aryl group, aryloxy group, nitro group, hydroxyl group And a cyano group.

  Particularly preferable basic compounds include, for example, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4-methylimidazole, N-methylimidazole, 2 -Phenylimidazole, 4,5-diphenylimidazole, 2,4,5-triphenylimidazole, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2- Diethylaminopyridine, 2- (aminomethyl) pyridine, 2-amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-amino Ethylpyridine, 4-aminoethylpyridine, 3-a Nopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-imino Piperidine, 1- (2-aminoethyl) pyrrolidine, pyrazole, 3-amino-5-methylpyrazole, 5-amino-3-methyl-1-p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methyl Pyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N-aminomorpholine and N- (2-aminoethyl) morpholine.

(5) A compound having a proton acceptor functional group and generating a compound which is decomposed by irradiation with actinic rays or radiation to decrease or disappear the proton acceptor, or change from proton acceptor to acidic ( PA)
The composition according to the present invention has a proton acceptor functional group as a basic compound and is decomposed by irradiation with actinic rays or radiation, resulting in a decrease, disappearance, or proton acceptor property. It may further contain a compound that generates a compound that has been changed to acidity (hereinafter also referred to as compound (PA)).

The proton acceptor functional group is a group that can interact electrostatically with a proton or a functional group having an electron. For example, a functional group having a macrocyclic structure such as a cyclic polyether or a π-conjugated group. It means a functional group having a nitrogen atom with an unshared electron pair that does not contribute. The nitrogen atom having an unshared electron pair that does not contribute to π conjugation is, for example, a nitrogen atom having a partial structure represented by the following general formula.

  Examples of a preferable partial structure of the proton acceptor functional group include a crown ether, an azacrown ether, a primary to tertiary amine, a pyridine, an imidazole, and a pyrazine structure.

  The compound (PA) is decomposed by irradiation with an actinic ray or radiation to generate a compound in which the proton acceptor property is lowered, disappeared, or changed from proton acceptor property to acidity. Here, the decrease or disappearance of the proton acceptor property or the change from the proton acceptor property to the acid is a change in the proton acceptor property caused by the addition of a proton to the proton acceptor functional group. Specifically, when a proton adduct is formed from a compound having a proton acceptor functional group (PA) and a proton, the equilibrium constant in the chemical equilibrium is reduced.

Proton acceptor property can be confirmed by measuring pH.
In the present invention, the acid dissociation constant pKa of the compound generated by decomposition of the compound (PA) upon irradiation with actinic rays or radiation preferably satisfies pKa <−1, more preferably −13 <pKa <−1. And more preferably −13 <pKa <−3.

  In the present invention, the acid dissociation constant pKa represents the acid dissociation constant pKa in an aqueous solution. For example, Chemical Handbook (II) (4th revised edition, 1993, edited by the Chemical Society of Japan, Maruzen Co., Ltd.) It shows that acid strength is so large that this value is low. Specifically, the acid dissociation constant pKa in an aqueous solution can be measured by measuring an acid dissociation constant at 25 ° C. using an infinitely diluted aqueous solution, and using the following software package 1, Hammett The values based on the substituent constants and the database of known literature values can also be obtained by calculation. The values of pKa described in this specification all indicate values obtained by calculation using this software package.

Software package 1: Advanced Chemistry Development (ACD / Labs) Software V8.14 for Solaris (1994-2007 ACD / Labs)
The compound (PA) generates, for example, a compound represented by the following general formula (PA-1) as the proton adduct generated by decomposition upon irradiation with actinic rays or radiation. The compound represented by the general formula (PA-1) has an acidic group as well as a proton acceptor functional group, so that the proton acceptor property is reduced or disappeared compared to the compound (PA), or from the proton acceptor property. It is a compound that has changed to acidic.

In general formula (PA-1),
Q represents -SO ₃ H, -CO ₂ H or _-X 1 NHX ₂ R _f,. Here, R _f represents an alkyl group, a cycloalkyl group or an aryl group, and X ₁ and X ₂ each independently represent —SO ₂ — or —CO—.
A represents a single bond or a divalent linking group.
X represents —SO ₂ — or —CO—.
n represents 0 or 1.
B represents a single bond, an oxygen atom, or -N (Rx) Ry-. Rx represents a hydrogen atom or a monovalent organic group, and Ry represents a single bond or a divalent organic group. It may combine with Ry to form a ring, or may combine with R to form a ring.
R represents a monovalent organic group having a proton acceptor functional group.

General formula (PA-1) is demonstrated still in detail.
The divalent linking group in A is preferably a divalent linking group having 2 to 12 carbon atoms, and examples thereof include an alkylene group and a phenylene group. More preferably, it is an alkylene group having at least one fluorine atom, and a preferable carbon number is 2 to 6, more preferably 2 to 4. The alkylene chain may have a linking group such as an oxygen atom or a sulfur atom. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms are substituted with fluorine atoms, and more preferably, the carbon atom bonded to the Q site has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

  The monovalent organic group in Rx preferably has 1 to 30 carbon atoms, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group. These groups may further have a substituent.

