KR101299020B1 - Active ray-sensitive or radiation-sensitive resin composition and pattern forming method using the same - Google Patents

Abstract

[PROBLEMS] To provide an actinic ray-sensitive or radiation-sensitive resin composition having excellent performance and a pattern forming method using the same.
SOLUTION The actinic ray-sensitive or radiation-sensitive resin composition by this invention contains resin containing the repeating unit (A) represented by following General formula (I). In 1st Embodiment, the said composition contains the compound which generate | occur | produces an acid by irradiation of actinic light or a radiation. In 2nd Embodiment, the said resin further contains the repeating unit (B) which generate | occur | produces an acid by irradiation of actinic light or a radiation.

Description

ACTIVE RAY-SENSITIVE OR RADIATION-SENSITIVE RESIN COMPOSITION AND PATTERN FORMING METHOD USING THE SAME}

The present invention relates to a photoactive radiation-sensitive or radiation-sensitive resin composition, and a pattern forming method using the same. More specifically, the present invention is suitably used for the manufacturing process of ultra LSI and high capacity microchips, the mold making process for nanoimprinting and the manufacturing process of high density information recording medium, and the like, and are used suitably for other microfabrication processes. A composition, and a pattern formation method using the same.

In addition, "active light" or "radiation" means here the light spectrum of a mercury lamp, the ultraviolet-ray represented by an excimer laser, extreme ultraviolet (EUV), an X-ray, or an electron beam (EB), for example. In addition, in this invention, "light" means actinic light or radiation.

In addition, unless otherwise indicated here, "exposure" means not only light irradiation by a mercury lamp, far ultraviolet rays, X-rays, EUV light, etc., but also drawing by particle beams, such as an electron beam and an ion beam.

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

In recent years, thinning is required due to the requirement of forming an ultrafine pattern in a submicron region or a quarter micron region due to the high integration of integrated circuits. However, the current situation is that the fall of dry etching resistance has become a problem by thinning, and it cannot fully satisfy | fill.

In addition, in electron beam (EB) lithography, it can be seen that by increasing the acceleration voltage of EB, the influence of electron scattering in the resist film, that is, forward scattering, is reduced. Therefore, in recent years, the acceleration voltage of EB tends to increase. However, when the acceleration voltage of EB is increased, the electron energy capture rate of a resist film may fall and a sensitivity may fall.

As one of the methods of solving these problems, use of resin which has a naphthalene frame | skeleton is examined (for example, refer Japanese patent documents 1-3). By using resin which has a naphthalene skeleton, it becomes possible to improve dry etching resistance and a sensitivity, for example.

However, if the acceleration voltage of EB is increased, the influence of forward scattering, that is, back scattering, increases in the resist substrate instead of decreasing the influence of forward scattering. And when the isolation pattern with a large exposure area is formed, the influence of this backscattering is especially large. Therefore, if the acceleration voltage of EB is increased, for example, there is a possibility that the resolution of the isolation pattern is lowered.

In addition, the adhesion to the substrate decreases as the ultrafine pattern is formed, and the resolution of the isolation pattern is deteriorated, and the resolution improvement of the isolation pattern is desired, but cannot be sufficiently satisfied.

In addition, in particular, electron beam lithography is positioned as a next generation or next generation pattern forming technology, and a high sensitivity and high resolution positive resist is desired. In particular, high sensitivity is a very important issue for shortening wafer processing time. However, in the case of pursuing high sensitivity in an electron beam positive resist, a resist that satisfies these characteristics simultaneously due to deterioration of line edge roughness as well as a reduction in resolution is generated. Development is strongly hoped. Here, the line edge roughness means that the edges of the pattern and the substrate interface of the resist fluctuate irregularly in the direction perpendicular to the line direction due to the characteristics of the resist, so that the edges appear uneven when viewed from the top. This unevenness is transferred by an etching process using the resist as a mask, thereby deteriorating the electrical properties, thereby lowering the yield. In particular, line edge roughness has become a very important improvement subject in the ultrafine region of 0.25 micrometer or less. High sensitivity, good pattern shape, and good line edge roughness are in a trade-off relationship, and how to simultaneously satisfy this is very important.

In addition, in lithography using X-rays, EUV light, and the like, it is important to simultaneously satisfy high sensitivity, good pattern shape, good line edge roughness, resolution of the isolated pattern, and dry etching resistance, and these solutions. This is necessary.

However, the present situation is that the combination of the known techniques currently known cannot sufficiently satisfy high sensitivity, good pattern shape, good line edge roughness and dry etching resistance simultaneously in electron beam, X-ray or EUV light lithography.

Moreover, use of resin which has a photo-acid generator in a polymer main chain or a side chain is examined (for example, refer patent document 4-10 and nonpatent literature 1). However, in the examination in Japanese Patent Document 4, since it is a mixed system of a resin having a photoacid generator and a dissolution inhibiting compound in which solubility in an alkaline developer is increased by acid decomposition, a good pattern shape is caused due to nonuniform mixing of these materials. It was difficult to get roughness or line edge.

On the other hand, Japanese Patent Literatures 5 to 9 disclose resins having a photoacid generator and a group in which the solubility in an alkali developer is increased by acid decomposition in the same molecule, but are sufficient for sensitivity to electron beams, X-rays, or EUV light. It was hard to say.

In addition, Japanese Patent Document 10 and Non-Patent Document 1 describe ternary copolymers of hydroxystyrene, adamantyl group-containing acrylate, and photoacid generator-containing acrylate. Patent Document 11 discloses a resist containing a resin containing a repeating unit which is sensitive to high energy rays or heat and generates sulfonic acid at the fluorine-containing end of the side chain in order to improve high resolution, roughness dependency and exposure margin.

However, in the presently known combination of well-known techniques, it is the present situation that in the electron beam, X-ray, or EUV optical lithography, high sensitivity, high resolution, good pattern shape, good line edge roughness and the like cannot be sufficiently satisfied at the same time.

Japanese Patent Publication No. 2008-169346 International Publication No. 2007-046453 Japanese Patent Publication No. 2008-50568 Japanese Patent Laid-Open No. 9-325497 Japanese Patent Laid-Open No. 10-221852 Japanese Patent Publication No. 2006-178317 Japanese Patent Publication No. 2007-197718 International Publication No. 06/121096 Brochure US Patent Application Publication No. 2006/121390 US Patent Application Publication No. 2007/117043 Japanese Patent Publication No. 2008-133448

 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 having excellent performance and a pattern forming method using the same.

This invention is as follows, for example. In addition, the "weight average molecular weight" here means the polystyrene conversion value measured by gel permeation chromatography (GPC).

According to the first embodiment of the present invention, actinic ray-sensitive or radiation-sensitive with a resin containing a repeating unit represented by the following general formula (I) and a compound which generates an acid by irradiation with actinic light or radiation A resin composition is provided.

In formula (I),

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 carboxyl group, an alkyloxycarbonyl group, an alkylcarbon A carbonyloxy 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 leaving by the action of an acid.

S ₂ represents a substituent (excluding hydrogen atoms), and in the case of r ≧ 2, the plurality of S ₂ may be the same as or different from each other.

p represents the integer of 1-5.

q represents the integer of 1-5.

r represents the integer of 0-4 which satisfy | fills the relationship which becomes p + r <= 5.

According to 2nd Embodiment of this invention, persimmon containing resin with the repeating unit (A) represented by the said General formula (I), and the repeating unit (B) which generate | occur | produces an acid by irradiation of actinic light or radiation. An actinic ray- or radiation-sensitive resin composition is provided.

According to the 3rd Embodiment of this invention, the resist film formed using the composition which concerns on 1st or 2nd Embodiment is provided.

According to the fourth embodiment of the present invention, there is provided a pattern forming method comprising forming a film using the composition according to the first or second embodiment, exposing the film and developing the exposed film.

According to this invention, it becomes possible to provide the actinic-ray-sensitive or radiation-sensitive resin composition which has the outstanding performance, and the pattern formation method using the same.

Hereinafter, embodiments of the present invention will be described in detail.

In addition, group and atom group which do not specify a substitution or unsubstitution here shall include both the thing which does not have a substituent, and the thing which has a substituent. For example, the "alkyl group" which does not specify a substituted or unsubstituted shall include not only the alkyl group (unsubstituted alkyl group) which does not have a substituent but the alkyl group (substituted alkyl group) which has a substituent.

The composition by 1st Embodiment of this invention contains the resin containing the repeating unit (A) mentioned later, and the compound (henceforth a photoacid generator) which generate | occur | produces an acid by irradiation of actinic light or a radiation.

The composition by 2nd Embodiment of this invention contains resin containing both the repeating unit (A) and repeating unit (B) mentioned later.

[1] resins

The actinic ray-sensitive or radiation-sensitive resin composition according to the present invention contains a repeating unit (A) represented by the following general formula (I). The repeating unit (A) has a group (hereinafter also referred to as an acid-decomposable group) that decomposes under the action of an acid to generate an alkali-soluble group, as described later.

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

In formula (I), R _a 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, a carboxyl group, An alkyloxycarbonyl group, an alkylcarbonyloxy group, or an aralkyl group is shown.

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 leaving by the action of an acid.

S ₂ represents a substituent (excluding hydrogen atoms), and in the case of r ≧ 2, the plurality of S ₂ may be the same as or different from each other.

p represents the integer of 1-5.

q represents the integer of 1-5.

r represents the integer of 0-4 which satisfy | fills the relationship which becomes 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 carboxyl group, or an alkyloxy, as described above. A carbonyl group, an alkylcarbonyloxy group, or an aralkyl group is shown.

The alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

The linear alkyl group preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. As such a linear alkyl group, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-jade Tyl group, n-nonyl group, and n-decanyl group are mentioned.

The branched alkyl group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms. As such a branched alkyl group, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, i-hexyl group, t-hexyl group, i-heptyl group, t -Heptyl group, i-octyl group, t-octyl group, i-nonyl group and t-decanoyl group.

As the alkoxy group, one having 1 to 8 carbon atoms is preferable. As such an alkoxy group, a methoxy group, an ethoxy group, a propoxy group, butoxy group, a pentyloxy group, and a hexyloxy group are mentioned, for example.

Examples of the halogen atom include fluorine atom, chlorine atom, bromine atom and iodine atom. Especially, a fluorine atom is especially preferable.

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

As an acyloxy group, a C2-C8 thing is preferable. As such an acyloxy group, an acetoxy group, propionyloxy group, butyryloxy group, valeryloxy group, pivaloyloxy group, hexanoyloxy group, octanoyloxy group, and benzoyloxy group are mentioned, for example.

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

As monocyclic cycloalkyl group, a C3-C8 thing is preferable. As such a cycloalkyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group are mentioned, for example.

As a polycyclic cycloalkyl group, group which has a bicyclo, tricyclo, or tetracyclo structure is mentioned, for example. As a polycyclic cycloalkyl group, a C6-C20 thing is preferable. As such a cycloalkyl group, an adamantyl group, norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, (alpha)-pinenel group, tricyclo decanyl group, tetracyclo dodecyl group, and androstanyl group is mentioned, for example. .

As these cycloalkyl groups, what is represented by a following formula is mentioned, for example.

As an aryl group, a C6-C14 thing is preferable. As such an aryl group, a phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group, and anthryl group is mentioned, for example.

As the alkyloxycarbonyl group, one having 2 to 8 carbon atoms is preferable. As such an alkyloxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, and a propoxycarbonyl group are mentioned, for example.

As the alkylcarbonyloxy group, one having 2 to 8 carbon atoms is preferable. As such an alkylcarbonyloxy group, a methylcarbonyloxy group and an ethylcarbonyloxy group are mentioned, for example.

As the aralkyl group, one having 7 to 16 carbon atoms is preferable. As such an aralkyl group, a benzyl group is mentioned, for example.

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

As this substituent, it is a hydroxyl group, for example; Halogen atoms such as fluorine, chlorine, bromine and iodine atoms; A nitro group; Cyano; Amide group; Sulfonamide groups; Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group; Alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; Acyl groups such as formyl group, acetyl group and benzoyl group; Acyloxy groups, such as an acetoxy group and a butyloxy group, and a carboxyl group are mentioned.

Y _a represents a divalent linking group as described above.

By interposing Y _a between the benzene ring constituting the polystyrene skeleton and Ar, for example, the strength of the π-π interaction in the vicinity of the main chain can be weakened to reduce the hydrophobicity of the resin, thereby improving the developability of the composition. Become.

As this linking group, for example, 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-, -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, alkylsulfonyl group, -CH = CH-, -C And -C-, aminocarbonylamino groups, aminosulfonylamino groups, and combinations of two or more thereof. Here, R represents a monovalent substituent. These linking groups may further have a substituent.

In addition, when Y _<a> has an asymmetric structure, Ar may couple | bond with either side of the coupling group illustrated previously. 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- , particularly preferably -CH ₂ O-, -COO- or -COOCH _2- . By adopting such a configuration, it becomes possible to further improve the sensitivity.

The number of atoms (excluding hydrogen atoms) contained in Y _a is preferably 1 to 15, more preferably 1 to 10, still more preferably 1 to 8, and particularly preferably 2 to 8. When the number of atoms is excessively large, the distance between the main chain of the resin and the acid-decomposable group to be described later becomes excessively large, which may reduce the roughness characteristics of the composition. When the number of atoms is made excessively small, the flexibility of the side chain (flexibility) may decrease, and the sensitivity of the composition may decrease.

"The minimum number of connection atom" for Y is _a 1-10 individuals, and preferably, 1 to 5 individuals is more preferred, and 2-4 individuals, it is more preferable, and preferably two or three. When this "minimum connection atom number" is made too large, the distance between the principal chain of resin and the acid-decomposable group mentioned later may become large too much, and the roughness characteristic of a composition may fall. When this "minimum connection atom number" is made too small, the side chain flexibility (flexibility) may decrease, and the sensitivity of a composition etc. may fall.

In addition, the "minimum connection atom number" of Y _a is a number determined as follows. That is, first, the heat of the atom which connects the atom couple | bonded with the benzene ring couple | bonded with the main chain of resin directly with the atom couple | bonded with Ar among the atoms which comprise Y _a is considered. Next, the number of atoms contained in each of these columns is obtained. And the minimum of these atoms is called "minimum connection atom number" of Y _a .

For example, when Y _a is -O-, the minimum number of connecting atoms is one. When Y _a is —CH ₂ O—, the minimum number of linked atoms is two. If Y _a is -COO-, the minimum number of linked atoms is two. If Y _a is —COOCH ₂ —, the minimum number of linked atoms is three. When Y _a is a 2-methyl-butylene group, the minimum number of linked atoms is four. When Y _a is a 1,4-cyclohexylene group, the minimum number of linking atoms is four. In addition, Y is _a minimum number of connected atoms in the case of a straight-chain alkylene date, Y _a is equal to the number of carbon atoms.

Ar represents the structural unit containing a some aromatic ring as mentioned above. These plural aromatic rings may be condensed to form a polycyclic structure, or may be connected to each other via a single bond. In addition, 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 sensitivity due to improvement in dry etching resistance and increase in secondary electron generation amount can be achieved.

As an aromatic ring which Ar may contain, a benzene ring, a thiophene ring, a pyrrole ring, a furan ring, an imidazole ring, a pyridine ring, and a pyrazole ring are mentioned, for example. In addition, a "benzene ring" here means a ring which consists of six carbon atoms and contains the largest number of non-integrated double bonds (most conjugated double bonds) in a ring.

As a polycyclic structure which a plurality of aromatic rings can be condensed, for example, a naphthalene ring, anthracene ring, a phenanthrene ring, a pyrene ring, a triphenylene ring, a tetracene ring, a pentacene ring, a chrysene ring, a tetraphen ring, a pisene ring, Pentaphen ring, perylene ring, helisen ring, coronene ring, indole ring, benzimidazole ring, carbazole ring and phenothiazine ring. Among these, indole ring, pyrene ring, phenanthrene ring, anthracene ring and naphthalene ring are more preferable, and anthracene ring and naphthalene ring are especially preferable.

As a structure in which several aromatic rings were mutually connected through a single bond, a biphenyl structure, a terphenyl structure, and a viologen structure are mentioned, for example. Especially, a biphenyl structure and a terphenyl structure are especially preferable.

The number of aromatic rings contained in Ar becomes like this. Preferably it is 2-5 pieces, More preferably, it is 2-4 pieces, Most preferably, they are two or three pieces. When the number of aromatic rings is excessively large, the hydrophobicity of the resin may be excessively high, and the dropability of the pattern may decrease, which may affect the deterioration of the pattern shape. In addition, "the number of aromatic rings" here is the number of a benzene ring or the monocyclic heteroaryl ring corresponding to this. For example, it is two of naphthalene residues, biphenyl residues and bipyridine residues, and three of anthracene residues, carbazole residues and phenothiazine residues.

Further, the ring direction contained in the Ar - (Y _b COOA ₃₎ may be further have a substituent other than _q. As this substituent, it is a hydroxyl group, for example; Halogen atoms such as fluorine, chlorine, bromine and iodine atoms; A nitro group; Cyano; Amide group; Sulfonamide groups; Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group; Alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; Acyl groups such as formyl group, acetyl group and benzoyl group; Acyloxy groups, such as an acetoxy group and a butyloxy group, and a carboxyl group are mentioned.

Y _b represents a single bond or a divalent linking group as described above. As this bivalent coupling group, the coupling group similar to what was demonstrated previously about Y _<a> is mentioned, for example.

Y _b is preferably a single bond, -CH ₂ O- or -COOCH _2- . The number of atoms (excluding hydrogen atoms) contained in Y _b is preferably 0 to 15, more preferably 0 to 10, and still more preferably 0 to 8. When the number of atoms is excessively large, the distance between the main chain of the resin and the acid-decomposable group to be described later becomes excessively large, which may reduce the roughness characteristics of the composition.

It is preferable that "minimum connection atom number" of Y _b is 0-10, It is more preferable that it is 0-5, It is still more preferable that it is 0-3. When this "minimum connection atom number" is made too large, the distance between the principal chain of resin and the acid-decomposable group mentioned later may become large too much, and the roughness characteristic of a composition may fall. In addition, Y _b of the "minimum number of connections atom" is a number which is determined by the same manner as that described with respect to _a Y.

A ₃ is a group which is released by the action of an acid as described above.

When an acid is made to react with resin containing the repeating unit represented by General formula (I), at least one part of A <_3> will leave and a carboxyl group which is an alkali-soluble group will be produced | generated. That is, this repeating unit has a group represented by "-COOA ₃ " as an acid-decomposable group.

It is preferable that A <_3> is a hydrocarbon group. The hydrocarbon group preferably has 1 to 30 carbon atoms, and more preferably 4 to 25 carbon atoms. 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 alkyl group substituted by an alicyclic group or an alicyclic group).

The alicyclic structure may be monocyclic or polycyclic. Specifically, a monocyclo, bicyclo, tricyclo, tetracyclo structure, etc. are mentioned as this alicyclic structure. Carbon number of this alicyclic structure is typically 5 or more, Preferably it is 6-30, Especially preferably, it is 7-25. In addition, the hydrocarbon group containing an alicyclic structure may further have a substituent.

Specific examples of the alicyclic structure may be mentioned first as described for the cycloalkyl group of R _a.

As a preferable alicyclic structure, an adamantyl group, a noadamantyl group, a decalin residue, a tricyclo decanyl group, a tetracyclo dodecanyl group, a norbornyl group, a cedrol group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, Cyclodecanyl group and cyclododecanyl group are mentioned. 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 mentioned. In addition, an alicyclic structure is described here as a monovalent alicyclic group.

As a substituent which these alicyclic structures can have, an alkyl group, a halogen atom, a hydroxyl group, an alkoxy group, a carboxyl group, and an alkoxycarbonyl group are mentioned, for example.

As the alkyl group, lower alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group and butyl group are preferable, and methyl group, ethyl group, propyl group and isopropyl group are more preferable.

As an alkoxy group, C1-C4 alkyl groups, such as a methoxy group, an ethoxy group, a propoxy group, and 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.

It is especially preferable that A <_3> is group represented by either of the following general formula (pI)-general formula (pV).

In general formula (pI)-(pV),

R ₁₁ represents a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group or sec-butyl group, and Z represents an atomic group necessary for forming a cycloalkyl group together with carbon atoms.

R <_12> -R <_16> represents a C1-C4 linear or branched alkyl group or a cycloalkyl group each independently. Provided that at least one of R ₁₂ to R ₁₄ represents a cycloalkyl group. Any one of R ₁₅ and R ₁₆ represents a cycloalkyl group.

R ₁₇ to R ₂₁ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. Provided that at least one of R ₁₇ to R ₂₁ represents a cycloalkyl group. In addition, any one of R <_19> and R <_21> represents a C1-C4 linear or branched alkyl group or a cycloalkyl group.

R ₂₂ to R ₂₅ each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 4 carbon atoms, or a cycloalkyl group. Provided that at least one of R ₂₂ to R ₂₅ represents a cycloalkyl group. In addition, R ₂₃ and R ₂₄ may be bonded to each other to form a ring.

As an alkyl group of R <_12> -R <_25> , a methyl group, an ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, and t-butyl group are mentioned, for example.

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 (fluorine atom, chlorine atom, bromine atom, iodine atom), acyl group, acyloxy group, cyano group, hydroxyl group, carboxyl group, alkoxycarbonyl group, and the like. Nitro group is mentioned.

Examples of the cycloalkyl group formed by Z and the carbon atom and the cycloalkyl group of R ₁₂ to R ₂₅ include the same as those described above for the cycloalkyl group of R _a .

Specific examples of A ₃ include the following groups.

S ₂ independently represents a substituent (excluding hydrogen atoms) when r ≧ ₂ . Types of substituents represented by S ₂ is not particularly limited. Examples of the substituent include an alkyl group, a cycloalkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, an aralkyl group, an aralkyloxy group, a hydroxyl group, a halogen atom, a cyano group, a nitro group, and a sulfonate. A vinyl group, an alkylthio group, an arylthio group, and an aralkylthio group are mentioned.

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

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

As an aralkyl group, a benzyl group is mentioned, for example.

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, thiophenecar Heterocyclic residues, such as a carbonyloxy group, a thiophenmethyl carbonyloxy group, and a pyrrolidone residue, are mentioned. Carbon number of this substituent becomes like this. Preferably it is 12 or less.

As an alkyl group, a cycloalkyl group, an aryl group, and an aralkyl group which have a substituent, for example, a cyclohexylethyl group, an alkylcarbonyloxymethyl group, an alkylcarbonyloxyethyl group, a cycloalkylcarbonyloxymethyl group, a cycloalkylcarbonyloxyethyl group, an arylcarbon Bonyloxyethyl 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, cycloalkylthioethyl group, arylthioethyl group and aralkylthioethyl group.

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

An example of the aralkylcarbonyloxyethyl group is a benzylcarbonyloxyethyl group. These groups may further have a substituent.

p is an integer of 1-5 as mentioned above. p is preferably 1 or 2, and particularly preferably 1.

q is an integer of 1-5 as mentioned above. q is preferably 1 or 2, and particularly preferably 1.

r is an integer of 1-4 which satisfy | fills the relationship which becomes p + r <= 5 as mentioned above. r is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

In the repeating unit (A), R _a is a hydrogen atom or a methyl group, preferably p = 1 and q = 1. That is, it is preferable that the repeating unit (A) 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 meanings as those described for general formula (I). r represents the integer of 0-4.

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 the group represented by "-Y _a -Ar-Y _b -COOA ₃ " is located in the para position of the benzene ring directly bonded to the main chain. It is preferable that it is substituted. That is, it is preferable that the repeating unit (A) 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 meanings as those described for general formula (I). r represents the integer of 0-4.

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

Although the specific example of a repeating unit (A) is shown below, the scope of the present invention is not limited to these.

The composition according to the present invention may be provided with a repeating unit (B) which generates an acid by irradiation of actinic light or radiation as described above.

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 is decomposed by actinic radiation or radiation to generate an acid anion.

R ₀₄ , R ₀₅ and R ₀₇ to R ₀₉ each independently represent 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 carboxyl 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 a nitrogen atom. R ₂₆ and R ₂₇ each independently represent 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 of a plurality thereof; Shows a coupling 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 an alkyl group of R <_04> , R <_05> and R <_07> -R ₀₉ , it is preferable that carbon number is 20 or less, and it is more preferable that carbon number is 8 or less. As such an alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group are mentioned, for example. In addition, these alkyl groups may further have a substituent.

The cycloalkyl group of R ₀₄ , R ₀₅ and R ₀₇ to R ₀₉ may be monocyclic or polycyclic. As this cycloalkyl group, C3-C8 is preferable. As such a cycloalkyl group, a cyclopropyl group, a cyclopentyl group, and a cyclohexyl group are mentioned, for example.

_Examples of the halogen atoms of R ₀₄ , R ₀₅ and R ₀₇ to R ₀₉ include fluorine, chlorine, bromine and iodine atoms. Of these, fluorine atoms are particularly preferred.

R _04, the alkyl group contained in the alkoxycarbonyl group of R ₀₅ and R ₀₇ ~ R _09, for example, it is preferable that the first listed as an alkyl group of R _04, R ₀₅ and R ₀₇ ~ R _09.

As an alkyl group of R <_25> -R <_27> and R <_33> , what was enumerated as the alkyl group of R <_04> , R <_05> and R <_07> -R ₀₉ , for example is preferable.

As the cycloalkyl group of R ₂₅ ~ R ₂₇ and R _33, for example, it is preferable that the first listed as the cycloalkyl group of R _04, R ₀₅ and R ₀₇ ~ R _09.

As an alkenyl group of R <_25> -R <_27> and R <_33> , a C2-C6 thing is preferable. As such an alkenyl group, a vinyl group, a propenyl group, an allyl group, butenyl group, a pentenyl group, and a hexenyl group are mentioned, for example.

As a cycloalkenyl group of R <_25> -R <_27> and R <_33> , a C3-C6 thing is preferable. The cycloalkenyl group includes, for example, 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. Further, aryl groups may be bonded to each other to form a heterocycle. As an aryl group of R <_25> -R <_27> and R <_33> , a phenyl group, a tolyl group, a chlorophenyl group, a methoxyphenyl group, and a naphthyl group are mentioned, for example.

As the aralkyl group of R ₂₅ to R ₂₇ and R ₃₃ , one having 7 to 15 carbon atoms is preferable. This aralkyl group may further have a substituent. As an aralkyl group of R <_25> -R <_27> and R <_33> , a benzyl group, a phenethyl group, and a cumyl group are mentioned, for example.

As a ring which R <_26> and R <_27> combine with each other and form together with a nitrogen atom, a 5-8 membered ring is preferable, Specifically, a pyrrolidine, a piperidine, and a piperazine are mentioned, for example.

As the arylene group of X ₁ to X ₃ , _one having 6 to 14 carbon atoms is preferable. As such arylene group, a phenylene group, a tolylene group, and a naphthylene group are mentioned, for example. These arylene groups may further have a substituent.

As an alkylene group of X <_1> -X <_3> , a C1-C8 thing is preferable. As such an alkylene group, a methylene group, an ethylene group, a propylene group, butylene group, hexylene group, and octylene group is mentioned, for example. These alkylene groups may further have a substituent.

As a cycloalkylene group, a C5-C8 thing is preferable. As such a cycloalkylene group, a cyclopentylene group and a cyclohexylene group are mentioned, for example. These cycloalkylene groups may further have a substituent.

As a preferable substituent which each group in said general formula (B1)-(B3) can have, it is a hydroxyl group, for example; Halogen atoms (fluorine, chlorine, bromine, iodine); A nitro group; Cyano; Amide group; Sulfonamide groups; Alkyl groups listed first as R ₀₄ , R ₀₅ and R ₀₇ to R ₀₉ ; An alkoxy group such as a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, a hydroxypropoxy group, and a butoxy group; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; Acyl groups such as formyl group, acetyl group and benzoyl group; Acyloxy groups, such as an acetoxy group and a butyloxy group, and a carboxyl group are mentioned. These substituents preferably have 8 or less carbon atoms.

A represents a structural site that is decomposed by irradiation of actinic radiation or radiation to generate an acid, and specifically, a photoinitiator for photocationic polymerization, a photoinitiator for photoradical polymerization, a photochromic agent for pigments, a photochromic agent, a microresist, and the like. The structural site which the compound which produces | generates an acid by the well-known light used is mentioned.

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

In general formula (ZI),

R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group.

_{Carbon number} of the organic group as R <_201> , R <_202> and R <_203> is 1-30 normally, Preferably it is 1-20. In addition, two of R ₂₀₁ to R _{203 may be} bonded to each other to form a ring structure, and the ring may include an oxygen atom, a sulfur atom, an ester bond, an amide bond, and a carbonyl group. As group which two of R <_201> -R <_203> combine and form, alkylene groups, such as a butylene group and a pentylene group, are mentioned, for example.

Z <^-> represents the acid anion which arises by decomposing | disassembled by irradiation of actinic light or a radiation. Z ^- is preferably an unconjugated anion. As a non-nucleophilic anion, a sulfonic acid anion, a carboxylic acid anion, a sulfonyl imide anion, a bis (alkylsulfonyl) imide anion, and a tris (alkylsulfonyl) methyl anion are mentioned, for example.

In addition, non-nucleophilic anion means the anion which is remarkably low in the ability to produce nucleophilic reaction. Use of non-nucleophilic anions can suppress degradation over time due to intramolecular nucleophilic reactions. Thereby, it becomes possible to improve stability with time of resin and a composition.

As an organic group of R <_201> , R <_202> and R <_203> , the corresponding group in group represented by (ZI-1), (ZI-2), (ZI-3) mentioned later is mentioned, for example.

As group represented by more preferable (ZI), the (ZI-1) group, the (ZI-2) group, the (ZI-3) group, and the (ZI-4) group demonstrated below are mentioned.

The (ZI-1) group is a group in which at least one of R ₂₀₁ to R ₂₀₃ in General Formula (ZI) is an arylsulfonium whose aryl group is a cation.

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

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

As an aryl group in arylsulfonium, a phenyl group or a naphthyl group is preferable, and a phenyl group is more preferable. The aryl group may have a heterocyclic structure containing hetero atoms such as oxygen atom, nitrogen atom and sulfur atom. Examples of the heterocyclic structure include pyrrole, furan, thiophene, indole, benzofuran and benzothiophene. When the 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 needed has a C1-C15 linear or branched alkyl group, or a C3-C15 cycloalkyl group is preferable. As such an alkyl group or a cycloalkyl group, a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, t-butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclohexyl group are mentioned, for example.

The aryl group, alkyl group or cycloalkyl group of R ₂₀₁ to R ₂₀₃ is an alkyl group (for example, having 1 to 15 carbon atoms), a cycloalkyl group (for example, having 3 to 15 carbon atoms), an aryl group (for example, having 6 to 14 carbon atoms) ), An alkoxy group (for example, 1 to 15 carbon atoms), a halogen atom, a hydroxyl group or a phenylthio group may be used as a substituent.

As a preferable substituent, a C1-C12 linear or branched alkyl group, a C3-C12 cycloalkyl group, and a C1-C12 linear, branched or cyclic alkoxy group are mentioned, for example. As a more preferable substituent, a C1-C4 alkyl group and a C1-C4 alkoxy group are mentioned, for example. The substituent may be substituted on any one of three R ₂₀₁ to R ₂₀₃ , and may be substituted on two or more of these. When R ₂₀₁ to R ₂₀₃ are phenyl groups, 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 General Formula (ZI) each independently represent an organic group containing no aromatic ring. Here, the aromatic ring also includes a heterocycle including a hetero atom.

The organic group which does not contain an aromatic ring as R ₂₀₁ to R ₂₀₃ generally has 1 to 30 carbon atoms, and preferably 1 to 20 carbon atoms.

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 straight or branched 2-oxoalkyl group, 2-oxocycloalkyl group or an alkoxycarbonylmethyl group, More preferably, they are a linear or branched 2-oxoalkyl group.

The alkyl group and the cycloalkyl group of R ₂₀₁ to R ₂₀₃ are preferably a linear or branched alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group or pentyl group), and cycloalkyl group having 3 to 10 carbon atoms. (For example, a cyclopentyl group, a cyclohexyl group, or norbornyl group) is mentioned. As this alkyl group, More preferably, a 2-oxoalkyl group and the alkoxycarbonylmethyl group are mentioned. As a cycloalkyl group, More preferably, a 2-oxocycloalkyl group is mentioned.

The 2-oxoalkyl group may be linear or branched. As 2-oxoalkyl group, Preferably, the group which has> C = O at the 2 position of the said alkyl group is mentioned. As a 2-oxocycloalkyl group, Preferably, the group which has> C = O at the 2-position of the said cycloalkyl group is mentioned.

As an alkoxy group in an alkoxycarbonylmethyl group, Preferably, a C1-C5 alkoxy group (for example, a methoxy group, an ethoxy group, a propoxy group, butoxy group, or a pentoxy group) is mentioned.

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

Next, the (ZI-3) group will be described.

(ZI-3) group is group represented by the following general formula (ZI-3), and is group which has 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 represent a hydrogen atom, an alkyl group or a cycloalkyl group.

R _x and R _y each independently represent 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. As a group which these couple | bond together and form, a butylene group and a pentylene group are mentioned, for example.

Zc <^-> represents a non-nucleophilic anion, For example, the same thing as Z <^-> in general formula (ZI) is mentioned.

As a specific structure of the cation part of general formula (ZI-3), cation of the acid generator illustrated by Paragraph 0047 and 0048 of Unexamined-Japanese-Patent No. 2004-233661, and Paragraph 0040-0046 of Unexamined-Japanese-Patent No. 2003-35948 See negative structure.

Next, the (ZI-4) group will be described.

(ZI-4) group is 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 represent a hydrogen atom or a substituent. At least one of R ¹ to R ¹³ is preferably a substituent containing an alcoholic hydroxyl group. In addition, an "alcoholic hydroxyl group" means the hydroxyl group couple | bonded with the carbon atom of an alkyl group here.

Z is a single bond or a divalent linking group.

Zc <^-> represents a non-nucleophilic anion, For example, the same thing as Z <^-> in general formula (ZI) is mentioned.

When R <^1> -R <^13> is a substituent containing an alcoholic hydroxyl group, it is preferable that R <^1> -R <^13> is group represented by-(WY). Wherein Y is an alkyl group substituted with a hydroxyl group and W is a single bond or a divalent linking group.

Preferred examples of the alkyl group represented by Y include ethyl group, propyl group and 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 is preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and an arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, an alkoxycarbonyl group or It is a divalent group which substituted arbitrary hydrogen atoms in a carbamoyl group by a single bond, More preferably, any hydrogen atom in a single bond, an acyloxy group, an alkylsulfonyl group, an acyl group, or an alkoxycarbonyl group is single. It is a bivalent group substituted by the bond.

R ¹ - R ¹³ is an alcoholic when the substituent containing a hydroxyl group, the number of carbon atoms contained is preferably from 2 to 10, more preferably 2 to a 6, particularly preferably from two to four.

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

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

When R ¹ to R ¹³ do not contain an alcoholic hydroxyl group, examples of the substituent for R ¹ to R ¹³ include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, Heterocyclic group, cyano group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (Including an anilino group), ammonia group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, aryl Thio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocycle 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 ], phosphate group [ -OPO (OH) ₂ ], a sulfate group (-OSO ₃ H), and other well-known substituents are mentioned.

When R ¹ to R ¹³ do not contain an alcoholic hydroxyl group, R ¹ to R ¹³ preferably represent 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, carboxyl 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 , Aminocarbonylamino group, alkoxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl and arylsulfonyl group, alkoxycarbonyl group or 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 nonaromatic hydrocarbon rings and heterocycles. These ring structures may further be 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 includes an alcoholic hydroxyl group, and more preferably at least one of R ⁹ to R ¹³ is an alcoholic hydroxyl group. It has a structure to include.

Z represents a single bond or a divalent linking group as described above. As this bivalent coupling group, an alkylene group, arylene group, carbonyl group, sulfonyl group, carbonyloxy group, carbonylamino group, sulfonylamide group, ether group, thioether group, amino group, disulfide group, acyl group, Alkylsulfonyl group, -CH = CH-, an aminocarbonylamino group, and an aminosulfonylamino group are mentioned.