  The alkyl group in Rx may have a substituent, preferably a linear or branched alkyl group having 1 to 20 carbon atoms, and has an oxygen atom, a sulfur atom, or a nitrogen atom in the alkyl chain. May be.

  Preferred examples of the divalent organic group for Ry include an alkylene group. Examples of the ring structure which Rx and Ry may be bonded to each other include a 5- to 10-membered ring containing a nitrogen atom, particularly preferably a 6-membered ring.

  Examples of the alkyl group having a substituent include groups in which a linear or branched alkyl group is substituted with a cycloalkyl group (for example, an adamantylmethyl group, an adamantylethyl group, a cyclohexylethyl group, a camphor residue, etc.). .

  The cycloalkyl group in Rx may have a substituent, preferably a cycloalkyl group having 3 to 20 carbon atoms, and may have an oxygen atom in the ring.

  The aryl group in Rx may have a substituent, and is preferably an aryl group having 6 to 14 carbon atoms.

  The aralkyl group in Rx may have a substituent, and preferably an aralkyl group having 7 to 20 carbon atoms.

  The alkenyl group in Rx may have a substituent, and examples thereof include a group having a double bond at an arbitrary position of the alkyl group mentioned as Rx.

  The proton acceptor functional group in R is as described above, and examples thereof include azacrown ether, primary to tertiary amines, groups having a heterocyclic aromatic structure containing nitrogen such as pyridine and imidazole.

  As the organic group having such a structure, a preferable carbon number is 4 to 30, and examples thereof include an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, and an alkenyl group.

  The alkyl group, the cycloalkyl group, the aryl group, the aralkyl group, the alkyl group in the alkenyl group, the cycloalkyl group, the aryl group, the aralkyl group, and the alkenyl group in R include a proton acceptor functional group or an ammonium group. Are the same as the alkyl group, cycloalkyl group, aryl group, aralkyl group and alkenyl group mentioned above.

  Examples of the substituent that each group may have include, for example, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), and an aryl group (preferably Has 6 to 14 carbon atoms, an alkoxy group (preferably 1 to 10 carbon atoms), an acyl group (preferably 2 to 20 carbon atoms), an acyloxy group (preferably 2 to 10 carbon atoms), an alkoxycarbonyl group (preferably And C2-C20) and aminoacyl groups (preferably C2-C20). As for the cyclic structure in the aryl group, cycloalkyl group and the like, and the aminoacyl group, examples of the substituent further include an alkyl group (preferably having 1 to 20 carbon atoms).

  When B is -N (Rx) Ry-, R and Rx are preferably bonded to each other to form a ring. By forming the ring structure, the stability is improved, and the storage stability of the composition using the ring structure is improved. The number of carbon atoms forming the ring is preferably 4 to 20, and may be monocyclic or polycyclic, and may contain an oxygen atom, a sulfur atom, or a nitrogen atom in the ring.

  Examples of the monocyclic structure include a 4-membered ring, a 5-membered ring, a 6-membered ring, a 7-membered ring, and an 8-membered ring containing a nitrogen atom. Examples of the polycyclic structure include a structure composed of a combination of two or three or more monocyclic structures. The monocyclic structure and polycyclic structure may have a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxy group, a carbonyl group, a cycloalkyl group (preferably having 3 to 10 carbon atoms), Aryl group (preferably having 6 to 14 carbon atoms), alkoxy group (preferably having 1 to 10 carbon atoms), acyl group (preferably having 2 to 15 carbon atoms), acyloxy group (preferably having 2 to 15 carbon atoms), alkoxycarbonyl A group (preferably having 2 to 15 carbon atoms), an aminoacyl group (preferably having 2 to 20 carbon atoms) and the like are preferable. As for the cyclic structure in the aryl group, cycloalkyl group and the like, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15). As for the aminoacyl group, examples of the substituent further include an alkyl group (preferably having a carbon number of 1 to 15).

As _{R f} in _-X 1 NHX ₂ R _f represented by Q, preferred is an alkyl group which may have a fluorine atom having 1 to 6 carbon atoms, more preferably perfluoroalkyl of 1 to 6 carbon atoms It is a group. Further, as X ₁ and X ₂ , at least one is preferably —SO ₂ —, and more preferably, both X ₁ and X ₂ are —SO ₂ —.

  Among the compounds represented by the general formula (PA-1), a compound in which the Q site is a sulfonic acid can be synthesized by using a general sulfonamidation reaction. For example, a method in which one sulfonyl halide part of a bissulfonyl halide compound is selectively reacted with an amine compound to form a sulfonamide bond, and then the other sulfonyl halide part is hydrolyzed, or a cyclic sulfonic acid anhydride is used. It can be obtained by a method of ring-opening by reacting with an amine compound.

The compound (PA) is preferably an ionic compound. The proton acceptor functional group may be contained in either the anion portion or the cation portion, but is preferably contained in the anion portion.
Preferred examples of the compound (PA) include compounds represented by the following general formulas (4) to (6).

In the general formulas (4) to (6), A, X, n, B, R, Rf, X ₁ and X ₂ have the same meanings as those in the general formula (PA-1).
C ⁺ represents a counter cation.

The counter cation is preferably an onium cation. More specifically, the sulfonium cation previously described as S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ) in the general formula (ZI), and I ⁺ (R ₂₀₄ ) (R ₂₀₅ ) in the general formula (ZII). Preferred examples include iodonium cations.

Hereinafter, although the specific example of a compound (PA) is shown, it is not limited to these.

Moreover, in this invention, compounds (PA) other than the compound which generate | occur | produces the compound represented by general formula (PA-1) can also be selected suitably. For example, an ionic compound that has a proton acceptor moiety in the cation moiety may be used. More specifically, a compound represented by the following general formula (7) is exemplified.

In the formula, A represents a sulfur atom or an iodine atom.
m represents 1 or 2, and n represents 1 or 2. However, when A is a sulfur atom, m + n = 3, and when A is an iodine atom, m + n = 2.
R represents an aryl group.
R _N represents an aryl group substituted with a proton acceptor functional group.
X ⁻ represents a counter anion.

X ^- include specific examples of, X in formula (ZI) ^- it includes the same as.
Specific examples of the aryl group of R and R _N is a phenyl group are preferably exemplified.

Specific examples of the proton acceptor functional group R _N are the same as those of the proton acceptor functional group described in the foregoing formula (PA-1).

  In the composition of the present invention, the compounding ratio of the compound (PA) in the whole composition is preferably 0.1 to 10% by mass, more preferably 1 to 8% by mass in the total solid content.

  Other examples that can be used in the composition according to the present invention include compounds synthesized in Examples of JP-A No. 2002-363146, and compounds described in paragraph 0108 of JP-A No. 2007-298869. It is done.

  A photosensitive basic compound may be used as the basic compound. As the photosensitive basic compound, for example, JP-T-2003-524799 and J. Org. Photopolym. Sci & Tech. Vol. 8, P.I. 543-553 (1995) etc. can be used.

  The molecular weight of the basic compound is usually 100-1500, preferably 150-1300, and more preferably 200-1000.

These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more types.
When the composition according to the present invention contains a basic compound, the content is preferably 0.01 to 8.0% by mass based on the total solid content of the composition, The content is more preferably 5.0% by mass, and particularly preferably 0.2 to 4.0% by mass.

  The molar ratio of the basic compound to the photoacid generator is preferably 0.01 to 10, more preferably 0.05 to 5, and still more preferably 0.1 to 3. If this molar ratio is excessively increased, sensitivity and / or resolution may be reduced. If this molar ratio is excessively small, there is a possibility that pattern thinning occurs between exposure and heating (post-bake). More preferably, it is 0.05-5, More preferably, it is 0.1-3.

(Surfactant)
The composition according to the present invention may further contain a surfactant. As this surfactant, fluorine-based and / or silicon-based surfactants are particularly preferable.

  Examples of the fluorine-based and / or silicon-based surfactant include Megafac F176 and Megafac R08 manufactured by Dainippon Ink and Chemicals, PF656 and PF6320 manufactured by OMNOVA, and Troisol S manufactured by Troy Chemical Co., Ltd. -366, FLORARD FC430 manufactured by Sumitomo 3M Limited, and polysiloxane polymer KP-341 manufactured by Shin-Etsu Chemical Co., Ltd.

  Surfactants other than fluorine and / or silicon may be used. Examples of the surfactant include nonionic surfactants such as polyoxyethylene alkyl ethers and polyoxyethylene alkyl aryl ethers.

  In addition, known surfactants can be used as appropriate. Examples of the surfactant that can be used include surfactants described in [0273] and after in US 2008 / 0248425A1.

One type of surfactant may be used alone, or two or more types may be used in combination.
When the composition according to the present invention further contains a surfactant, the amount used is preferably 0.0001 to 2% by mass, more preferably 0.001 to 2, based on the total solid content of the composition. 1% by mass.

(dye)
The composition according to the present invention may further contain a dye.
Suitable dyes include, for example, oily dyes and basic dyes. Specifically, for example, oil yellow # 101, oil yellow # 103, oil pink # 312, oil green BG, oil blue BOS, oil blue # 603, oil black BY, oil black BS, and oil black T-505 (or above) Orient Chemical Industry Co., Ltd.), crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000), and methylene blue (CI522015).

(Photobase generator)
The composition according to the present invention may further contain a photobase generator. When a photobase generator is contained, a more favorable pattern can be formed.

  Examples of the photobase generator include JP-A-4-151156, JP-A-4-162040, JP-A-5-197148, JP-A-5-5995, JP-A-6-194634, JP-A-8-146608, and JP-A-10-83079. And compounds described in European Patent No. 622682. Preferred photobase generators include 2-nitrobenzyl carbamate, 2,5-dinitrobenzyl cyclohexyl carbamate, N-cyclohexyl-4-methylphenylsulfonamide and 1,1-dimethyl-2-phenylethyl- N-isopropyl carbamate may be mentioned.

(Antioxidant)
The composition according to the present invention may further contain an antioxidant. When the antioxidant is contained, it is possible to suppress the oxidation of the organic material in the presence of oxygen.