This divalent linking group may have a substituent. As these substituents, the thing similar to what was enumerated about R <^1> -R <^13> first is mentioned, for example.

Z is preferably a bond or group having no electron withdrawing properties such as a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, -CH = CH-, an aminocarbonylamino group and an aminosulfonylamino group More preferably, they are a single bond, an ether group, or a thioether group, Especially preferably, they are a single bond.

Next, general formula (ZII) will be described.

In General Formula (ZII), R ₂₀₄ to R ₂₀₅ each independently represent an aryl group, an alkyl group, or a cycloalkyl group.

Specific examples, preferred forms, and the like of the aryl group, alkyl group, and cycloalkyl group of R ₂₀₄ to R ₂₀₇ are the same as those described for R ₂₀₁ to R ₂₀₃ in the compound (ZI-1) described above.

The aryl group, alkyl group and cycloalkyl group represented by R ₂₀₄ to R ₂₀₇ may have a substituent. As this substituent, the same thing as what was demonstrated about R <_201> -R <_203> in the above-mentioned compound (ZI-1) is mentioned.

Z <^-> represents the acid anion which decomposes | disassembles by irradiation of actinic light or a radiation, A non-nucleophilic anion is preferable, For example, the same thing as Z <^-> in general formula (ZI) is mentioned.

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

In the formula (ZCI),

R ₃₀₁ and R ₃₀₂ each independently represent an organic group. Carbon number of this organic group is 1-30 normally, Preferably it is 1-20. 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 which R ₃₀₁ and R ₃₀₂ may combine with each other to form include an alkylene group such as a butylene group and a pentylene group.

As an organic group of R <_301> and R <_302> , the aryl group, alkyl group, and cycloalkyl group listed as an example of R <_201> -R <_203> in general formula (ZI) are mentioned, for example.

M represents the atomic group which forms an acid by the addition of protons. More specifically, the structure represented by either of general formula AN1-AN3 mentioned later is mentioned. Among these, the structure represented by general formula AN1 is especially preferable.

R ₃₀₃ represents an organic group. The carbon number of the organic group as R ₃₀₃ is generally 1-30, preferably 1-20. Specifically as an organic group of R <_303> , the aryl group, alkyl group, cycloalkyl group, etc. which were listed as specific examples of R <_204> , R <_{205> in} the said general formula (ZII) are mentioned, for example.

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 photo-acid generator has is mentioned, for example. As this photo-acid generator, the compound of the following (1)-(3) is mentioned, for example.

(1) M. TUNOOKA et al., Polymer Preprints Japan, 35 (8); G. Berner et al., J. Rad. Curing, 13 (4); W. J. Mijs et al., Coating Technol., 55 (697), 45 (1983); H. Adachi et al., Polymer Preprints, Japan, 37 (3); European Patent Nos. 0199,672, 84515, 199,672, 044,115, 0101,122, U.S. Patents 618,564, 4,371,605, 4,431,774, and Japanese Patent Application Publication No. 64-18143. And a compound which is photodegraded to generate sulfonic acid, such as iminosulfonate described in each publication such as Japanese Patent Application Laid-Open No. Hei 2-245756 and Japanese Patent Application Laid-Open No. Hei 4-365048.

(2) The disulfone compound described in Japanese Patent Application Laid-open No. 61-166544.

(3) V. N. R. Pillai, Synthesis, (1), 1 (1980); A. Abad et al, Tetrahedron Lett., (47) 4555 (1971); D. H. R. Barton et al., J. Chem. Soc., (C), 329 (1970); US Patent No. 3,779,778; And compounds which generate acids by light described in European Patent No. 126,712 and the like.

It is preferable that the repeating unit (B) has a structural site which is converted into an acid anion by irradiation with actinic light or radiation. For example, it is preferable that A in the said general formula (B1)-(B3) is a structural site converted into an acid anion by irradiation of actinic light or a radiation.

That is, the repeating unit (B) is more preferably a structure in which acid anions are generated in the side chain of the resin by irradiation with actinic light or radiation. By adopting such a structure, diffusion of generated acid anions can be suppressed, and the resolution, roughness characteristics and the like can be further improved.

Each region -X ₃ -A in the formula (B1) site -X ₁ -A, formula (B2) site -X ₂ -A, and the general formula (B3) in the in the following general It is preferable that it is represented by any one of formula (L1), (L2), and (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 is a hydrogen atom or an alkyl group), a divalent nitrogen-containing nonaromatic heterocyclic group, or a combination thereof.

The alkyl group of R may be linear or branched. In addition, 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 even more preferably 3 or less carbon atoms. As such an alkyl group, a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group, and dodecyl group are mentioned, for example. As R, a hydrogen atom, a methyl group or an ethyl group is particularly preferable.

In addition, a bivalent nitrogen-containing non-aromatic heterocyclic group means preferably a 3-8 membered non-aromatic heterocyclic group which has at least 1 nitrogen atom.

X ₁₁ is more preferably -O-, -CO-, -NR- (R is a hydrogen atom or an alkyl group) or a combination thereof, particularly preferably -COO- or -CONR- (R is a hydrogen atom or an alkyl group). desirable.

L ₁₁ represents an alkylene group, an alkenylene group, a divalent aliphatic hydrocarbon ring group or a group in which two or more thereof are combined. In the above combined group, two or more groups to be combined may be the same as or different from each other. In addition, these groups include -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing nonaromatic heterocyclic group, a divalent aromatic ring group or a combination thereof. It may be connected via a flag.

The alkylene group of L ₁₁ may be linear or branched. The alkylene group preferably has 1 to 8 carbon atoms, more preferably 1 to 6 carbon atoms, and even more preferably 1 to 4 carbon atoms.

As an alkenylene group of L <_11>, the group provided with the double bond in arbitrary positions of the said alkylene group is mentioned, for example.

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. It is preferable that this aromatic ring group has 6-14 carbon atoms. This aromatic ring group may further have a substituent.

In addition, non-aromatic heterocyclic group containing 2 -NR- and bivalent linking group is nitrogen as, for example, as each of the above-described X _11.

L _{11 is an} alkylene group, a divalent aliphatic hydrocarbon ring group or a group in which an alkylene group and a divalent aliphatic hydrocarbon ring group are combined via -OCO-, -O- or -CONH-FMF (for example, -alkylene group-O-alkylene group). -, -Alkylene group-OCO-alkylene group- or -divalent aliphatic hydrocarbon ring group-O-alkylene group-, -alkylene group-CONH-alkylene group-) are particularly preferable.

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

As X _{12, a} single bond, -S-, -O-, -CO-, -SO ₂ -or a combination thereof is more preferable, and a single bond, -S-, -OCO- or -OSO ₂ -is particularly preferable. .

Examples of _{X 13 -O-, -CO-, -SO 2} - group or a combination thereof and more preferably, -OSO ₂ - is particularly preferred.

Ar ₁ represents a divalent aromatic ring. The divalent aromatic ring group may be an arylene group or a heteroarylene group. This divalent aromatic ring group may further have a substituent. As this substituent, an alkyl group, an alkoxy group, and an aryl group are mentioned, for example.

As Ar _1, an aralkylene group having a C 6-18 arylene group which may have a substituent or a C 6-18 arylene group and a C 1-4 alkylene is more preferable, and a phenylene group, a naphthylene group, or a biphenyl Particular preference is given to phenylene groups substituted with ylene groups or phenyl groups.

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 thereof, and some or all of the hydrogen atoms of the group are a fluorine atom, an fluorinated alkyl group, a nitro group, And a substituent selected from a cyano group. In the above combined group, two or more groups to be combined may be the same as or different from each other. In addition, these groups include -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing nonaromatic heterocyclic group, a divalent aromatic ring group or a combination thereof. It may be connected via a flag.

As L ₁₂ , an alkylene group in which part or all of hydrogen atoms are substituted with fluorine atoms or fluorinated alkyl groups (more preferably perfluoroalkyl groups), divalent aromatic ring groups, or a combination thereof is more preferable, and part or all of hydrogen atoms is more preferable. The alkylene group or bivalent aromatic ring group substituted with the fluorine atom is especially preferable. As L _12, an alkylene group or a divalent aromatic ring group in which 30 to 100% of the number of hydrogen atoms is substituted with a fluorine atom is particularly preferable.

The alkylene group of 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.

As an alkenylene group of L <_12>, the group provided with the double bond in arbitrary positions of the said alkylene group is mentioned, for example.

The divalent aliphatic hydrocarbon ring group of L ₁₂ may be monocyclic or polycyclic. As this bivalent aliphatic hydrocarbon ring group, a C3-C17 thing is preferable.

As a bivalent aromatic ring group of L <_12> , the same thing as what was demonstrated previously as a coupling group in L <_11> is mentioned, for example.

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

Z <_1> shows the site | part which becomes a sulfonic acid group by irradiation of actinic light or a radiation, Specifically, the structure represented by said formula (ZI) is mentioned, for example.

Next, the site | part represented by general formula (L2) is demonstrated.

Ar ₂ represents a bivalent aromatic ring. The divalent aromatic ring group may be an arylene group or a heteroarylene group. It is preferable that these divalent aromatic ring groups have 6-18 carbon atoms. These divalent aromatic ring groups may further have a substituent.

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

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

X ₂₁ as _{-O-, -S-, -CO-, -SO 2} - or a combination thereof, and more preferred groups, -O-, -OCO- or -OSO ₂ - is particularly preferred.

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

X ₂₂ as _{-O-, -S-, -CO-, -SO 2} - or a combination thereof, and more preferred groups, -O-, -OCO- or -OSO ₂ - is particularly preferred.

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 above combined group, two or more groups to be combined may be the same as or different from each other. In addition, these groups include -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing nonaromatic heterocyclic group, a divalent aromatic ring group or a combination thereof. It may be connected via a flag.

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

The divalent aromatic ring group of L ₂₁ may be an arylene group or a heteroarylene group. It is preferable that this bivalent aromatic ring group has 6-14 carbon atoms.

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

L _{21 is 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 them (for example, an -alkylene group-divalent aromatic ring group- or -divalent aliphatic hydrocarbon ring group). -Alkylene group-) or a group in which two or more of these are combined via a linking group such as -OCO-, -COO-, -O- and -S- (for example, an aromatic ring group of -alkylene group-OCO-2) -, -Alkylene group-S-2valent aromatic ring group- or -alkylene group-O-alkylene group-2valent aromatic ring group-) is 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 thereof, and some or all of the hydrogen atoms of the group are a fluorine atom, an fluorinated alkyl group, a nitro group, And a substituent selected from a cyano group. In the above combined group, two or more groups to be combined may be the same as or different from each other. In addition, these groups include -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing nonaromatic heterocyclic group, a divalent aromatic ring group or a combination thereof. It may be connected via a flag.

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

Specific examples of the alkylene group represented by L ₂₂ , the alkenylene group, the aliphatic hydrocarbon ring group, the divalent aromatic ring group, and the group in which two or more of them are combined include the specific examples exemplified earlier as L ₁₂ in General Formula (VI). The same group can be mentioned.

Moreover, the same specific example as each in X <_11> mentioned above is mentioned as -NR- and bivalent nitrogen containing non-aromatic heterocyclic group of the coupling group in L <_22> , and a preferable example is also the same.

Z <_2> represents the site which becomes a sulfonic acid group by irradiation of actinic light or a radiation. Specific examples of Z ₂ include the same as those described above for Z ₁ .

Next, the site | part represented by general formula (L3) is demonstrated.

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

Examples of the -NR- and divalent nitrogen-containing non-aromatic heterocyclic groups in each of X ₃₁ and X ₃₂ include the same ones as those described above for X ₁₁ .

As X _{31, a} single bond, -O-, -CO-, -NR- (R is a hydrogen atom or an alkyl group) or a group combining them is more preferable, and a single bond, -COO- or -CONR- (R is a hydrogen atom or Alkyl groups) are particularly preferred.

As X _32, -O-, -S-, -CO-, -SO _2- , a divalent nitrogen-containing non-aromatic heterocyclic group or a combination thereof are more preferable, and -O-, -OCO- or -OSO _2- 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 above combined group, two or more groups to be combined may be the same as or different from each other. In addition, these groups include -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing nonaromatic heterocyclic group, a divalent aromatic ring group or a combination thereof. It may be connected via a flag.

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

Moreover, the same specific example as each in X <_11> mentioned above is mentioned as -NR- and bivalent nitrogen containing non-aromatic heterocyclic group of the coupling group in L <_31> , and a preferable example is 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 thereof. In the above combined group, two or more groups to be combined may be the same as or different from each other. In addition, these groups include -O-, -S-, -CO-, -SO _2- , -NR- (R is a hydrogen atom or an alkyl group), a divalent nitrogen-containing nonaromatic heterocyclic group, a divalent aromatic ring group or a combination thereof. It may be connected via a flag.

L ₃₂ in the alkylene group, an alkenylene group, a bivalent aliphatic hydrocarbon ring group, a divalent direction group or some or all of the fluorine atom, a fluorinated alkyl group is a hydrogen atom which is a combination of two or more of them, a nitro group in, and cyano It is preferable to substitute by the substituent selected.

As L ₃₂ , an alkylene group 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), a divalent aromatic ring group, or a combination thereof is more preferable, and part or all of the hydrogen atoms are more preferable. The alkylene group or bivalent aromatic ring group substituted with the fluorine atom is especially preferable.

Examples of the alkylene group, alkenylene group, divalent aliphatic hydrocarbon ring group, divalent aromatic ring group, and a combination of two or more of them, for example, L ₃₂ include those similar to those described earlier for L ₁₂ . Examples of the -NR- and divalent nitrogen-containing non-aromatic heterocyclic groups of the linking group in L ₃₂ include the same specific examples as in X ₁₁ described above, and preferred examples thereof are also the same.

Further, X ₃ is a single bond Further, in the case of L ₃₁ is the direction of ventilation, R if ₃₂ is formed in the direction of ventilation and exchange of L _31, the alkylene group is preferably a carbon number of 1-8 individuals represented by R ₃₂ And it is more preferable that it is C1-C4, and it is still more preferable that it is C1-C2.

Z <_3> represents the onium salt which turns into an imide acid group or a methic acid group by irradiation of actinic light or a radiation. As an onium salt represented by Z <_3> , a sulfonium salt or an iodonium salt is preferable, and the structure represented by the following general formula (ZIII) or (ZIV) is preferable.

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

Rz ₁ , Rz ₂ and Rz ₃ each independently represent an alkyl group, a monovalent aliphatic hydrocarbon ring group, an aryl group or an aralkyl group. More preferably, some or all of the hydrogen atoms are substituted with fluorine atoms or fluoroalkyl groups (more preferably perfluoroalkyl groups).

The alkyl group 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 of Rz ₁ , Rz ₂ and Rz ₃ preferably has 3 to 10 carbon atoms, and more preferably 3 to 6 carbon atoms.

The aryl groups of Rz ₁ , Rz ₂ and Rz ₃ preferably have 6 to 18 carbon atoms, and more preferably 6 to 10 carbon atoms. As this aryl group, a phenyl group is especially preferable.

Rz _1, Rz ₂ Rz ₃ and preferred examples of the aralkyl group may be mentioned the combined group having 1 to 8 alkylene group wherein the aryl group. The aralkyl group which the C1-C6 alkylene group and the said aryl group couple | bonded is more preferable, The aralkyl group which the C1-C4 alkylene group and the said aryl group couple | bonded is especially preferable.

A ⁺ represents a sulfonium cation or an iodonium cation. As a preferable example of A <^+>, the sulfonium cation in general formula (ZI) or the iodonium cation structure in general formula (ZII) is mentioned.

Although the specific example of a repeating unit (B) is given to the following, the scope of the present invention is not limited to these.

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

M shows the integer of 0-4 in general formula (A1). n represents the integer of 1-5 which satisfy | fills the relationship which becomes m + n <= 5. S ₁ represents a substituent (excluding hydrogen atoms), and in the case of m ≧ 2, a plurality of S ₁ may be the same as or different from each other. A ₁ represents a group which is released by the action of a hydrogen atom or an acid, and when n ≧ 2, a plurality of the A _{1 's} may be the same as or different from each other.

In general formula (A2), X 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 carboxyl group, An alkyloxycarbonyl group, an alkylcarbonyloxy group, or an aralkyl group is shown. A ₂ represents a group leaving by the action of an acid.

First, the repeating unit represented by general formula (A1) is demonstrated.

m is an integer of 0-4 as mentioned above. m is preferably 0 to 2, more preferably 0 or 1, and particularly preferably 0.

n is an integer of 1-5 which satisfy | fills the relationship which m + n <= 5 as mentioned above. n is preferably 1 or 2, and particularly preferably 1.

S ₁ represents a substituent (excluding hydrogen atoms) as described above. As this substituent, the thing similar to what was previously demonstrated about S <_2> in General formula (I) is mentioned, for example.

A ₁ represents a group released by the action of a hydrogen atom or an acid as described above. When A ₁ is a group 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 containing no acid-decomposable group.

Examples of the group 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₎ it may be an acetal represented by -OZ ^2.

Hereinafter, formula _{-C (L 1) (L 2} ) will be described acetal groups represented by -OZ ^2. In the formulas, 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. In addition, Z ² and L ¹ may be bonded to each other to form a 5- or 6-membered ring.

The alkyl group may be a straight chain alkyl group or a branched chain alkyl group.

The linear alkyl group preferably has 1 to 30 carbon atoms, and more preferably 1 to 20 carbon atoms. As such a linear alkyl group, for example, a methyl group, an ethyl group, n-propyl group, n-butyl group, sec-butyl group, t-butyl group, n-pentyl group, n-hexyl group, n-heptyl group, n-jade Tyl group, n-nonyl group, and n-decanyl group are mentioned.