  Examples of antioxidants include phenolic antioxidants, antioxidants composed of organic acid derivatives, sulfur-containing antioxidants, phosphorus antioxidants, amine antioxidants, and antioxidants composed of amine-aldehyde condensates. And an antioxidant comprising an amine-ketone condensate. Of these antioxidants, it is particularly preferable to use an antioxidant comprising a phenolic antioxidant and an organic acid derivative. If it carries out like this, the function as antioxidant can be expressed, without reducing the performance of a composition.

  As the phenolic antioxidant, for example, substituted phenols, bis, tris, or polyphenols can be used.

  Examples of substituted phenols include 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol, 2,6- Di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, butylhydroxyanisole, 2- (1-methylcyclohexyl) -4,6-dimethylphenol, 2,4- Dimethyl-6-tert-butylphenol, 2-methyl-4,6-dinonylphenol, 2,6-di-tert-butyl-α-dimethylamino-p-cresol, 6- (4-hydroxy-3,5-di -Tert-butylanilino) 2,4-bisoctyl-thio-1,3,5-triazine, n-octadecyl 3- (4'-hydroxy-3 ', 5'-di -tert- butyl-phenyl) propionate, octyl phenol, aralkyl-substituted phenols, alkylated -p- cresol, and hindered phenols and the like.

  Examples of bis, tris, or polyphenols include 4,4′-dihydroxydiphenyl, methylene bis (dimethyl-4,6-phenol), and 2,2′-methylene-bis- (4-methyl-6-tert-butylphenol). 2,2′-methylene-bis- (4-methyl-6-cyclohexyl phenol), 2,2′-methylene-bis- (4-ethyl-6-tert-butylphenol), 4,4′-methylene- Bis- (2,6-di-tert-butylphenol), 2,2′-methylene-bis- (6-alphamethyl-benzyl-p-cresol), methylene-bridged polyhydric alkylphenol, 4,4′-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1-bis- (4-hydroxyphenyl) -cyclohexane Sun, 2,2′-dihydroxy-3,3′-di- (α-methylcyclohexyl) -5,5′-dimethyldiphenylmethane, alkylated bisphenol, hindered bisphenol, 1,3,5-trimethyl-2,4 , 6-Tris (3,5-di-tert-butyl-4-hydroxybenzyl) benzene, tris- (2-methyl-4-hydroxy-5-tert-butylphenyl) butane, and tetrakis- [methylene-3- (3 ′, 5′-di-tert-butyl-4′-hydroxyphenyl) propionate] methane.

  The antioxidant is preferably 2,6-di-t-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, 2,2′-methylenebis (4-methyl- 6-t-butylphenol), butylhydroxyanisole, t-butylhydroquinone, 2,4,5-trihydroxybutyrophenone, nordihydroguaiaretic acid, propyl gallate, octyl gallate, lauryl gallate, and isopropyl citrate. Can be mentioned. Of these, 2,6-di-t-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, butylhydroxyanisole, and t-butylhydroquinone are more preferable. Di-t-butyl-4-methylphenol or 4-hydroxymethyl-2,6-di-t-butylphenol is more preferred.

One type of antioxidant may be used alone, or two or more types may be used in combination.
When the composition according to the present invention contains an antioxidant, the amount added is preferably 1 ppm or more, more preferably 5 ppm or more, still more preferably 10 ppm or more, and even more preferably 50 ppm or more, particularly Preferably it is 100 ppm or more, Most preferably, it is 100-1000 ppm.

(solvent)
The composition according to the present invention may further contain a solvent.
Typically, an organic solvent is used as this solvent. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylate, alkylene glycol monoalkyl ether, alkyl lactate ester, alkyl alkoxypropionate, cyclic lactone (preferably having 4 to 10 carbon atoms), and a ring. Good monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonate, alkyl alkoxyacetate, and alkyl pyruvate are mentioned.

  Examples of the alkylene glycol monoalkyl ether carboxylate include propylene glycol monomethyl ether acetate (PGMEA; also known as 1-methoxy-2-acetoxypropane), 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.

  Examples of the alkylene glycol monoalkyl ether include propylene glycol monomethyl ether (PGME; also known as 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol monomethyl ether, and And ethylene glycol monoethyl ether.

Examples of the lactate alkyl ester include methyl lactate, ethyl lactate, propyl lactate and butyl lactate.
Examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxypropionate.

  Examples of the cyclic lactone include β-propiolactone, β-butyrolactone, γ-butyrolactone, α-methyl-γ-butyrolactone, β-methyl-γ-butyrolactone, γ-valerolactone, γ-caprolactone, and γ-octano. And iclactone and α-hydroxy-γ-butyrolactone.

  Examples of the monoketone compound which may contain a ring include 2-butanone, 3-methylbutanone, pinacolone, 2-pentanone, 3-pentanone, 3-methyl-2-pentanone, 4-methyl-2-pentanone, 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-decanone, 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 and 3- And methylcycloheptanone.

Examples of the alkylene carbonate include propylene carbonate, vinylene carbonate, ethylene carbonate, and butylene carbonate.
Examples of the alkyl alkoxyacetate include 2-methoxyethyl acetate, 2-ethoxyethyl acetate, 2- (2-ethoxyethoxy) ethyl acetate, 3-methoxy-3-methylbutyl acetate, and 1-methoxy acetate. -2-propyl.
Examples of the alkyl pyruvate include methyl pyruvate, ethyl pyruvate, and propyl pyruvate.

  As the solvent, it is preferable to use a solvent having a boiling point of 130 ° C. or higher under normal temperature and pressure. Specifically, for example, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, PGMEA, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate, acetic acid-2 -(2-Ethoxyethoxy) ethyl and propylene carbonate are mentioned.

  These solvents may be used alone or in combination of two or more. In the latter case, it is preferable to use a mixed solvent of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group.

  Examples of the solvent containing a hydroxyl group include ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, PGME, propylene glycol monoethyl ether, and ethyl lactate. Of these, PGME and ethyl lactate are particularly preferred.

  Examples of the solvent not containing a hydroxyl group include PGMEA, ethylethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide and the like. Among these, propylene glycol monomethyl ether acetate, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone and butyl acetate can be mentioned. Of these, PGMEA, ethyl ethoxypropionate and 2-heptanone are particularly preferred.

  When using a mixed solvent of a solvent containing a hydroxyl group and a solvent not containing a hydroxyl group, these mass ratios are preferably 1/99 to 99/1, more preferably 10/90 to 90/10, More preferably, it is set to 20/80 to 60/40.

  When a mixed solvent containing 50% by mass or more of a solvent not containing a hydroxyl group is used, particularly excellent coating uniformity can be achieved. The solvent is particularly preferably a mixed solvent of PGMEA and one or more other solvents.

<Pattern formation method>
The composition according to the present invention is typically used as follows. That is, the composition according to the present invention is typically applied on a support such as a substrate to form a film.
The thickness of this film is preferably 0.02 to 0.1 μm. As a method of coating on the substrate, spin coating is preferable, and the rotation speed is preferably 1000 to 3000 rpm.

  This composition is applied onto a substrate (eg, silicon / silicon dioxide coating, silicon nitride and chromium-deposited quartz substrate, etc.) used in the manufacture of precision integrated circuit elements using a spinner and a coater. Is done. Thereafter, this is dried to form an actinic ray-sensitive or radiation-sensitive film (hereinafter also referred to as a photosensitive film). In addition, a known antireflection film can be applied in advance.

  Next, the photosensitive film is irradiated with actinic rays or radiation, and preferably baked (usually 80 to 150 ° C., more preferably 90 to 130 ° C.), followed by development. By performing baking, a more favorable pattern can be obtained.

Examples of actinic rays or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. As these actinic rays or radiation, for example, those having a wavelength of 250 nm or less, particularly 220 nm or less are more preferable. Examples of such actinic rays or radiation include KrF excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157 nm), X-rays, and electron beams. Preferable actinic rays or radiations include, for example, KrF excimer laser, electron beam, X-ray and EUV light.

In the development process, an alkaline developer is usually used.
Examples of the alkaline developer include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia, primary amines such as ethylamine and n-propylamine, diethylamine and Secondary amines such as di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcohol amines such as dimethylethanolamine and triethanolamine, and fourth amines such as tetramethylammonium hydroxide and tetraethylammonium hydroxide. Examples include alkaline aqueous solutions containing a quaternary ammonium salt or cyclic amines such as pyrrole and pihelidine.

  An appropriate amount of alcohols and / or surfactant may be added to the alkaline developer.

  The concentration of the alkali developer is usually from 0.1 to 20% by mass. The pH of the alkali developer is usually from 10.0 to 15.0.

  For details of the process for producing an imprint mold using the composition according to the present invention, see, for example, Japanese Patent No. 4109085, Japanese Patent Application Laid-Open No. 2008-162101, and “Nanoimprint Basics and Technology Development”・ Application development-Nanoimprint substrate technology and latest technological development-Editing: Yoshihiko Hirai (Frontier Publishing)

  Hereinafter, the embodiments of the present invention will be described in more detail by way of examples, but the contents of the present invention are not limited thereto.

<Resin>
Resins P-1 to P-41 listed above were synthesized as follows.

[Synthesis Example 1: Resin P-14]
Resin P-14 was synthesized according to the following scheme.

<Synthesis of Compound (4)>
To 25.00 g of compound (1), 225 g of acetic anhydride and 105.09 g of pyridine were added and stirred at room temperature for 12 hours. This was cooled to 0 ° C. and distilled water was added to precipitate a solid. The solid was removed by filtration, 1000 mL of 1N hydrochloric acid was added, and the mixture was stirred at room temperature for 30 minutes. Thereafter, the obtained solid was removed by filtration. Distilled water (1000 mL) was added to the solid, stirred at room temperature for 30 minutes, and then filtered to take out the solid. The obtained solid was dissolved in ethyl acetate and dried using anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 25.00 g of compound (2).