The branched alkyl group preferably has 3 to 30 carbon atoms, and more preferably 3 to 20 carbon atoms. As such a branched alkyl group, for example, i-propyl group, i-butyl group, t-butyl group, i-pentyl group, t-pentyl group, i-hexyl group, t-hexyl group, 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. As this substituent, it is a hydroxyl group, for example; Halogen atoms such as fluorine, chlorine, bromine and iodine atoms; A nitro group; Cyano; Amide group; Sulfonamide groups; Alkyl groups such as methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, sec-butyl group, hexyl group, 2-ethylhexyl group, octyl group and dodecyl group; Alkoxy groups such as methoxy group, ethoxy group, hydroxyethoxy group, propoxy group, hydroxypropoxy group and butoxy group; Alkoxycarbonyl groups such as methoxycarbonyl group and ethoxycarbonyl group; Acyl groups such as formyl group, acetyl group and benzoyl group; Acyloxy groups, such as an acetoxy group and a butyloxy group, and a carboxyl group are mentioned.

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

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

As monocyclic cycloalkyl group, a C3-C8 thing is preferable. As such a cycloalkyl group, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclobutyl group, and a cyclooctyl group are mentioned, for example.

As a polycyclic cycloalkyl group, group which has a bicyclo, tricyclo, or tetracyclo structure is mentioned, for example. As a polycyclic cycloalkyl group, a C6-C20 thing is preferable. As such a cycloalkyl group, an adamantyl group, norbornyl group, isobornyl group, campanyl group, dicyclopentyl group, (alpha)-pinenel group, tricyclo decanyl group, tetracyclo dodecyl group, and androstanyl group is mentioned, for example. .

As a specific example of a cycloalkyl group, the same thing as what was listed about R _<a> in General formula (I) is mentioned, for example first. These cycloalkyl groups may further have a substituent. As this substituent, the same thing as what was demonstrated as a substituent which an alkyl group may have, for example is mentioned first. As a cycloalkyl group, a cyclohexyl group is especially preferable.

As an aralkyl group in L <_1> , L <_2> and Z <^2> , the thing of 7-15 carbon atoms, such as a benzyl group and a phenethyl group, is mentioned, for example.

These aralkyl groups may further have a substituent. As this substituent, Preferably, 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 are mentioned. As an aralkyl group which has a substituent, an alkoxybenzyl group, a hydroxybenzyl group, and a phenylthio phenethyl group are mentioned, for example. The carbon number of the substituent which these aralkyl groups may have is preferably 12 or less.

As a 5- or 6-membered ring which Z <^2> and L <_1> couple | bond with each other and can form, a tetrahydropyran ring and a tetrahydrofuran ring are mentioned, for example. Among them, tetrahydropyran ring is particularly preferable.

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

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

Next, the repeating unit represented by general formula (A2) is demonstrated. This repeating unit has an acid-decomposable group as described later.

X 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, carboxyl group, alkyloxycarbonyl group as described above. , An alkylcarbonyloxy group or an aralkyl group. As these groups or atoms, the same thing as what was previously demonstrated about R _<a> in General formula (I) is mentioned, for example.

A ₂ represents a group 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. As A <_2> , the same thing as what was previously demonstrated about A <_3> in general formula (I) is mentioned, for example.

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

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

It is preferable that the repeating unit represented by general formula (A2) is a repeating unit of t-butyl methacrylate or ethylcyclopentyl methacrylate. Moreover, it is also preferable that the repeating unit represented by general formula (A2) is a repeating unit represented with 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.

AR is a phenyl group, a naphthyl group, or an anthryl group as mentioned above. When AR is a naphthyl group or anthryl group, there is no restriction | limiting in particular in the bonding position of AR and the carbon atom which Rn couple | bonds. For example, when AR is a naphthyl group, this carbon atom may be couple | bonded with the (alpha) position of a naphthyl group, and may be couple | bonded with the (beta) position. Alternatively, when AR is an anthryl group, this carbon atom may be bonded to one position of the anthryl group, may be bonded to two positions, or may be bonded to nine positions.

The phenyl group, naphthyl group, and anthryl group as AR may each have one or more substituents.

As this substituent, C1-C20, such as a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, octyl group, and dodecyl group, is mentioned, for example. Individual linear or branched alkyl groups, cycloalkyl groups such as alkoxy groups including these alkyl group moieties, cyclopentyl groups and cyclohexyl groups, cycloalkoxy groups containing these cycloalkyl group moieties, hydroxyl groups, halogen atoms, aryl groups, and cyan No group, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group, thiophencarbonyloxy group, thiophenemethylcarbonyloxy group, and pyrrolidone Heterocyclic residues, such as a residue, are mentioned. As this substituent, the C1-C5 linear or branched alkyl group or the alkoxy group containing these alkyl-group parts from a viewpoint of the resolution of a composition is preferable.

AR is preferably a phenyl group, para methylphenyl group or para methoxyphenyl group.

Rn represents an alkyl group, a cycloalkyl group or an aryl group as described above.

The alkyl group of Rn may be a straight chain alkyl group or a branched chain alkyl group. As this alkyl group, Preferably carbon number, such as a methyl group, an ethyl group, a propyl group, isopropyl group, n-butyl group, isobutyl group, t-butyl group, pentyl group, hexyl group, cyclohexyl group, octyl group, and dodecyl group, One to 20 things can be mentioned.

As a cycloalkyl group of Rn, a C3-C15 thing, such as a cyclopentyl group and a cyclohexyl group, is mentioned, for example.

As an aryl group of Rn, C6-C14 is preferable, for example, a phenyl group, xylyl group, toluyl group, cumenyl group, naphthyl group, and anthryl group.

Each of these alkyl groups, cycloalkyl groups, and aryl groups may further have a substituent. Examples of the substituent include an alkoxy group, hydroxyl group, halogen atom, nitro group, acyl group, acyloxy group, acylamino group, sulfonylamino group, alkylthio group, arylthio group, aralkylthio group and thiophencarbo Heterocyclic residues, such as a silyloxy group, a thiophenmethylcarbonyloxy group, and a pyrrolidone residue, are mentioned. Especially, 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 especially preferable.

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

As an alkyl group and a cycloalkyl group of A, the same thing as what was demonstrated previously about Rn is mentioned, for example. Each of these alkyl groups and cycloalkyl groups may have a substituent. As this substituent, the same thing as what was demonstrated previously about Rn is mentioned, for example.

When A is an alkyl group or a cycloalkyl group having a substituent, particularly preferred A include CF ₃ group, alkyloxycarbonylmethyl group, alkylcarbonyloxymethyl group, hydroxymethyl group and alkoxymethyl group.

Examples of the halogen atom of A include fluorine, chlorine, bromine and iodine atoms. Especially, a fluorine atom is especially preferable.

As the alkyl group moiety included in the alkyloxycarbonyl group of A, for example, a structure enumerated as an alkyl group of A can be adopted.

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

It is preferable that the said resin further contains the repeating unit represented by following General formula (A4) other than a repeating unit (A) and (B). By adopting such a configuration, for example, it becomes possible to further improve the film quality and further suppress the film reduction of the unexposed part.

In general formula (A4), R <_2> represents a hydrogen atom, a methyl group, a cyano group, a halogen atom, or a C1-C4 perfluoro group. 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 the integer of 0-4. W represents a group which will not be decomposed by the action of an acid (hereinafter also referred to as an acid stabilizer).

As the acid stabilizer of W, for example, 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 aryl jade A time period, an arylamide methyl group, and an arylamide 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, and more preferably an acyl group, an alkylcarbonyloxy group, an alkyloxy group or a cyclo Alkyloxy group or aryloxy group.

The alkyl group of W is preferably one having 1 to 4 carbon atoms such as methyl group, ethyl group, propyl group, n-butyl group, sec-butyl group and t-butyl group.

As a cycloalkyl group of W, a C3-C10 thing, such as a cyclopropyl group, a cyclobutyl group, a cyclohexyl group, and an adamantyl group, is preferable.

As the alkenyl group of W, one having 2 to 4 carbon atoms such as a vinyl group, a propenyl group, an allyl group, and a butenyl group is preferable.

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

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

Although the specific example of the repeating unit represented by general formula (A4) is given below, it is not limited to these.

In addition to the repeating units (A) and (B), the resin may further include a repeating unit made 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.

The resin may further include a repeating unit having an acid-decomposable group represented by the formula -C (= 0) -X ₁ -R ₀ in addition to the repeating units (A) and (B). Here, X ₁ represents an oxygen atom, a sulfur atom, -NH-, -NHSO ₂ -or -NHSO ₂ NH-. R ₀ is a group leaving by the action of an acid, for example, tertiary alkyl groups such as t-butyl group and t-amyl group, isobornyl group, 1-ethoxyethyl group, 1-butoxyethyl group, 1- Alkoxymethyl groups, such as 1-alkoxyethyl groups, 1-methoxymethyl group, and 1-ethoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkyl, such as isobutoxyethyl group and 1-cyclohexyloxyethyl group And silyl ester groups, 3-oxocyclohexyl ester groups, 2-methyl-2-adamantyl groups, and mevalonic lactone residues.

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

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%, more preferably 15 to 50 mol% based on all repeating units. It is particularly preferable to.

The content of the repeating unit (A) in the resin is preferably 1 to 70 mol%, more preferably 1 to 50 mol%, more preferably 1 to 30 mol%, based on all repeating units. Particularly preferred.

The content of the repeating unit (B) in the resin is preferably 0.1 to 80 mol%, more preferably 0.5 to 60 mol%, more preferably 1 to 40 mol%, based on all repeating units. Particularly preferred.

When the said resin contains the repeating unit represented by general formula (A1), it is preferable to set it as 20-90 mol%, and, as for the content rate, based on all repeating units, it is more preferable to set it as 30-80 mol%. And it is especially preferable to set it as 40-70 mol%.

When the said resin contains the repeating unit represented by general formula (A2), it is preferable to make the content rate into 1-90 mol% based on all the repeating units, and it is more preferable to set it as 5-75 mol%. And it is especially preferable to set it as 10-60 mol%.

When the said resin contains the repeating unit represented by general formula (A4), it is preferable to set it as 1-50 mol% with respect to all the repeating units, and it is more preferable to set it as 1-40 mol%. It is especially preferable to set it as 1-30 mol%.

It is preferable that the weight average molecular weight (Mw) of the said resin exists in the range of 1000-200000, It is more preferable to exist in the range of 1000-100000, It is still more preferable to exist in the range of 1000-50000, The range of 1000-25000 It is particularly preferable to be in. When this weight average molecular weight is enlarged excessively, the dissolution rate with respect to alkali of resin and the sensitivity of a composition may fall.

It is preferable that the dispersion degree (Mw / Mn) of the said resin is 1.0-3.0, It is more preferable that it is 1.0-2.5, It is still more preferable that it is 1.0-2.0.

Resin with high dispersibility can be synthesized as follows, for example. That is, by radical polymerization using an azo polymerization initiator, resin of dispersion degree 1.2-2.0 can be synthesized, for example. Moreover, resin of dispersion degree 1.0-1.5 can be synthesize | combined by using a living radical polymerization method, for example.

The said resin may be used individually by 1 type, and may be used in combination of 2 or more type. The total amount of these resins is 10-99 mass% normally on the basis of the total solid of a composition, Preferably it is 20-99 mass%, Especially preferably, it is 30-99 mass%.

Although the specific example of resin which concerns on 1st Embodiment is shown below, it is not limited to these.

Although the specific example of resin which concerns on 1st or 2nd embodiment is shown below, it is not limited to these.

[2] photoacid generators

The composition according to the present invention may contain a photoacid generator as described above.

As the photoacid generator, for example, a known compound which generates an acid by irradiation with actinic rays or radiation used in a photoinitiator of photocationic polymerization, a photoinitiator of photoradical polymerization, a photochromic agent, a photochromic agent, a microresist, and the like, and those Mixtures may be selected as appropriate. Examples thereof include an onium salt such as a sulfonium salt and an iodonium salt, and a diazodisulfone compound such as bis (alkylsulfonyldiazomethane).

As a preferable example of a photoacid generator, the compound represented by the following general formula (ZI), (ZII), and (ZIII) is mentioned.

In the general formula (ZI), R ₂₀₁ , R ₂₀₂ and R ₂₀₃ each independently represent an organic group. _{Carbon number} of the organic group as R <_201> , R <_202> and R <_203> is 1-30 pieces, for example, Preferably it is 1-20 pieces.

Two of R ₂₀₁ to R ₂₀₃ may be bonded to each other through a single bond or a linking group to form a ring structure. As a coupling group in this case, an ether bond, a thioether bond, an ester bond, an amide bond, a carbonyl group, a methylene group, and an ethylene group are mentioned, for example. Examples of the group formed by bonding of two of R ₂₀₁ to R ₂₀₃ include alkylene groups such as a butylene group and a pentylene group.

As a specific example of R <_201> , R <_202> and R <_203> , the corresponding group in compound (ZI-1), (ZI-2), or (ZI-3) mentioned later is mentioned.

X ^- represents an acetylenic anion. Examples of X ⁻ include sulfonic acid anions, bis (alkylsulfonyl) amide anions, tris (alkylsulfonyl) methed anions, 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 represented by following AN1-AN3 is mentioned, for example.

Expression of the AN3 AN1 ~, ₁ ~ Rc Rc ₃ represents an organic group independently. As this organic group, a C1-C30 thing is mentioned, for example, Preferably it is an alkyl group, an aryl group, or group in which several of these were connected via the coupling group. Furthermore, the linking group as, for example, a single bond, -O-, -CO ₂ - there may be mentioned -, -S-, -SO ₃ - and -SO ₂ N (Rd _1). Here, Rd ₁ represents a hydrogen atom or an alkyl group, an alkyl group or an aryl group and may form a ring structure bonded.

The organic group of Rc ₁ to Rc ₃ may be an alkyl group substituted in one 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 raise the acidity of the acid generated by light irradiation. Thus, the sensitivity of the actinic ray-sensitive or radiation-sensitive resin composition can be improved. Rc ₁ to Rc ₃ may be bonded to another alkyl group, aryl group, or the like to form a ring.

Moreover, the sulfonic acid anion represented by following General formula (SA1) or (SA2) is mentioned as preferable X <^-> .

In the formula (SA1)

Ar ₁ represents an aryl group and may further have a substituent other than the-(DB) group.

n represents an integer of 1 or more. n becomes like this. Preferably it is 1-4, More preferably, it is 2-3, Most preferably, it is 3.

D represents a single bond or a divalent linking group. The divalent linking group is an ether group, a thioether group, a carbonyl group, a sulfoxide group, a sulfone group, a sulfonate ester group or an ester group.

B represents a hydrocarbon group.

In the formula (SA2)

Xf each independently represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.

R ₁ and R ₂ each independently represent a group selected from a hydrogen atom, a fluorine atom, an alkyl group, and an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and in the case where a plurality of R ₁ and R ₂ are present, each of R ₁ and R ₂ may be the same as each other, May be different.

L represents a single bond or a divalent linking group, and when there are a plurality of L's, they may be the same as or different from each other.

E represents a group having a cyclic structure.

x represents the integer of 1-20, y represents the integer of 0-10, z represents the integer of 0-10.

First, the sulfonic acid anion represented by formula (SA1) will be described in detail.

In formula (SA1), Ar ₁ is preferably an aromatic ring having 6 to 30 carbon atoms. Specifically, Ar ₁ is, for example, a benzene ring, a naphthalene ring, a pentalene ring, an indene ring, an azulene ring, a heptylene ring, an indencene ring, a perylene ring, a pentacene ring, an acenaphthalene ring, a phenanthrene ring, an anthracene ring, a naphthacene ring , Chrysene ring, triphenylene ring, fluorene ring, biphenyl ring, pyrrole ring, furan ring, thiophene ring, imidazole ring, oxazole ring, thiazole ring, pyridine ring, pyrazine ring, pyrimidine ring, pyridazine ring, Indolidine ring, indole ring, benzofuran ring, benzothiophene ring, isobenzofuran ring, quinolidine ring, quinoline ring, phthalazine ring, naphthyridine ring, quinoxaline ring, quinoxazoline ring, isoquinoline ring It is a basel ring, a phenanthridine ring, an acridine ring, a phenanthroline ring, a thianthrene ring, a chromen ring, a xanthene ring, a phenoxatiin ring, a phenothiazine ring, or a phenazine ring. Especially, a benzene ring, a naphthalene ring, or an anthracene ring is preferable from a viewpoint of both roughness improvement and high sensitivity, and a benzene ring is more preferable.

Ar ₁ is - if they have further a substituent other than (DB) group, as a substituent, for example, include the following. That is, as this substituent, Halogen atoms, such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; Alkoxy groups such as methoxy, ethoxy and tert-butoxy groups; An aryloxy group such as a phenoxy group and a p-tolyloxy group; An alkyloxy group such as a methylthio group, an ethylthio group and a tert-butylthio group; Arylthioxy groups such as phenylthio group and p-tolylthioxy group; Alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group and a phenoxycarbonyl group; An acetoxy group; Straight chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; Branched alkyl groups; Alkenyl groups such as a vinyl group, a propenyl group and a hexenyl group; An acetylene group; Alkynyl groups such as propynyl and hexynyl; An aryl group such as a phenyl group and a tolyl group; A hydroxyl group; A carboxyl group; And sulfonic acid groups. Especially, a linear alkyl group and a branched alkyl group are preferable from a viewpoint of roughness improvement.

In formula (SA1), D is preferably a single bond or an ether group or an ester group. More preferably, D is a single bond.

In formula (SA1), B is an alkyl group, an alkenyl group, an alkynyl group, an aryl group, or a cycloalkyl group, for example. B is preferably an alkyl group or a cycloalkyl group. The alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B may have a substituent.

The alkyl group as B is preferably a branched alkyl group. As this branched alkyl group, for example, isopropyl group, tert-butyl group, tert-pentyl group, neopentyl group, sec-butyl group, isobutyl group, isohexyl group, 3,3-dimethylpentyl group and 2-ethyl Hexyl group is mentioned.

The cycloalkyl group as B may be a monocyclic cycloalkyl group or a polycyclic cycloalkyl group. As a monocyclic cycloalkyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group is mentioned, for example. Examples of the polycyclic cycloalkyl group include, for example, adamantyl, norbornyl, boryl, camphor, decahydronaphthyl, tricyclodecanyl, tetracyclodecanyl, camphoroyl, dicyclohexyl, and pineneyl groups. Can be mentioned.