  25.00 g of compound (2) was dissolved in 288 g of toluene. To the obtained solution, 22.08 g of N, N-dimethylformamide di-tert-butyl acetal was added dropwise at room temperature over 15 minutes. After stirring for 9 hours under heating and refluxing, filtration was performed. A 1N aqueous sodium hydroxide solution was added to the obtained filtrate. Extraction with ethyl acetate was carried out three times, and distilled water was added to the obtained organic layer for washing, followed by drying over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 9.5 g of compound (3). Obtained.

  9.5 g of compound (3) was dissolved in 85 g of methanol. To the obtained solution, 6.88 g of potassium carbonate was added and stirred at room temperature for 3 hours. The solid obtained by distilling off the solvent was dissolved in 85 g of acetone. To the obtained solution, 6.88 g of potassium carbonate and 6.08 g of chloromethylstyrene were added, and the mixture was stirred for 4 hours with heating under reflux. The reaction solution was filtered, and the solvent contained in the obtained filtrate was distilled off. Ethyl acetate was added thereto, and the organic layer was washed 3 times with distilled water, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained solid was washed with hexane three times and then filtered. The obtained solid was dried to obtain 5.82 g of compound (4).

<Synthesis of Compound (9)>
100.00 g of compound (5) was dissolved in 400 g of ethyl acetate. The resulting solution was cooled to 0 ° C., and 47.60 g of sodium methoxide (28% methanol solution) was added dropwise over 30 minutes. This was then stirred at room temperature for 5 hours. Ethyl acetate was added to the reaction solution, and the organic layer was washed 3 times with distilled water and then dried over anhydrous sodium sulfate, and the solvent was distilled off. In this way, 131.70 g of compound (6) (54% ethyl acetate solution) was obtained.

  56.00 g of ethyl acetate was added to 18.52 g of compound (6) (54% ethyl acetate solution). To this, 31.58 g of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride was added and cooled to 0 ° C. A solution prepared by dissolving 12.63 g of triethylamine in 25.00 g of ethyl acetate was added dropwise over 30 minutes, and the mixture was stirred for 4 hours while maintaining the liquid temperature at 0 ° C. Ethyl acetate was added, and the organic layer was washed 3 times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was evaporated. In this way, 32.90 g of Compound (7) was obtained.

  35.00 g of compound (7) was dissolved in 315 g of methanol, cooled to 0 ° C., 245 g of 1N aqueous sodium hydroxide solution was added, and the mixture was stirred at room temperature for 2 hours. After the solvent was distilled off, ethyl acetate was added, and the organic layer was washed 3 times with saturated brine and then dried over anhydrous sodium sulfate, and the solvent was distilled off. In this way, 34.46 g of Compound (8) was obtained.

  28.25 g of compound (8) was dissolved in 254.25 g of methanol, 23.34 g of triphenylsulfonium bromide was added, and the mixture was stirred at room temperature for 3 hours. The solvent was distilled off, distilled water was added, and the mixture was extracted 3 times with chloroform. The obtained organic layer was washed 3 times with distilled water, and then the solvent was distilled off. In this way, 42.07 g of Compound (9) was obtained.

<Synthesis of Resin (P-14)>
54.36 g of p-hydroxystyrene (53.1% propylene glycol monomethyl ether solution), 16.22 g of compound (4), 10.15 g of compound (9), 4.84 g of polymerization initiator V- 601 (manufactured by Wako Pure Chemical Industries, Ltd.) was dissolved in 77.53 g of propylene glycol monomethyl ether (PGME). 25.76 g of PGME was placed in the reaction vessel and dropped into the system at 85 ° C. over 4 hours under a nitrogen gas atmosphere. The reaction solution was heated and stirred for 2 hours, and then allowed to cool to room temperature.

  The reaction solution was diluted by adding 92 g of acetone. The diluted solution was dropped into 2800 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and filtered. The filtered solid was washed with 700 g of hexane / ethyl acetate = 8/2. The obtained solid was dissolved in 100 g of acetone and dropped into 1000 g of methanol / distilled water = 1/9 to precipitate the polymer, followed by filtration. The filtered solid was washed with 250 g of methanol / distilled water = 1/9. Thereafter, the washed solid was subjected to vacuum drying to obtain 16.56 g of Resin P-14.

  About this resin P-14, the weight average molecular weight (Mw) and dispersion degree (Mw / Mn) were measured using GPC (The Tosoh Corporation make; HLC-8120; Tsk gel Multipore HXL-M). The results are shown in Table 1 below. In this GPC measurement, THF was used as a solvent.

[Synthesis Example 2: Other resins]
Each of Resins P-1 to P-13 and P-15 to P-41 was synthesized in the same manner as described in Synthesis Example 1. These resins were evaluated in the same manner as described in Synthesis Example 1. The results are shown in Table 1 below.

Table 1 below summarizes the weight average molecular weight, composition ratio, and degree of dispersion of the resins P-1 to P-41.

For comparison, the following comparative compounds C-1 to C-3 were prepared.

<Photo acid generator>
As the photoacid generator, any of B-1 to B-120 mentioned above was used.

<Basic compound>
Any of the following N-1 to N-7 was used as the basic compound. N-7 corresponds to the compound (PA) described above.

[Synthesis Example 3: Compound N-7]
Compound N-7 was synthesized based on [0354] of JP-A-2006-330098.

<Surfactant>
Any of the following W-1 to W-4 was used as the surfactant.
W-1: Megafuck R08 (Dainippon Ink Chemical Co., Ltd .; fluorine and silicon)
W-2: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd .; silicon-based)
W-3: Troisol S-366 (manufactured by Troy Chemical Co .; fluorine type)
W-4: PF6320 (manufactured by OMNOVA; fluorine-based)
<Solvent>
As the solvent, any one of the following S-1 to S-4 was appropriately mixed and used.

S-1: PGMEA (bp = 146 ° C.)
S-2: PGME (bp = 120 ° C.)
S-3: Methyl lactate (bp = 145 ° C.)
S-4: Cyclohexanone (bp = 157 ° C.)
<Resist evaluation (EB)>
Each component shown in the following Table 2 was dissolved in the solvent shown in the same table to prepare a solution having a solid content concentration of 3.0% by mass. This solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a positive resist solution.

  The numerical value of “mass%” shown in Table 2 is a value based on the total solid content of the composition. In addition, the usage-amount of surfactant is 0.01 mass% with respect to the total solid content density | concentration.

  The positive resist solution was applied onto a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. This was heated and dried on a hot plate at 110 ° C. for 90 seconds to obtain a resist film having an average film thickness of 100 nm.

[Sensitivity, pattern shape, roughness characteristics, and isolated pattern resolution]
The resist film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd .; acceleration voltage 50 keV). Immediately after irradiation, it was heated on a hot plate at 130 ° C. for 90 seconds. Thereafter, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried. Thereby, a line and space pattern (line: space = 1: 1) or an isolated line pattern (line: space = 1:> 100) was formed.

(sensitivity)
First, the cross-sectional shape of the obtained line and space pattern was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). And the minimum irradiation energy at the time of resolving a line with a line width of 100 nm was calculated | required, and this value was made into "sensitivity ((micro | micron | mu) C / cm < ² >)."

(Pattern shape)
The cross-sectional shape of a 100 nm line pattern (line: space = 1: 1) at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). Then, the shape was evaluated in two stages of “rectangle” or “taper”.

(Roughness characteristics: Line edge roughness (LER))
The 100 nm line pattern (line: space = 1: 1) was observed using a scanning electron microscope (S-9260, manufactured by Hitachi, Ltd.). And the distance between the reference line which should have an edge and the actual edge was measured about 30 points | pieces equally spaced in the length direction 50 micrometers. And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. This 3σ was defined as “LER (nm)”.

(Resolution of isolated pattern; resolution)
The critical resolving power (minimum line width at which the line and space were separated and resolved) of the isolated pattern (line: space = 1:> 100) at the irradiation dose showing the above sensitivity was obtained. This value was defined as “resolution (nm)”.

[Etching resistance]
After a positive resist film having a thickness of 200 nm is formed on the wafer, a mixed gas of C ₄ F ₆ (20 mL / min) and O ₂ (40 mL / min) is used for 30 seconds at a temperature of 23 ° C. Plasma etching was performed throughout. Thereafter, the remaining film amount was determined, and the etching rate was calculated. And etching resistance was evaluated based on the following criteria.

(Criteria)
○ (Good): When the etching rate is less than 15 Å / sec. X (Insufficient): When the etching rate is 15 Å / sec or more These evaluation results are shown in Table 2 below.

  As shown in Table 2, the compositions of the examples were superior in all of sensitivity, pattern shape, LER, resolution of isolated patterns, and etching resistance as compared with the compositions of the comparative examples.

<Resist evaluation (EUV)>
Each component shown in the following Table 3 was dissolved in the solvent shown in the same table to prepare a solution having a solid content concentration of 3.0% by mass. This solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 μm to obtain a positive resist solution.

  The numerical value of “mass%” shown in Table 3 is a value based on the total solid content of the composition. In addition, the usage-amount of surfactant is 0.01 mass% with respect to the total solid content density | concentration.

  The positive resist solution was applied onto a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. This was heated and dried on a hot plate at 120 ° C. for 90 seconds to obtain a resist film having an average film thickness of 100 nm.

[Sensitivity, pattern shape and roughness characteristics]
The resist film was irradiated with EUV light using an EUV exposure apparatus. Immediately after irradiation, it was heated on a hot plate at 130 ° C. for 90 seconds. Thereafter, development was performed at 23 ° C. for 60 seconds using an aqueous tetramethylammonium hydroxide solution having a concentration of 2.38% by mass, rinsed with pure water for 30 seconds, and then dried. Thereby, a line and space pattern (line: space = 1: 1) was formed.

(sensitivity)
First, the cross-sectional shape of the obtained line and space pattern was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). And the minimum irradiation energy at the time of resolving a line with a line width of 100 nm was calculated | required, and this value was made into "sensitivity (mJ / cm < ² >)."

(Pattern shape)
The cross-sectional shape of a 100 nm line pattern (line: space = 1: 1) at the irradiation dose showing the above sensitivity was observed using a scanning electron microscope (S-4800, manufactured by Hitachi, Ltd.). Then, the shape was evaluated in two stages of “rectangle” or “taper”.