When the alkyl group, alkenyl group, alkynyl group, aryl group or cycloalkyl group as B has a substituent, the following are mentioned as this substituent, for example. That is, examples of the substituent include a halogen atom such as a fluorine atom, a chlorine atom, a bromine atom and an iodine atom; Alkoxy groups such as methoxy, ethoxy and tert-butoxy groups; Aryloxy groups such as phenoxy group and p-tolyloxy group; Alkyl thioxy groups such as methyl thioxy group, ethyl thioxy group and tert-butyl thioxy group; Aryl thioxy groups, such as a phenyl thioxy group and p-tolyl thioxy group; Alkoxycarbonyl groups such as methoxycarbonyl group, butoxycarbonyl group and phenoxycarbonyl group; Acetoxy group; Straight chain alkyl groups such as methyl group, ethyl group, propyl group, butyl group, heptyl group, hexyl group, dodecyl group and 2-ethylhexyl group; Branched alkyl groups; Cycloalkyl groups such as cyclohexyl group; Alkenyl groups such as vinyl group, propenyl group and hexenyl group; An acetylene group; Alkynyl groups such as propynyl and hexynyl; Aryl groups such as phenyl group and tolyl group; A hydroxyl group; A carboxyl group; Sulfonic acid groups; And a carbonyl group. Especially, a linear alkyl group and a branched alkyl group are preferable from a viewpoint of coexistence of roughness improvement and high sensitivity.

Next, the sulfonic acid anion represented by formula (SA2) will be described in detail.

In formula (SA2), Xf is a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. The alkyl group preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms. The alkyl group substituted with a fluorine atom is preferably a perfluoroalkyl group.

Xf is preferably a fluorine atom or a perfluoroalkyl group having 1 to 4 carbon atoms. Specifically, Xf is preferably a fluorine atom, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH _{2 CF 3, CH 2 CH 2} CF 3, CH 2 C 2 F 5, CH 2 CH 2 C 2 F 5, CH 2 C 3 F 7, CH 2 CH 2 C 3 F 7, CH 2 C 4 F 9 , or CH ₂ CH ₂ C ₄ F ₉ . Among them, a fluorine atom or CF ₃ is preferable, and a fluorine atom is most preferable.

In formula (SA2), each of R ₁ and R ₂ is a group selected from a hydrogen atom, a fluorine atom, an alkyl group, and an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom. As an alkyl group which may be substituted by this fluorine atom, a C1-C4 thing is preferable. Moreover, as an alkyl group substituted by the fluorine atom, a C1-C4 perfluoroalkyl group is especially preferable. Specifically, CF ₃ , C ₂ F ₅ , C ₃ F ₇ , C ₄ F ₉ , C ₅ F ₁₁ , C ₆ F ₁₃ , C ₇ F ₁₅ , C ₈ F ₁₇ , CH ₂ CF ₃ , CH ₂ CH ₂ CF ₃ , CH ₂ C ₂ F ₅ , CH ₂ CH ₂ C ₂ F ₅ , CH ₂ C ₃ F ₇ , CH ₂ CH ₂ C ₃ F ₇ , CH ₂ C ₄ F ₉ or CH ₂ CH ₂ C ₄ F ₉ And CF ₃ is particularly preferable.

In formula (SA2), 1-8 are preferable and, as for x, 1-4 are more preferable. 0-4 are preferable and, as for y, 0 is more preferable. 0-8 are preferable and, as for z, 0-4 are more preferable.

In formula (SA2), L represents a single bond or a divalent linking group. As the divalent linking group, e.g., -COO-, -OCO-, -CO-, -O-, -S-, -SO-, -SO 2 - may be mentioned, an alkylene group, a cycloalkylene group and the alkenylene group . Among them, -COO-, -OCO-, -CO-, -O-, -S-, -SO- or -SO ₂ - is preferable, -COO-, -OCO- or -SO ₂ - is more preferable Do.

In formula (SA2), E represents a group having a ring structure. As E, group which has a cyclic aliphatic group, an aryl group, and a heterocyclic structure is mentioned, for example.

The cyclic aliphatic group as E may have a monocyclic structure or may have a polycyclic structure. As a cyclic aliphatic group which has a monocyclic structure, monocyclic cycloalkyl groups, such as a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group, are preferable. As a cyclic aliphatic group which has a polycyclic structure, polycyclic cycloalkyl groups, such as a norbornyl group, a tricyclo decanyl group, a tetracyclo decanyl group, a tetracyclo dodecanyl group, and an adamantyl group, are preferable. In particular, when E is used as a cyclic aliphatic group having a bulky structure of 6 or more rings, the diffusibility in the film in the PEB (post-exposure heating) step is suppressed, and the resolution and EL (exposure latitude) can be further improved.

The aryl group as E is a benzene ring, a naphthalene ring, a phenanthrene ring, or an anthracene ring, for example.

The group which has a heterocyclic structure as E may have aromaticity, and does not need to have aromaticity. The hetero atom contained in this group is preferably a nitrogen atom or an oxygen atom. Specific examples of the heterocyclic structure include furan ring, thiophene ring, benzofuran ring, benzothiophene ring, dibenzofuran ring, dibenzothiophene ring, pyridine ring, piperidine ring and morpholine ring. Among them, furan ring, thiophen ring, pyridine ring, piperidine ring and morpholine ring are preferable.

E may have a substituent. As this substituent, an alkyl group (any of linear, branched, or cyclic may be sufficient, for example, C1-C12 is preferable), an aryl group (preferably C6-C14), a hydroxyl group, an alkoxy group, ester group , Amide group, urethane group, ureido group, thioether group, sulfonamide group and sulfonic acid ester group.

As a sulfonic acid anion represented by general formula (SA1) or (SA2), the following are mentioned, for example.

As a photo-acid generator, you may use the compound which has two or more structures represented by general formula (ZI). For example, the compound represented by formula (ZI) R ₂₀₁ ~ R ₂₀₃ of at least one is the general formula (ZI) a compound having a structure that combines and one at least one of R ₂₀₁ ~ R ₂₀₃ of another compound represented by the It may be.

As a more preferable (ZI) component, the compound (ZI-1)-(ZI-4) demonstrated below is mentioned.

In the compound (ZI-1), at least one of R ₂₀₁ to R ₂₀₃ of General Formula (ZI) is an aryl group. That is, compound (ZI-1) is an arylsulfonium compound, ie, a compound having arylsulfonium as a cation.

All of R ₂₀₁ to R ₂₀₃ may be an aryl group, or a part of R ₂₀₁ to R ₂₀₃ may be an aryl group, and the compound (ZI-1) may be an alkyl group other than these. When the compound (ZI-1) has a plurality of aryl groups, these aryl groups may be the same or different.

As a compound (ZI-1), a triarylsulfonium compound, a diarylalkylsulfonium compound, and an aryldialkylsulfonium compound are mentioned, for example.

As an aryl group in a compound (ZI-1), heteroaryl groups, such as a phenyl group, a naphthyl group, or an indole residue, and a pyrrole residue, are preferable, and a phenyl group, a naphthyl group, or an indole residue is especially preferable.

As an alkyl group which compound (ZI-1) has as needed, a C1-C15 linear, branched or cycloalkyl group is preferable, For example, a methyl group, an ethyl group, a propyl group, n-butyl group, sec-butyl group, t -Butyl group, cyclopropyl group, cyclobutyl group, and cyclohexyl group are mentioned.

These aryl groups and alkyl groups may have a substituent. Examples of the substituent include an alkyl group (preferably 1 to 15 carbon atoms), an aryl group (preferably 6 to 14 carbon atoms), an alkoxy group (preferably 1 to 15 carbon atoms), a halogen atom, and a hydroxyl group. And a phenylthio group.

As a preferable substituent, a C1-C12 linear, branched or cyclic alkyl group, and a C1-C12 linear, branched or cyclic alkoxy group are mentioned. Especially preferable substituents are a C1-C6 alkyl group and a C1-C6 alkoxy group. The substituent may be substituted on any one of three R ₂₀₁ to R ₂₀₃ , or may be substituted on all three. In the case where R ₂₀₁ to R ₂₀₃ are phenyl groups, the substituent is preferably substituted at the p-position of the aryl group.

Moreover, the form whose one or two of R <_201> , R <_202> and R <_203> may have a substituent and the remaining group is a linear, branched or cyclic alkyl group is also preferable. As a specific example of this structure, Paragraph 0141 of Unexamined-Japanese-Patent No. 2004-210670-the structure of 0153 can be mentioned.

At this time, specifically as said aryl group, it is the same as the aryl group as R <_201> , R <_202> and R <_203> , and a phenyl group or a naphthyl group is preferable. Moreover, it is preferable that an aryl group has either a hydroxyl group, an alkoxy group, or an alkyl group as a substituent. As a substituent, More preferably, it is a C1-C12 alkoxy group, More preferably, it is a C1-C6 alkoxy group.

The linear, branched or cyclic alkyl group as the remaining group is preferably an alkyl group having 1 to 6 carbon atoms. These groups may further have a substituent. In addition, when two said remaining groups exist, these two may combine with each other and may form the ring structure.

Compound (ZI-1) is a compound represented by the following general formula (ZI-1A), for example.

Of the general formula (ZI-1A)

R ₁₃ represents a hydrogen atom, a fluorine atom, a hydroxyl group, an alkyl group, a cycloalkyl group, an alkoxy group, a cycloalkyloxy group or an alkoxycarbonyl group.

R _14, when present in plural, independently represents an alkyl group, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group or a cycloalkylsulfonyl group.

And each R ₁₅ independently represents an alkyl group or a cycloalkyl group. Two R _{15 's} may be bonded to each other to form a ring structure.

and l represents an integer of 0 to 2.

r represents the integer of 0-8.

X <^-> represents a non-nucleophilic anion, For example, the same thing as X <^-> in general formula (ZI) is mentioned.

The alkyl group of R ₁₃ , R ₁₄ or R ₁₅ may be a straight chain alkyl group or a branched chain alkyl group. As this alkyl group, a C1-C10 thing is preferable, For example, a methyl group, an ethyl group, n-propyl group, i-propyl group, n-butyl group, 2-methylpropyl group, 1-methylpropyl group, t-butyl The group, n-pentyl group, neopentyl group, n-hexyl group, n-heptyl group, n-octyl group, 2-ethylhexyl group, n-nonyl group, and n-decyl group are mentioned. Among these, a methyl group, an ethyl group, n-butyl group, and t-butyl group are especially preferable.

Examples of the cycloalkyl group of R ₁₃ , R ₁₄ or R ₁₅ include cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclododecanyl, cyclopentenyl, cyclohexenyl and cyclooctadiete. And a silyl group. Among these, cyclopropyl, cyclopentyl, cyclohexyl and cyclooctyl groups are particularly preferred.

As an alkyl group part of the alkoxy group of R <_13> or R <_14> , what was listed as an alkyl group of R <_13> , R <_14> or R <_15> is mentioned, for example first. As this alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, and n-butoxy group are especially preferable.

As the cycloalkyl group of R ₁₃ portion of the cycloalkyloxy groups may be, for example, that described previously as the cycloalkyl group of R _13, R ₁₄ or R _15. As the cycloalkyloxy group, a cyclopentyloxy group and a cyclohexyloxy group are particularly preferable.

As an alkoxy group part of the alkoxycarbonyl group of R <_13> , what was demonstrated previously as an alkoxy group of R <_13> or R <_14> is mentioned, for example. The alkoxycarbonyl group is particularly preferably a methoxycarbonyl group, an ethoxycarbonyl group or an n-butoxycarbonyl group.

As the alkyl group of R ₁₄ portion of the alkylsulfonyl group includes, for example, that described previously as the alkyl group of R _13, R ₁₄ or R _15. In addition, as part of a cycloalkyl cycloalkyl group alkylsulfonyl group of R _14, may be selected from among that described previously as the cycloalkyl group of R _13, R ₁₄ or R _15. As the alkylsulfonyl or cycloalkylsulfonyl group, a methanesulfonyl group, an ethanesulfonyl group, an n-propanesulfonyl group, an n-butanesulfonyl group, a cyclopentanesulfonyl group and a cyclohexanesulfonyl group are particularly preferable.

1 is preferably 0 or 1, and more preferably 1. r is preferably 0 to 2.

Each group of R ₁₃ , R ₁₄ and R ₁₅ may further have a substituent. Examples of the substituent include halogen atoms such as fluorine atoms, hydroxyl groups, carboxyl groups, cyano groups, nitro groups, alkoxy groups, cycloalkyloxy groups, alkoxyalkyl groups, cycloalkyloxyalkyl groups, alkoxycarbonyl groups, cycloalkyloxycarbonyl groups, Alkoxycarbonyloxy group and a cycloalkyloxycarbonyloxy group are mentioned.

The alkoxy group may be straight-chain or branched. As this alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, 2-methylpropoxy group, 1-methylpropoxy group, t-butoxy group, etc. are mentioned, for example. C1-C20 thing is mentioned.

As a cycloalkyloxy group, C3-C20 things, such as a cyclopentyloxy group and a cyclohexyloxy group, are mentioned, for example.

The alkoxyalkyl group may be straight-chain or branched. As this alkoxyalkyl group, C2-C21 things, such as a methoxymethyl group, an ethoxymethyl group, 1-methoxyethyl group, 2-methoxyethyl group, 1-ethoxyethyl group, and 2-ethoxyethyl group, are mentioned, for example. .

As a cycloalkyloxyalkyl group, C4-C21 things, such as a cyclohexyloxymethyl group, a cyclopentyloxymethyl group, and a cyclohexyloxyethyl group, are mentioned, for example.

The alkoxycarbonyl group may be straight chain or branched chain. As this alkoxycarbonyl group, a methoxycarbonyl group, an ethoxycarbonyl group, n-propoxycarbonyl group, i-propoxycarbonyl group, n-butoxycarbonyl group, 2-methylpropoxycarbonyl group, 1-methylpropoxycarbonyl group, and t- C2-C21 things, such as a butoxycarbonyl group, are mentioned.

As a cycloalkyloxycarbonyl group, C4-C21 things, such as a cyclopentyloxycarbonyl group and cyclohexyloxycarbonyl, are mentioned, for example.

The alkoxycarbonyloxy group may be straight-chain or branched. As this alkoxycarbonyloxy group, a methoxycarbonyloxy group, an ethoxycarbonyloxy group, n-propoxycarbonyloxy group, i-propoxycarbonyloxy group, n-butoxycarbonyl octa, for example C2-C21 thing, such as a timing and a t-butoxycarbonyloxy group, is mentioned.

As a cycloalkyloxycarbonyloxy group, C4-C21 things, such as a cyclopentyloxycarbonyloxy group and a cyclohexyloxycarbonyloxy group, are mentioned, for example.

As a ring structure which two R <_15> can combine with each other, and form the 5-membered ring or 6-membered ring, especially preferably 5-membered ring (that is, tetrahydrothiophene ring) with S atom in general formula (ZI-1A), The structure to make is preferable.

This ring structure may further have a substituent. As this substituent, a hydroxyl group, a carboxyl group, a cyano group, a nitro group, an alkoxy group, an alkoxyalkyl group, an alkoxycarbonyl group, and an alkoxycarbonyloxy group are mentioned, for example.

As R ₁₅ , a methyl group, an ethyl group, and a divalent group which forms a tetrahydrothiophene ring structure together with two R _{15 s} are combined together with a sulfur atom are particularly preferable.

Alkyl group of R _13, cycloalkyl group, alkoxy group and alkoxycarbonyl group, alkyl group of R _14, a cycloalkyl group, an alkoxy group, an alkylsulfonyl group and cycloalkyl sulfonyl group may further have a substituent. As this substituent, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group, and a halogen atom (especially a fluorine atom) are preferable.

Hereinafter, preferred specific examples of the cation in the compound represented by the general formula (ZI-1A) are shown.

Next, the compound (ZI-2) is described.

Compound (ZI-2) is a compound in case R ₂₀₁ to R ₂₀₃ in Formula (ZI) each independently represent an organic group containing no aromatic ring. Here, the aromatic ring includes an aromatic ring containing a hetero atom.

The organic group containing no aromatic ring as R ₂₀₁ to R ₂₀₃ is, for example, 1 to 30 carbon atoms, preferably 1 to 20 carbon atoms.

R ₂₀₁ to R ₂₀₃ are each independently an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group, or a vinyl group. More preferably, they are a linear, branched or cyclic 2-oxoalkyl group or an alkoxycarbonylmethyl group, Especially preferably, they are a linear or branched 2-oxoalkyl group.

The alkyl group as R ₂₀₁ to R ₂₀₃ may be any of straight chain, branched chain and cyclic, and is preferably a straight or branched chain alkyl group having 1 to 10 carbon atoms (for example, methyl group, ethyl group, propyl group, butyl group or pentyl group). And a C3-C10 cycloalkyl group (cyclopentyl group, cyclohexyl group, or norbornyl group).

The 2-oxoalkyl group as R ₂₀₁ to R ₂₀₃ may be any of straight chain, branched chain and cyclic, and preferably groups having> C═O at the 2-position of the alkyl group.

As a preferable example of the alkoxy group in the alkoxycarbonylmethyl group as R <_201> -R <_203>, a C1-C5 alkoxy group (methoxy group, an ethoxy group, a propoxy group, butoxy group, a pentoxy group) is mentioned.

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

Two of R ₂₀₁ to R ₂₀₃ 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. As a group which two of R <_201> -R <_203> combine and form, an alkylene group (for example, butylene group or a pentylene group) is mentioned, for example.

Next, the compound (ZI-3) is described.

The compound (ZI-3) is a compound represented by the following general formula (ZI-3) and has a phenacylsulfonium salt structure.

In the formula, each of R _1c to R _5c independently represents a hydrogen atom, an alkyl group, an alkoxy group or a halogen atom. As for carbon number of an alkyl group and an alkoxy group, 1-6 are preferable.

R _6c and R _7c represent a hydrogen atom or an alkyl group. As for carbon number of an alkyl group, 1-6 are preferable.

R _x and R _y each independently represent an alkyl group, a 2-oxoalkyl group, an alkoxycarbonylmethyl group, an allyl group or a vinyl group. As for carbon number of these atomic groups, 1-6 are preferable.

Any two or more of R _1c to R _7c may be bonded to each other to form a ring structure. In addition, R _x and R _y may be bonded to each other to form a ring structure. These ring structures may contain an oxygen atom, a sulfur atom, an ester bond and / or an amide bond.

In the formula (ZI-3) X ^- X is in formula (ZI) ^- are as defined.

As a specific example of a compound (ZI-3), the compound described in the compound illustrated by stage 0047 and 0048 of Unexamined-Japanese-Patent No. 2004-233661, or paragraph 0040-0046 of Unexamined-Japanese-Patent No. 2003-35948 is mentioned. .

Next, a compound (ZI-4) is demonstrated.

Compound (ZI-4) is a compound having a cation represented by the following General Formula (ZI-4). This compound (ZI-4) is effective for inhibiting outgas.

Among the general formula (ZI-4)

R ¹ to R ¹³ each independently represent a hydrogen atom or a substituent. At least one of R ¹ to R ¹³ is preferably a substituent containing an alcoholic hydroxyl group. In addition, an "alcoholic hydroxyl group" means the hydroxyl group couple | bonded with the carbon atom of an alkyl group here.

Z is a single bond or a divalent linking group.

When R <^1> -R <^13> is a substituent containing an alcoholic hydroxyl group, it is preferable that R <^1> -R <^13> is group represented by-(WY). Wherein Y is an alkyl group substituted with a hydroxyl group and W is a single bond or a divalent linking group.

Preferred examples of the alkyl group represented by Y include ethyl group, propyl group and 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 is preferably a single bond, an alkoxy group, an acyloxy group, an acylamino group, an alkyl and an arylsulfonylamino group, an alkylthio group, an alkylsulfonyl group, an acyl group, an alkoxycarbonyl group or It is a divalent group which substituted arbitrary hydrogen atoms in a carbamoyl group by a single bond, More preferably, any hydrogen atom in a single bond, an acyloxy group, an alkylsulfonyl group, an acyl group, or an alkoxycarbonyl group is single. It is a bivalent group substituted by the bond.

R ¹ - R ¹³ is an alcoholic when the substituent containing a hydroxyl group, the number of carbon atoms contained is preferably from 2 to 10, more preferably 2 to a 6, particularly preferably from two to four.

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

The number of alcoholic hydroxyl group with a compound represented by formula (ZI-4) is R ¹ to R ¹³ rolled into a 1 to 10 all, preferably from 1 to and 6, more preferably 1 to 3 Dog.

When R ¹ to R ¹³ do not contain an alcoholic hydroxyl group, examples of the substituent for R ¹ to R ¹³ include a halogen atom, an alkyl group, a cycloalkyl group, an alkenyl group, a cycloalkenyl group, an alkynyl group, an aryl group, Heterocyclic group, cyano group, nitro group, carboxyl group, alkoxy group, aryloxy group, silyloxy group, heterocyclic oxy group, acyloxy group, carbamoyloxy group, alkoxycarbonyloxy group, aryloxycarbonyloxy group, amino group (Including an anilino group), ammonia group, acylamino group, aminocarbonylamino group, alkoxycarbonylamino group, aryloxycarbonylamino group, sulfamoylamino group, alkyl and arylsulfonylamino group, mercapto group, alkylthio group, aryl Thio group, heterocyclic thio group, sulfamoyl group, sulfo group, alkyl and arylsulfinyl group, alkyl and arylsulfonyl group, acyl group, aryloxycarbonyl group, alkoxycarbonyl group, carbamoyl group, aryl and heterocycle 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 ], phosphate group [ -OPO (OH) ₂ ], a sulfate group (-OSO ₃ H), and other well-known substituents are mentioned.

When R ¹ to R ¹³ do not contain an alcoholic hydroxyl group, R ¹ to R ¹³ preferably represent 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, carboxyl 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 , Aminocarbonylamino group, alkoxycarbonylamino group, alkyl and arylsulfonylamino group, alkylthio group, sulfamoyl group, alkyl and arylsulfonyl group, alkoxycarbonyl group or 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 nonaromatic hydrocarbon rings and heterocycles. These ring structures may further be combined to form a condensed ring.

Compound (ZI-4) preferably has a structure in which at least one of R ¹ to R ¹³ includes an alcoholic hydroxyl group, and more preferably at least one of R ⁹ to R ¹³ is an alcoholic hydroxyl group. Has a structure comprising a.

Z represents a single bond or a divalent linking group as described above. As this bivalent coupling group, an alkylene group, arylene group, carbonyl group, sulfonyl group, carbonyloxy group, carbonylamino group, sulfonylamide group, ether group, thioether group, amino group, disulfide group, acyl group, Alkylsulfonyl group, -CH = CH-, an aminocarbonylamino group, and an aminosulfonylamino group are mentioned.

This divalent linking group may have a substituent. As these substituents, the thing similar to what was enumerated about R <^1> -R <^13> first is mentioned, for example.

Z is preferably a bond or group having no electron withdrawing properties such as a single bond, an alkylene group, an arylene group, an ether group, a thioether group, an amino group, -CH = CH-, an aminocarbonylamino group and an aminosulfonylamino group More preferably, they are a single bond, an ether group, or a thioether group, Especially preferably, they are a single bond.

Hereinafter, general formulas (ZII) and (ZIII) will be described.

In formulas (ZII) and (ZIII), each of R ₂₀₄ to R ₂₀₇ independently represents an aryl group, an alkyl group or a cycloalkyl group. These aryl groups, alkyl groups and cycloalkyl groups may have a substituent.

Preferred examples of the aryl group as R ₂₀₄ to R ₂₀₇ include the same groups as listed above for R ₂₀₁ to R ₂₀₃ in the compound (ZI-1).

As a preferable example of the alkyl group and cycloalkyl group as R <_204> -R <_207> , the linear, branched or cycloalkyl group listed about R <_201> -R <_203> in the compound (ZI-2) is mentioned first.

Further, in the general formula (ZII) and (ZIII) X ^- X is in formula (ZI) ^- are as defined.

As another preferable example of a photo-acid generator, the compound represented by the following general formula (ZIV), (ZV) or (ZVI) is mentioned.

Among the general formulas (ZIV) to (ZVI)

Ar ₃ and Ar ₄ each independently represent a substituted or unsubstituted aryl group.

R ₂₀₈ each independently represents an alkyl group, a cycloalkyl group or an aryl group in formulas (ZV) and (ZVI). These alkyl groups, cycloalkyl groups, and aryl groups may be substituted or may not be substituted.

These groups are preferably substituted by fluorine atoms. This makes it possible to increase the strength of the acid generated by the photoacid generator.

R ₂₀₉ and R ₂₁₀ each independently represent an alkyl group, a cycloalkyl group, an aryl group or an electron withdrawing group. These alkyl groups, cycloalkyl groups, aryl groups and electron withdrawing groups may or may not be substituted.

Preferred R ₂₀₉ includes a substituted or unsubstituted aryl group.

Preferred 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 groups, alkenylene groups, and arylene groups may have a substituent.

Moreover, the compound which has two or more structures represented by general formula (ZVI) as a photo-acid generator is also preferable. As such a compound, for example, a compound having an R ₂₀₉ or structure R ₂₁₀ are bonded to each other in the other one of the compound represented by R ₂₀₉ or R ₂₁₀ and the general formula (ZVI) of the compound represented by the general formula (ZVI) Can be mentioned.

As a photo-acid generator, the compound represented by general formula (ZI)-(ZIII) is more preferable, The compound represented by general formula (ZI) is still more preferable, A compound (ZI-1)-(ZI-3) is especially desirable.

Although the specific example of a photo-acid generator is shown below, the scope of the present invention is not limited to these.

Moreover, the composition by this invention may further contain the compound which generate | occur | produces a carboxylic acid by irradiation of actinic light or a radiation as a photo-acid generator. As such a compound, the following are mentioned, for example.

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 the compounds which generate | occur | produce two types of organic acids in which 2 or more whole atomic numbers except hydrogen atoms are combined.

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 to 30% by mass, more preferably based on the total solids of the composition. Preferably it is 1-20 mass%.

<Other ingredients>

The composition according to the present invention may further contain a basic compound, a surfactant, a solvent, a dye, a photobase generator, an antioxidant, a solvent, and the like. Hereinafter, these components are demonstrated.

(Basic compound)

The composition according to the present invention may further contain a basic compound. The basic compound is preferably a compound which is more basic than phenol. Moreover, it is preferable that this basic compound is an organic basic compound, and it is more preferable that it is 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)-(4) can be used.

(1) a compound represented by the following General Formula (BS-1)

In the general formula (BS-1)

Each R independently represents a hydrogen atom or an organic group. Provided that at least one of the three Rs is an organic group. The 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 pieces, Preferably it is 1-12 pieces.

Although carbon number of the cycloalkyl group as R is not specifically limited, Usually, it is 3-20 pieces, Preferably it is 5-15 pieces.

Although carbon number of the aryl group as R is not specifically limited, Usually, it is 6-20 pieces, Preferably it is 6-10 pieces. Specific examples thereof 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 pieces, Preferably it is 7-11 pieces. Specific examples thereof include a benzyl group and the like.

The alkyl group, cycloalkyl group, aryl group and aralkyl group as R may be a hydrogen atom substituted by a substituent. As this substituent, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, a hydroxyl group, a carboxyl group, an alkoxy group, an aryloxy group, an alkylcarbonyloxy group, an alkyloxycarbonyl group, etc. are mentioned, for example.

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

Specific examples of the compound represented by 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-dibutyl aniline, N, N- dihexyl aniline, 2,6- diisopropyl aniline, and 2,4,6- tri (t-butyl) aniline are mentioned.

Moreover, as a preferable basic compound represented by general formula (BS-1), what is at least 1 R is an alkyl group substituted by the hydroxyl group. Specific examples thereof include triethanolamine and N, N-dihydroxyethylaniline.

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 the compounds exemplified after line 60 of column 3 of the US6040112 specification can be given.

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

The nitrogen-containing heterocycle may or may not have aromatics. In addition, a plurality of nitrogen atoms may be contained. It may also contain heteroatoms other than nitrogen. Specifically, for example, a compound having an imidazole structure (2-phenylbenzoimidazole, 2,4,5-triphenylimidazole, etc.), a compound having a piperidine structure [N-hydroxyethylpiperi Dine and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate and the like], compounds having a pyridine structure (such as 4-dimethylaminopyridine), and compounds having an antipyrine structure (antipyrine And hydroxyantipyrine and the like).

Also, compounds having two or more ring structures can be suitably used. Specifically, 1, 5- diazabicyclo [4.3.0] nona-5-ene and 1,8- diazabicyclo [5.4.0]-undeca-7-ene are mentioned, for example.

(3) An amine compound having a phenoxy group

The amine compound which has a phenoxy group is a compound which has a phenoxy group in the terminal opposite to the N atom of the alkyl group which an amine compound contains. The phenoxy group may have a substituent such as an alkyl group, an alkoxy group, a halogen atom, a cyano group, a nitro group, a carboxyl group, a carboxylic acid ester group, a sulfonate ester group, an aryl group, an aralkyl group, an acyloxy group and an aryloxy group You can have it.

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 to 9, and more preferably 4 to 6. Of the oxyalkylene chains, -CH ₂ CH ₂ O- is particularly preferred.

As a specific example, 2- [2- {2- (2,2-dimethoxy-phenoxyethoxy) ethyl} -bis- (2-methoxyethyl)]-amine, and paragraph [of US2007 / 0224539 A1 specification] The compound (C1-1)-(C3-3) illustrated by [0066] can be mentioned.

The amine compound having a phenoxy group is reacted by heating a primary or secondary amine having a phenoxy group with a haloalkyl ether, and after addition of an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide and tetraalkylammonium, It is obtained by extraction with organic solvents, such as ethyl acetate and chloroform. In addition, the amine compound having a phenoxy group is reacted by heating a primary or secondary amine with a haloalkyl ether having a phenoxy group at the terminal, and after adding an aqueous solution of a strong base such as sodium hydroxide, potassium hydroxide and tetraalkylammonium, It can also be obtained by extracting with organic solvents such as ethyl acetate and chloroform.

(4) Ammonium salt

Ammonium salts may also be suitably used.

As an anion of an ammonium salt, halide, sulfonate, borate, and phosphate are mentioned, for example. Of these, halides and sulfonates are particularly preferred.

As the halide, chloride, bromide and iodide are particularly preferred.

As the sulfonate, an organic sulfonate having 1 to 20 carbon atoms is particularly preferable. As an organic sulfonate, a C1-C20 alkylsulfonate and an arylsulfonate are mentioned, for example.

The alkyl group contained in the alkylsulfonate may have a substituent. As this substituent, a fluorine atom, a chlorine atom, a bromine atom, an alkoxy group, an acyl group, and an aryl group are mentioned, for example. As the alkylsulfonate, specifically methanesulfonate, ethanesulfonate, butanesulfonate, hexanesulfonate, octanesulfonate, benzylsulfonate, trifluoromethanesulfonate, pentafluoroethanesulfonate and nonafluorobutane Sulfonate.

As an aryl group contained in an aryl sulfonate, a phenyl group, a naphthyl group, and an anthryl group are mentioned, for example. 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, methyl, ethyl, n-propyl, isopropyl, n-butyl, i-butyl, t-butyl, n-hexyl and cyclohexyl groups are preferable, for example. As another substituent, a C1-C6 alkoxy group, a halogen atom, cyano, nitro, an acyl group, and an acyloxy group is mentioned.

This ammonium salt may be hydroxide or carboxylate. In this case, this ammonium salt is tetraalkylammonium hydroxide, such as tetraalkylammonium hydroxide (tetramethylammonium hydroxide and tetraethylammonium hydroxide, tetra- (n-butyl) ammonium hydroxide of 1-8 carbons). Particularly preferred is a seed.

Preferable basic compounds include, for example, guanidine, aminopyridine, aminoalkylpyridine, aminopyrrolidine, indazole, imidazole, pyrazole, pyrazine, pyrimidine, purine, imidazoline, pyrazoline, Furane and aminoalkyl morpholine. These may further have a substituent. Preferred examples of the substituent include amino, aminoalkyl, alkylamino, aminoaryl, arylamino, alkyl, alkoxy, acyl, acyloxy, aryl, aryloxy, nitro, hydroxyl, and cyano .

Particularly preferred basic compounds are, for example, guanidine, 1,1-dimethylguanidine, 1,1,3,3-tetramethylguanidine, imidazole, 2-methylimidazole, 4- Aminopyridine, 4-aminopyridine, 2-aminopyridine, 2-aminopyridine, 2-phenylimidazole, Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2- Aminopyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethylpiperidine, Aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-iminopiperidine, 1- Amino-3-methyl-1-p-tolylpyrazole, 3-amino- Sol, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine, 2-pyrazoline, 3-pyrazoline, N- Aminomorpholine and N- (2-aminoethyl) morpholine.

(5) Compounds having a proton acceptor functional group and decomposed by irradiation with actinic radiation or radiation to produce a compound whose proton acceptor deteriorates, disappears or changes from proton acceptor to acidic.

The composition according to the present invention is a compound having a proton acceptor functional group as a basic compound and decomposed by irradiation with actinic light or radiation to generate a compound whose degradation of proton acceptor is reduced, lost or changed from proton acceptor to acidic. It may further contain [hereinafter also called a compound (PA)].

A proton acceptor functional group is a functional group having an electron or a group capable of electrostatically interacting with a proton, for example, a functional group having a macrocyclic structure such as a cyclic polyether, or a nitrogen having a non-covalent electron pair not contributing to the? It means the functional group which has an atom. The nitrogen atom which has a lone pair which does not contribute to (pi) conjugation is a nitrogen atom which has a partial structure represented by the following general formula, for example.

As a preferable partial structure of a proton acceptor functional group, a crown ether, an aza crown ether, 1-3 tertiary amine, a pyridine, imidazole, a pyrazine structure, etc. are mentioned, for example.

Compound (PA) is decomposed by irradiation of actinic light or radiation to generate a compound whose degradation of proton acceptor property is reduced, lost or changed from proton acceptor property to acidity. Here, the decrease, loss, or change of proton acceptor properties from acid to proton acceptor is a change in proton acceptor due to the addition of protons to the proton acceptor functional group, specifically, a proton acceptor functional group. When a proton adduct is produced | generated from the compound (PA) and proton which it has, it means that the equilibrium constant in the chemical equilibrium is reduced.

The proton acceptor property can be confirmed by performing pH measurement.

In the present invention, it is preferable that the acid dissociation constant pKa of the compound generated by decomposition of compound (PA) by irradiation of actinic rays or radiation satisfies pKa <-1, more preferably -13 <pKa <-1. More preferably, it is -13 <pKa <-3.

In the present invention, the acid dissociation constant pKa represents an acid dissociation constant pKa in an aqueous solution, and is described in, for example, the Chemical Handbook (II) (Rev. 4, 1993, Japanese Society for Japanese Studies, Maruzen Corporation). The lower the value, the larger the acid strength. The acid dissociation constant pKa in aqueous solution can be actually measured by measuring the acid dissociation constant at 25 degreeC using an infinite dilution aqueous solution, and also the database of the substituent constant of Hammet and the well-known document value using the following software package 1 The value based on can also be obtained by calculation. All pKa values described in this specification represent values calculated by calculation using this software package.

Software Package 1: Advanced Chemistry Development (ACD / Labs) Software V8. 14 for Solaris (1994-2007 ACD / Labs)

Compound (PA) is the proton adduct that is decomposed and generated by irradiation with actinic light or radiation, and generates a compound represented by the following general formula (PA-1), for example. The compound represented by the general formula (PA-1) is a compound which has an acidic group together with a proton acceptor functional group, thereby reducing the proton acceptor property, losing or changing from proton acceptor property to acidic acid, as compared with the compound (PA). .

In the 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 means 0 or 1;

B represents a single bond, an oxygen atom, or -N (Rx) Ry-. Rx represents a hydrogen atom or monovalent organic group, and Ry represents a single bond or a divalent organic group. You may combine with Ry and form a ring, or you may combine with R and form a ring.