(Roughness characteristics: LER)
The 100 nm line pattern (line: space = 1: 1) was observed using a scanning electron microscope (S-9260, manufactured by Hitachi, Ltd.). And the distance between the reference line which should have an edge and the actual edge was measured about 30 points | pieces equally spaced in the length direction 50 micrometers. And the standard deviation of this distance was calculated | required and 3 (sigma) was computed. This 3σ was defined as “LER (nm)”.

These evaluation results are shown in Table 3 below.

  As shown in Table 3, the compositions of the examples were superior in all of sensitivity, pattern shape, and LER as compared with the compositions of the comparative examples.

Claims (12)

Actinic ray-sensitive or radiation-sensitive resin comprising a resin comprising a repeating unit (A) represented by the following general formula (I) and a repeating unit (B) that generates an acid upon irradiation with actinic rays or radiation Composition.

In formula (I),
R _a is a hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, An alkylcarbonyloxy group or an aralkyl group is represented.
Y _a represents a divalent linking group.
Ar represents a structural unit including a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or are connected to each other through a single bond.
Y _b represents a single bond or a divalent linking group.
A ₃ represents a group capable of leaving by the action of an acid.
S ₂ represents a substituent (excluding a hydrogen atom), and when r ≧ 2, the plurality of S ₂ may be the same as or different from each other.
p represents an integer of 1 to 5.
q represents the integer of 1-5.
r represents an integer of 0 to 4 that satisfies the relationship of p + r ≦ 5. The composition according to claim 1, wherein R _a is a hydrogen atom or a methyl group, p = 1, and q = 1. The composition according to claim 2, wherein the repeating unit (A) is represented by the following general formula (III).

In formula (III),
R _a represents a hydrogen atom or a methyl group.
Y _a represents a divalent linking group.
Ar represents a structural unit including a plurality of aromatic rings, and the plurality of aromatic rings are condensed to form a polycyclic structure or are connected to each other through a single bond.
Y _b represents a single bond or a divalent linking group.
A ₃ represents a group capable of leaving by the action of an acid.
S ₂ represents a substituent (excluding a hydrogen atom), and when r ≧ 2, the plurality of S ₂ may be the same as or different from each other.
r represents an integer of 0 to 4.   4. The composition of claim 3, wherein r = 0. The composition according to any one of claims 1 to 4, wherein Y _a represents -O-, -CH ₂ O-, -COO-, or -COOCH _2- . The composition according to claim 5, wherein Y _b represents a single bond, —CH ₂ O— or —COOCH ₂ —.   The composition according to any one of claims 1 to 6, wherein Ar represents a structural unit containing a naphthalene or anthracene ring, or a biphenyl or terphenyl structure. 8. The method according to claim 1, wherein at least a part of the repeating unit (B) is represented by at least one selected from the group consisting of the following general formulas (B1), (B2), and (B3). The composition as described.

Where
A represents a structural site that decomposes upon irradiation with actinic rays or radiation to generate an acid anion.
R ₀₄ , R ₀₅ and R _{07 to} R ₀₉ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, a halogen atom, a cyano group or an alkoxycarbonyl group.
R ₀₆ represents a cyano group, a carboxy group, —CO—OR ₂₅ or —CO—N (R ₂₆ ) (R ₂₇ ). R ₂₅ represents an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group. R ₂₆ and R ₂₇ may be bonded to each other to form a ring together with the nitrogen atom. R ₂₆ and R ₂₇ each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.
X _{1 to} X ₃ are each independently a single bond, an arylene group, an alkylene group, a cycloalkylene group, —O—, —SO ₂ —, —CO—, —N (R ₃₃ ) —, or a combination thereof. Represents a divalent linking group. R ₃₃ represents a hydrogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an aryl group or an aralkyl group.   The composition according to claim 8, wherein A is a structural moiety having a sulfonium salt structure or an iodonium salt structure.   The composition according to claim 8 or 9, wherein A is a structural site that is converted to an acid anion by irradiation with actinic rays or radiation. The composition according to any one of claims 1 to 10, wherein the resin further includes at least one of a repeating unit represented by the following general formula (A1) and a repeating unit represented by the general formula (A2). object.

In general formula (A1),
m represents an integer of 0 to 4.
n represents an integer of 1 to 5 that satisfies the relationship m + n ≦ 5.
S ₁ represents a substituent (excluding a hydrogen atom), and when m ≧ 2, the plurality of S ₁ may be the same as or different from each other.
A ₁ represents a hydrogen atom or a group capable of leaving by the action of an acid. When n ≧ 2, the plurality of A ₁ may be the same as or different from each other.
In general formula (A2),
X is hydrogen atom, alkyl group, hydroxyl group, alkoxy group, halogen atom, cyano group, nitro group, acyl group, acyloxy group, cycloalkyl group, cycloalkyloxy group, aryl group, carboxy group, alkyloxycarbonyl group, alkyl Represents a carbonyloxy group or an aralkyl group.
A ₂ represents a group capable of leaving by the action of an acid. Forming a film using the composition according to any one of claims 1 to 11,
Exposing the film;
Developing a pattern of the exposed film.