R represents a monovalent organic group having a proton accepting functional group.

General formula (PA-1) is demonstrated in more detail.

As a bivalent coupling group in A, Preferably it is a C2-C12 bivalent coupling group, For example, an alkylene group, a phenylene group, etc. are mentioned. More preferably, it is an alkylene group which has at least 1 fluorine atom, Preferable carbon number is 2-6, More preferably, it is C2-C4. You may have coupling groups, such as an oxygen atom and a sulfur atom, in an alkylene chain. The alkylene group is particularly preferably an alkylene group in which 30 to 100% of the number of hydrogen atoms is substituted with a fluorine atom, and more preferably a carbon atom bonded to a Q moiety has a fluorine atom. Further, a perfluoroalkylene group is preferable, and a perfluoroethylene group, a perfluoropropylene group, and a perfluorobutylene group are more preferable.

As monovalent organic group in Rx, Preferably it is C1-C30, For example, an alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned. These groups may further have a substituent.

As an alkyl group in Rx, it may have a substituent, Preferably it is a C1-C20 linear and branched alkyl group, and may have an oxygen atom, a sulfur atom, and a nitrogen atom in an alkyl chain.

As a bivalent organic group in Ry, Preferably, an alkylene group is mentioned. As a ring structure which Rx and Ry may combine with each other, the 5-10 membered ring containing a nitrogen atom, Especially preferably, a 6 membered ring is mentioned.

In addition, examples of the alkyl group having a substituent include groups in which a cycloalkyl group is substituted (for example, adamantylmethyl group, adamantylethyl group, cyclohexylethyl group, camphor residues, etc.).

As a cycloalkyl group in Rx, you may have a substituent, Preferably it is a C3-C20 cycloalkyl group, and may have an oxygen atom in a ring.

As an aryl group in Rx, you may have a substituent, Preferably it is a C6-C14 aryl group.

As an aralkyl group in Rx, you may have a substituent, Preferably, a C7-20 aralkyl group is mentioned.

As an alkenyl group in Rx, you may have a substituent, For example, group which has a double bond in the arbitrary position of the alkyl group enumerated as Rx is mentioned.

The proton acceptor functional group in R is as above-mentioned, The group which has a heterocyclic aromatic structure containing nitrogen such as aza crown ether, primary-tertiary amine, pyridine, and imidazole, etc. are mentioned.

As an organic group which has such a structure, preferable carbon number is 4-30, An alkyl group, a cycloalkyl group, an aryl group, an aralkyl group, an alkenyl group, etc. are mentioned.

Alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group, alkyl group, cycloalkyl group, aryl group, aralkyl group, alkenyl group containing a proton accepting functional group or an ammonium group in R are alkyl groups listed as Rx. And a cycloalkyl group, an aryl group, an aralkyl group and an alkenyl group.

As a substituent which each said group may have, a halogen atom, a hydroxyl group, a nitro group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably C3-C10), an aryl group (preferably C6-C6) ~ 14), alkoxy group (preferably 1 to 10 carbon atoms), acyl group (preferably 2 to 20 carbon atoms), acyloxy group (preferably 2 to 10 carbon atoms), alkoxycarbonyl group (preferably And C2-C20), an amino acyl group (preferably C2-C20), etc. are mentioned. About a cyclic structure and an aminoacyl group in an aryl group, a cycloalkyl group, an alkyl group (preferably C1-C20) is mentioned as a substituent.

When B is -N (Rx) Ry-, it is preferable that R and Rx combine with each other and form the ring. Stability improves by forming ring structure, and storage stability of the composition using this improves. 4-20 carbon atoms are preferable, monocyclic or polycyclic may be sufficient as a ring, and the ring may contain the oxygen atom, the sulfur atom, and the nitrogen atom.

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 including a nitrogen atom. As a polycyclic structure, the structure which consists of a combination of 2 or 3 or more monocyclic structures is mentioned. The monocyclic structure and the polycyclic structure may have a substituent, for example, a halogen atom, a hydroxyl group, a cyano group, a carboxyl group, a carbonyl group, a cycloalkyl group (preferably 3 to 10 carbon atoms), an aryl group (preferably Is 6 to 14 carbon atoms, alkoxy group (preferably 1 to 10 carbon atoms), acyl group (preferably 2 to 15 carbon atoms), acyloxy group (preferably 2 to 15 carbon atoms), alkoxycarbonyl group (Preferably 2 to 15 carbon atoms), aminoacyl group (preferably 2 to 20 carbon atoms) and the like are preferable. About the cyclic structure in an aryl group, a cycloalkyl group, an alkyl group (preferably C1-C15) is mentioned further as a substituent. About an aminoacyl group, an alkyl group (preferably C1-C15) is mentioned further as a substituent.

Preferably used as the R _f of the NHX ₁ -X ₂ R _f represented by Q is an alkyl group which also take the number of carbon atoms 1 to 6 fluorine atoms, more preferably alkyl groups having 1 to 6 perfluoroalkyl. Moreover, as X <_1> and X <_2> , it is preferable that at least one is -SO <_2> -, More preferably, it is a case where both of X <_1> and X <_2> are -SO <_2> -.

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

It is preferable that compound (PA) is an ionic compound. Although a proton acceptor functional group may be contained in either an anion part or a cation part, it is preferable that it is contained in an anion part.

As a compound (PA), The compound preferably represented by following General formula (4)-(6) is mentioned.

In General Formulas (4) to (6), A, X, n, B, R, R _f , X ₁ and X ₂ have the same meanings as those in General Formula (PA-1).

C ⁺ represents a counter cation.

As a counter cation, an onium cation is preferable. More specifically, the sulfonium cation first described as S ⁺ (R ₂₀₁ ) (R ₂₀₂ ) (R ₂₀₃ ) in general formula (ZI), I ⁺ (R ₂₀₄ ) (R in general formula (ZII) Iodine cation described as ₂₀₅ ) is preferable.

Specific examples of the compound (PA) are shown below, but the present invention is not limited thereto.

In addition, in this invention, compound (PA) other than the compound which produces the compound represented by general formula (PA-1) can also be selected suitably. For example, you may use the compound which has a proton acceptor site | part as a ionic compound. More specifically, the compound etc. which are represented by following General formula (7) are mentioned.

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 by a proton acceptor functional group.

X ⁻ represents a counter anion.

X ^- Specific examples of X in the above-mentioned general formula (ZI) ^- may be mentioned, such as.

Specific examples of the aryl group of R and R _N examples include preferably a phenyl group.

As a specific example of the proton accepting functional group which R _N has, it is the same as the proton accepting functional group demonstrated by Formula (PA-1) mentioned above.

In the composition of this invention, 0.1-10 mass% is preferable in all solid content, and, as for the compounding ratio in the whole composition of compound (PA), More preferably, it is 1-8 mass%.

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

Further, as the basic compound, a photosensitive basic compound may be used. As a photosensitive basic compound, the compound as described in Unexamined-Japanese-Patent No. 2003-524799, VIII. Photopolym. Sci & Tech. Vol. 8, p.543-553 (1995) etc. can be used, for example.

The molecular weight of a basic compound is 100-1500 normally, Preferably it is 150-1300, More preferably, it is 200-1000.

These basic compounds may be used individually by 1 type, and may be used in combination of 2 or more type.

When the composition by this invention contains a basic compound, it is preferable that it is 0.01-8.0 mass% on the basis of the total solid of a composition, It is more preferable that it is 0.1-5.0 mass%, It is 0.2-4.0 mass Particularly preferred is%.

The molar ratio of the basic compound to the photoacid generator is preferably 0.01 to 10, more preferably 0.05 to 5, still more preferably 0.1 to 3. If the molar ratio is excessively large, sensitivity and / or resolution may decrease. If the molar ratio is made excessively small, there is a possibility that a thickening of the pattern may occur between exposure and heating (post baking). More preferably, it is 0.05-5, More preferably, it is 0.1-3.

(Surfactants)

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

As the fluorine-based and / or silicon-based surfactant, for example, Dainippon Ink & Chemicals, Inc. Megaface F176 and Megaface R08 from OMNOVA, PF656 and PF6320 from OMNOVA, Troysol S-366 from Troy Chemical, Sumitomo 3M Inc. Products of Florad FC430, and Shin-Etsu Chemical Co., Ltd. The polysiloxane polymer KP-341 of a product is mentioned.

You may use surfactant other than a fluorine type and / or a silicon type. As this surfactant, nonionic surfactant, such as polyoxyethylene alkyl ethers and polyoxyethylene alkylaryl ethers, is mentioned, for example.

In addition, well-known surfactant can be used suitably. As the surfactant that can be used, for example, the surfactants described after the specification of US Patent 2008 / 0248425A No. 1 may be mentioned.

Surfactant may be used individually by 1 type, and may be used in combination of 2 or more type.

When the composition according to the present invention further contains a surfactant, the amount thereof is preferably 0.0001 to 2% by mass, more preferably 0.001 to 1% by mass, based on the total solids of the composition.

(dyes)

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 (more And Orient Chemical Industries Co., Ltd.) and crystal violet (CI42555), methyl violet (CI42535), rhodamine B (CI45170B), malachite green (CI42000) and methylene blue (CI52015).

(Photobase generator)

The composition according to the present invention may further contain a photobase generator. By containing a photobase generator, it becomes possible to form a more favorable pattern.

As a photobase generator, For example, Unexamined-Japanese-Patent No. 4-151156, 4-162040, 5-197148, 5-5995, 6-194834, 8-146608, 10 -83079 and the compounds described in European Patent 622682. Preferred photobase generators are specifically 2-nitrobenzylcarbamate, 2,5-dinitrobenzylcyclohexylcarbamate, N-cyclohexyl-4-methylphenylsulfamide and 1,1-dimethyl-2-phenyl Ethyl-N-isopropylcarbamate.

(Antioxidant)

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

Examples of the antioxidant include phenolic antioxidants, antioxidants composed of organic acid derivatives, sulfur-containing antioxidants, phosphorus antioxidants, amine antioxidants, antioxidants consisting of amine-aldehyde condensates, and amine-ketone condensates. The antioxidant which consisted of these is mentioned. It is especially preferable to use the antioxidant which consists of a phenolic antioxidant and organic acid derivative among these antioxidants. In this way, the function as an antioxidant can be expressed, without reducing the performance of a composition.

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

Examples of the substituted phenols include 1-oxy-3-methyl-4-isopropylbenzene, 2,6-di-tert-butylphenol, 2,6-di-tert-butyl-4-ethylphenol and 2,6 -Di-tert-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, butylhydroxyanisole, 2- (1-methylcyclohexyl) -4,6-dimethyl Phenol, 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-butylphenyl) propionate, octylated phenol, aralkyl substituted phenols, alkylated p-cresols, and hindered phenols.

Examples of the bis, tris or polyphenols include 4,4'-dihydroxydiphenyl, methylenebis (dimethyl-4,6-phenol), 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 crosslinked polyvalent alkylphenol , 4,4'-butylidenebis- (3-methyl-6-tert-butylphenol), 1,1-bis- (4-hydroxyphenyl) -cyclohexane, 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.

As antioxidant, Preferably, 2, 6- di-t- butyl- 4-methyl phenol, 4-hydroxymethyl- 2, 6- di-t- butyl phenol, 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. Among these, 2,6-di-t-butyl-4-methylphenol, 4-hydroxymethyl-2,6-di-t-butylphenol, butylhydroxyanisole and t-butylhydroquinone are more preferable, More preferred are 2,6-di-t-butyl-4-methylphenol or 4-hydroxymethyl-2,6-di-t-butylphenol.

Antioxidant may be used individually by 1 type, and may be used in combination of 2 or more type.

In the case of containing the antioxidant in the composition according to the present invention, the amount of addition is preferably 1 ppm or more, more preferably 5 ppm or more, still more preferably 10 ppm or more, even more preferably 50 ppm or more. Especially preferably, it is 100 ppm or more, Most preferably, it is 100-1000 ppm.

(solvent)

The composition by this invention may contain the solvent further.

As this solvent, the organic solvent is used typically. Examples of the organic solvent include alkylene glycol monoalkyl ether carboxylates, alkylene glycol monoalkyl ethers, lactic acid alkyl esters, alkyl alkoxypropionates, cyclic lactones (preferably having 4 to 10 carbon atoms) and rings. Monoketone compounds (preferably having 4 to 10 carbon atoms), alkylene carbonates, alkyl alkoxyacetic acid and alkyl pyruvate.

Examples of the alkylene glycol monoalkyl ether carboxylates include propylene glycol monomethyl ether acetate (PGMEA; alias 1-methoxy-2-acetoxy propane), propylene glycol monoethyl ether acetate, propylene glycol monopropyl ether acetate, Propylene glycol monobutyl ether acetate, propylene glycol monomethyl ether propionate, propylene glycol monoethyl ether propionate, ethylene glycol monomethyl ether acetate and ethylene glycol monoethyl ether acetate are preferable.

As alkylene glycol monoalkyl ether, for example, propylene glycol monomethyl ether (PGME; alias 1-methoxy-2-propanol), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, ethylene glycol Monomethyl ether and ethylene glycol monoethyl ether.

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

Examples of the alkyl alkoxypropionate include ethyl 3-ethoxypropionate, methyl 3-methoxypropionate, methyl 3-ethoxypropionate and ethyl 3-methoxypropionate.

As the cyclic lactone, there may be mentioned, for example,? -Propiolactone,? -Butyrolactone,? -Butyrolactone,? -Methyl-? -Butyrolactone,? -Methyl-? -Butyrolactone,? -Valerolactone ,? -caprolactone,? -octanoic lactone and? -hydroxy-? -butyrolactone.

As a monoketone compound which may contain the ring, for example, 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-hexe-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-dimethylcyclo Hexanon, 2,2,6-trimethylcyclohexanone, cycloheptanone, 2-methylcyclo There may be mentioned heptanone and 3-methyl-bicyclo-heptanone.

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- And acetic acid-1-methoxy-2-propyl.

The alkyl pyruvate includes, for example, methyl pyruvate, ethyl pyruvate and pyruvic acid.

As a solvent, it is preferable to use what has a boiling point of 130 degreeC or more under normal temperature and normal pressure. Specifically, for example, cyclopentanone, γ-butyrolactone, cyclohexanone, ethyl lactate, ethylene glycol monoethyl ether acetate, PGMEA, ethyl 3-ethoxypropionate, ethyl pyruvate, 2-ethoxyethyl acetate And acetic acid-2- (2-ethoxyethoxy) ethyl and propylene carbonate.

These solvents may be used individually by 1 type, and may mix and use two or more types. 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.

As a solvent containing a hydroxyl group, ethylene glycol, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, propylene glycol, PGME, propylene glycol monoethyl ether, ethyl lactate, etc. are mentioned, for example. Of these, PGME and ethyl lactate are particularly preferred.

Examples of the solvent not containing a hydroxyl group include PGMEA, ethyl ethoxypropionate, 2-heptanone, γ-butyrolactone, cyclohexanone, butyl acetate, N-methylpyrrolidone, N, N-dimethylacetamide, dimethyl sulfoxide, etc. are mentioned, Among them, propylene glycol monomethyl ether acetate, ethyl ethoxy propionate, 2-heptanone, (gamma) -butyrolactone, cyclohexanone, and butyl acetate are mentioned. Can be. Among these, PGMEA, ethyl ethoxy propionate and 2-heptanone are particularly preferable.

When using the mixed solvent of the solvent containing a hydroxyl group and the solvent not containing a hydroxyl group, these mass ratio becomes like this. Preferably it is 1 / 99-99 / 1, More preferably, it is 10 / 90-90 It is / 10, More preferably, it is 20/80-60/40.

Moreover, especially the outstanding coating uniformity can be achieved when using the mixed solvent which contains 50 mass% or more of solvents which do not contain a hydroxyl group. In addition, the solvent is particularly preferably a mixed solvent of PGMEA and at least one other solvent.

&Lt; 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 onto a support such as a substrate to form a film.

As for the thickness of this film | membrane, 0.02-0.1 micrometer is preferable. As a method of apply | coating on a board | substrate, spin coating is preferable and the rotation speed of 1000-3000 rpm is preferable.

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

Next, actinic light or a radiation is irradiated to the said photosensitive film, Preferably it bakes (80-150 degreeC normally, More preferably, it is 90-130 degreeC), and develops. By baking, a better pattern can be obtained.

Examples of the active light or radiation include infrared light, visible light, ultraviolet light, far ultraviolet light, X-rays, and electron beams. As these actinic rays or radiation, it is more preferable to have a wavelength of 250 nm or less, especially 220 nm or less. Examples of such active light 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 examples of the active ray or radiation include KrF excimer laser, electron beam, X-ray and EUV light.

In the developing step, 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, first amines such as ethylamine and n-propylamine, diethylamine and di-n. 2nd amines, such as butylamine, 3rd amines, such as triethylamine and methyldiethylamine, alcohol amines, such as dimethylethanolamine and triethanolamine, agent, such as tetramethylammonium hydroxide and tetraethylammonium hydroxide And alkaline aqueous solutions containing cyclic amines such as quaternary ammonium salts or pyrrole and piperidine.

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

The density | concentration of alkaline developing solution is 0.1-20 mass% normally. PH of alkaline developing solution is 10.0-15.0 normally.

In addition, about the detail of the process at the time of making the mold for imprinting using the composition by this invention, For example, Unexamined-Japanese-Patent No. 4109085, Unexamined-Japanese-Patent No. 2008-162101, and "Tiling technology development of nanoimprint, for example. Application Development-Nanoimprint Substrate Technology and Latest Technology Development-Hirai Yoshihiko (Frontier Publishing).

<< Example >>

EMBODIMENT OF THE INVENTION Hereinafter, although the form of this invention is demonstrated in more detail by an Example, the content of this invention is not limited by this.

(First Embodiment)

<Resin>

Synthesis Example 1-1 Resin A-14

Resin A-14 was synthesized according to the following scheme.

225 g of acetic anhydride and 105.09 g of pyridine were added to 25.00 g of Compound (1), followed by stirring at room temperature for 12 hours. This was cooled to 0 ° C, distilled water was added to precipitate a solid. Filtration took out the solid, 1000 mL of 1 N hydrochloric acid was added, and it stirred at room temperature for 30 minutes. Then, the obtained solid was taken out by filtration. 1000 mL of distilled water was added to this solid, and after stirring at room temperature for 30 minutes, it filtered and extracted the solid. The obtained solid was dissolved in ethyl acetate, dried over 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. 22.08 g of N, N-dimethylformamide di-tert-butylacetal was added dropwise to the obtained solution at room temperature over 15 minutes. After stirring for 9 hours under reflux, the mixture was filtered. 1 N sodium hydroxide aqueous solution was added to the obtained filtrate. Extraction using ethyl acetate was performed three times. Distilled water was added to the obtained organic layer, the mixture was washed, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 9.5 g of Compound (3).

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

13.79 g of p-acetoxystyrene, 5.41 g of compound (4) and 1.38 g of polymerization initiator V-601 (manufactured by Wako Pure Chemical Industries, Ltd.) were dissolved in 61.40 g of PGMEA. 15.4 g of PGMEA was put in a reaction vessel, and it was dripped over 4 hours in 85 degreeC system in nitrogen gas atmosphere. After dripping and stirring for 2 hours, the reaction solution was cooled to room temperature. 31.98 g of methanol and 1.54 g of sodium methoxide (28% methanol solution) were added to the reaction solution, followed by stirring at room temperature for 3 hours. 1 N hydrochloric acid was added to make acid, ethyl acetate was added, the organic layer was washed three times with distilled water, and the solvent was distilled off. 70 g of acetone was added to dissolve and the mixture was dropped in 800 g of hexane / ethyl acetate = 8/2 to precipitate a polymer. This was filtered, washed with 200 g of hexane / ethyl acetate = 8/2, and dried under reduced pressure to obtain 11.38 g of Resin A-14.

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

Synthesis Example 1-2: Resin A-11

Resin A-11 was synthesized according to the following scheme.

280.00 g of N-methylpyrrolidone, 47.64 g of p-chloromethylstyrene, and 51.77 g of potassium carbonate were added to 50.00 g of Compound (6), and the mixture was heated and stirred at 80 ° C for 5 hours. After cooling to room temperature, this was poured into 3 L of distilled water, and the resulting solid was taken out by filtration. Acetone was added to this, the solid was removed by filtration, and the solvent of the filtrate was distilled off. Diisopropyl ether was added, the solid was removed by filtration, and the solvent of the filtrate was distilled off. Diisopropyl ether was added again, the solid was removed by filtration, and the solvent of the filtrate was distilled off. Acetone was added to this, it was dripped at distilled water, and it filtered and obtained solid. The resulting solid was dried under reduced pressure to obtain 33.78 g of compound (7).

57.00 g of N-methylpyrrolidone, 10.21 g of Compound (8), and 7.50 g of potassium carbonate were added to 10.00 g of Compound (7), followed by heating and stirring at 80 ° C over 4 hours. The mixture was allowed to cool to room temperature, ethyl acetate was added, the organic layer was washed three times with distilled water, dried over anhydrous magnesium sulfate, and the solvent was distilled off. Purification by column chromatography (hexane / ethyl acetate) gave 13.08 g of Compound (9).

Hereinafter, the compound (10) and the resin A-11 were obtained like Example 1-1 except having used the compound (9) instead of the compound (4).

About this resin A-11, the same evaluation as previously demonstrated in the synthesis example 1-1 was performed. The results are shown in Table 1 below.

Synthesis Example 1-3: Other Resin

Each of resins A-1 to A-10, A-12, A-13, and A-15 to A-33 was synthesized in the same manner as described in Synthesis Examples 1-1 and 1-2. In addition, these resins were evaluated in the same manner as those described in Synthesis Examples 1-1 and 1-2.

The weight average molecular weight, composition ratio, and dispersion degree of resin A-1-A-33 are put together in following Table 1.

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

Molar composition ratio 65/35, weight average molecular weight 15000, dispersion degree 1.55

Molar composition ratio 60/40, weight average molecular weight 10000, dispersion degree 1.40

Molar composition ratio 42/45/13, weight average molecular weight 6000, dispersion degree 1.50

&Lt;

As the photo-acid generator, any of B-1 to B-120 listed above was used.

&Lt; Basic compound >

As the basic compound, any one of the following N-1 to N-7 was used. In addition, N-7 corresponds to the compound (PA) mentioned above.

Synthesis Example 1-4 Compound N-7

Compound N-7 was synthesized based on Japanese Patent Application Laid-Open No. 2006-330098.

<Surfactant>

As the surfactant, any one of the following W-1 to W-4 was used.

W-1: Megaface R08 (manufactured by Dainippon Ink & Chemicals, Inc .; fluorine and silicon based)

W-2: Polysiloxane polymer KP-341 (product of Shin-Etsu Chemical Co., Ltd., silicon system)

W-3: Troysol S-366 from Troy Chemical; Fluorine

W-4: PF6320 (product of OMNOVA; fluorine-based)

<Solvent>

As a solvent, any one of following S-1-S-4 was mixed and used suitably.

S-1: PGMEA (b.p. = 146 DEG C)

S-2: PGME (b.p. = 120 ° C)

S-3: Methyl lactate (b.p. = 145 ° C)

S-4: cyclohexanone (b.p. = 157 degreeC)

Resist Evaluation (EB)

Each component shown in following Table 2 was melt | dissolved in the solvent shown in the same table, and the solution whose solid content concentration is 3.0 mass% was prepared. This solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 mu m to obtain a positive resist solution.

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

The positive resist solution was applied onto a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. This was heated to dry 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 Isolation Pattern Resolution]

This resist film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd .; an acceleration voltage of 50 keV). Immediately after irradiation, it was heated on a hotplate at 130 ° C. for 90 seconds. Then, it developed for 60 second at 23 degreeC using the tetramethylammonium hydroxide aqueous solution of 2.38 mass% of concentration, and rinsed with pure water for 30 second, and dried. As a result, 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 the scanning electron microscope (S-4800 by Hitachi, Ltd.). And the minimum irradiation energy at the time of resolving a line of 100 nm line width was calculated | required, and this value was called "sensitivity (microC / cm <2>)".

(Pattern shape)

The cross-sectional shape of the 100 nm line pattern (line: space = 1: 1) in the irradiation amount which shows the said sensitivity was observed using the scanning electron microscope (S-4800 by Hitachi, Ltd.). Then, the shape was evaluated in two stages of "rectangle" or "taper".

(Roughness characteristic: line edge roughness (LER))

The above 100 nm line pattern (line: space = 1: 1) was observed using a scanning electron microscope (S-9260, Hitachi, Ltd.). And the distance between the reference line which should have an edge and an actual edge was measured about 30 points of equal intervals contained in the 50 micrometers of longitudinal directions. Then, the standard deviation of this distance was calculated, and 3σ was calculated. And this 3σ was called "LER (nm)."

(Resolution of isolation pattern; resolution)

The limit resolution (the minimum line width at which the line and the space are resolved separately) of the isolation pattern (line: space = 1:> 100) in the irradiation dose indicating the sensitivity was obtained. And this value was called "resolution (nm)."

<Etching Resistance>

After forming a positive resist film with a film thickness of 200 nm on the wafer, plasma was mixed for 30 seconds under a temperature of 23 ° C. using a mixed gas of C ₄ F ₆ (20 mL / min) and O ₂ (40 mL / min). Etching was performed. Thereafter, the amount of the remaining film 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 s / sec

× (insufficient): when the etching rate is 15 kV / sec or more

These evaluation results are shown in Table 2 below.

As shown in Table 2, the composition of the Example was excellent in all of the sensitivity, pattern shape, LER, resolution of the isolated pattern, and etching resistance compared with the composition of the comparative example.

&Lt; Resist evaluation (EUV) >

Each component shown in following Table 3 was melt | dissolved in the solvent shown in the same table, and the solution whose solid content concentration is 3.0 mass% was prepared. This solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 mu m to obtain a positive resist solution.

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

The positive resist solution was applied onto a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. This was heat-dried on a hotplate at 120 degreeC for 90 second, and the resist film which has an average film thickness of 100 nm was obtained.

[Sensitivity, pattern shape, and roughness characteristics]

This resist film was irradiated with EUV light using an EUV exposure apparatus. Immediately after irradiation, it was heated on a hotplate at 130 ° C. for 90 seconds. Then, it developed for 60 second at 23 degreeC using the tetramethylammonium hydroxide aqueous solution of 2.38 mass% of concentration, and rinsed with pure water for 30 second, and dried. As a result, 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 the scanning electron microscope (S-4800 by Hitachi, Ltd.). And the minimum irradiation energy at the time of resolving the line of 100 nm line width was calculated | required, and this value was called "sensitivity (mJ / cm <2>)".

(Pattern shape)

The cross-sectional shape of the 100 nm line pattern (line: space = 1: 1) in the irradiation amount which shows the said sensitivity was observed using the scanning electron microscope (S-4800 by Hitachi, Ltd.). Then, the shape was evaluated in two stages of "rectangle" or "taper".

(Roughness characteristic: LER)

The above 100 nm line pattern (line: space = 1: 1) was observed using a scanning electron microscope (S-9260, Hitachi, Ltd.). And the distance between the reference line which should have an edge and an actual edge was measured about 30 points of equal intervals contained in the 50 micrometers of longitudinal directions. Then, the standard deviation of this distance was calculated, and 3σ was calculated. And this 3σ was called "LER (nm)."

These evaluation results are shown in Table 3 below.

As shown in Table 3, the composition of the Example was excellent in all of a sensitivity, a pattern shape, and LER compared with the composition of a comparative example.

(Second Embodiment)

<Resin>

Resin P-1-P-41 enumerated first was synthesize | combined as follows.

Synthesis Example 2-1 Resin P-14

Resin P-14 was synthesized according to the following scheme.

<Synthesis of Compound (4)>

225 g of acetic anhydride and 105.09 g of pyridine were added to 25.00 g of Compound (1), followed by stirring at room temperature for 12 hours. This was cooled to 0 ° C, distilled water was added to precipitate a solid. Filtration took out the solid, 1000 mL of 1 N hydrochloric acid was added, and it stirred at room temperature for 30 minutes. Then, the obtained solid was taken out by filtration. 1000 mL of distilled water was added to this solid, and after stirring at room temperature for 30 minutes, it filtered and extracted 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. 22.08 g of N, N-dimethylformamide di-tert-butylacetal was added dropwise to the obtained solution at room temperature over 15 minutes. After heating for 9 hours under reflux, the mixture was filtered. 1 N sodium hydroxide aqueous solution was added to the obtained filtrate. Extraction using ethyl acetate was performed three times. Distilled water was added to the obtained organic layer, the mixture was washed, dried over anhydrous magnesium sulfate, and then the solvent was distilled off to obtain 9.5 g of Compound (3).

9.5 g of compound (3) was dissolved in 85 g of methanol. 6.88 g of potassium carbonate was added to the obtained solution, and the mixture was stirred at room temperature for 3 hours. The solid obtained by distilling off the solvent was dissolved in 85 g of acetone. 6.88 g of potassium carbonate and 6.08 g of chloromethyl styrene were added to the obtained solution, and the mixture was stirred for 4 hours under reflux. The reaction solution was filtered, and the solvent contained in the obtained filtrate was distilled off. Ethyl acetate was added thereto, the organic layer was washed three times with distilled water, dried over anhydrous magnesium sulfate, and the solvent was distilled off. The obtained solid was washed three times with hexane 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 obtained solution was cooled to 0 degreeC, and 47.60g sodium methoxide (28% methanol solution) was dripped over 30 minutes. Then, this was stirred at room temperature over 5 hours. Ethyl acetate was added to the reaction solution, the organic layer was washed three times with distilled water, dried over anhydrous sodium sulfate, and the solvent was distilled off. Thus, 131.70 g of compound (6) (54% ethyl acetate solution) was obtained.

To 18.52 g of compound 6 (54% ethyl acetate solution), 56.00 g of ethyl acetate was added. 31.58 g of 1,1,2,2,3,3-hexafluoropropane-1,3-disulfonyldifluoride was added thereto and cooled to 0 ° C. The solution which melt | dissolved 12.63 g of triethylamine in 25.00 g of ethyl acetate was dripped over 30 minutes, and it stirred over 4 hours, maintaining liquid temperature at 0 degreeC. Ethyl acetate was added, the organic layer was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. Thus, 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 1 N sodium hydroxide aqueous solution was added, and the mixture was stirred at room temperature for 2 hours. After the solvent was distilled off, ethyl acetate was added, the organic layer was washed three times with saturated brine, dried over anhydrous sodium sulfate, and the solvent was distilled off. Thus, 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 three times with chloroform. The solvent was distilled off after wash | cleaning the obtained organic layer three times with distilled water. Thus, 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), and 4.84 g of polymerization initiator V-601 (Wako Pure Chemical) Industries, Ltd.) was dissolved in 77.53 g of propylene glycol monomethyl ether (PGME). 25.76 g of PGME was added to the reaction vessel, and it was dripped over 4 hours in 85 degreeC system in nitrogen gas atmosphere. After stirring and heating the reaction solution over 2 hours, this was cooled to room temperature.

The reaction solution was diluted by adding 92 g of acetone. The diluted solution was added dropwise into 2800 g of hexane / ethyl acetate = 8/2 to precipitate the polymer and to filter. The washing was carried out while spraying the filtered solid with 700 g of hexane / ethyl acetate = 8/2. The obtained solid was dissolved in 100 g of acetone, and added dropwise into 1000 g of methanol / distilled water = 1/9 to precipitate the polymer and filter. The washing was performed while sprinkling on a solid filtered using 250 g of methanol / distilled water = 1/9. Thereafter, the washed solid was subjected to drying under a reduced pressure 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 (made by TOSHO CO., INC .; HLC-8120; Tsk gel Multipore HXL-M). The results are shown in Table 4 below. In this GPC measurement, THF was used as the solvent.

Synthesis Example 2-2: Other Resin

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 2-1. In addition, these resins were evaluated in the same manner as described in Synthesis Example 2-1. The weight average molecular weight, composition ratio, and dispersion degree of resin P-1-P-41 are put together in following Table 4.

For comparison, comparative compounds C-1 to C-3 as used in the examples according to the first embodiment were prepared. Moreover, the photoacid generator, basic compound, surfactant, and solvent which were used in the Example by 1st Embodiment were prepared.

Resist Evaluation (EB)

Each component shown in following Table 5 was melt | dissolved in the solvent shown in the same table, and the solution whose solid content concentration is 3.0 mass% was prepared. This solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 mu m to obtain a positive resist solution.

The numerical value of "mass%" shown in Table 5 is a value based on the total solid of a composition. In addition, the usage-amount of surfactant is 0.01 mass% with respect to total solid concentration.

The positive resist solution was applied onto a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. This was heated to dry 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 Isolation Pattern Resolution]

This resist film was irradiated with an electron beam using an electron beam irradiation apparatus (HL750 manufactured by Hitachi, Ltd .; an acceleration voltage of 50 keV). Immediately after irradiation, it was heated on a hotplate at 130 ° C. for 90 seconds. Then, it developed for 60 second at 23 degreeC using the tetramethylammonium hydroxide aqueous solution of 2.38 mass% of concentration, and rinsed with pure water for 30 second, and dried. As a result, 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 the scanning electron microscope (S-4800 by Hitachi, Ltd.). And the minimum irradiation energy at the time of resolving a line of 100 nm line width was calculated | required, and this value was called "sensitivity (microC / cm <2>)".

(Pattern shape)

The cross-sectional shape of the 100 nm line pattern (line: space = 1: 1) in the irradiation amount which shows the said sensitivity was observed using the scanning electron microscope (S-4800 by Hitachi, Ltd.). Then, the shape was evaluated in two stages of "rectangle" or "taper".

(Roughness characteristic: line edge roughness (LER))

The above 100 nm line pattern (line: space = 1: 1) was observed using a scanning electron microscope (S-9260, Hitachi, Ltd.). And the distance between the reference line which should have an edge and an actual edge was measured about 30 points of equal intervals contained in the 50 micrometers of longitudinal directions. Then, the standard deviation of this distance was calculated, and 3σ was calculated. And this 3σ was called "LER (nm)."

(Resolution of isolation pattern; resolution)

The limit resolution (the minimum line width at which the line and the space are resolved separately) of the isolation pattern (line: space = 1:> 100) in the irradiation dose indicating the sensitivity was obtained. And this value was called "resolution (nm)."

[Etching Resistance]

After forming a positive resist film with a film thickness of 200 nm on the wafer, plasma etching was performed for 30 seconds at a temperature of 23 ° C. using a mixed gas of C ₄ F ₆ (20 mL / min) and O ₂ (40 mL / min). Done. Thereafter, the amount of the remaining film 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 s / sec

× (insufficient): when the etching rate is 15 kV / sec or more

The evaluation results are shown in Table 5 below.

As shown in Table 5, the composition of the Example was excellent in all of the sensitivity, pattern shape, LER, resolution of the isolated pattern, and etching resistance compared with the composition of the comparative example.

&Lt; Resist evaluation (EUV) >

Each component shown in following Table 6 was melt | dissolved in the solvent shown in the same table, and the solution whose solid content concentration is 3.0 mass% was prepared. This solution was filtered using a polytetrafluoroethylene filter having a pore size of 0.1 mu m to obtain a positive resist solution.

The numerical value of the "mass%" shown in Table 6 is a value based on the total solid of a composition. In addition, the usage-amount of surfactant is 0.01 mass% with respect to total solid concentration.

The positive resist solution was applied onto a silicon substrate subjected to hexamethyldisilazane treatment using a spin coater. This was heat-dried on a hotplate at 120 degreeC for 90 second, and the resist film which has an average film thickness of 100 nm was obtained.

[Sensitivity, pattern shape, and roughness characteristics]

EUV light was irradiated to this resist film using the EUV exposure apparatus. Immediately after irradiation, it was heated on a hotplate at 130 ° C. for 90 seconds. Then, it developed for 60 second at 23 degreeC using the tetramethylammonium hydroxide aqueous solution of 2.38 mass% of concentration, and rinsed with pure water for 30 second, and dried. As a result, 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 the scanning electron microscope (S-4800 by Hitachi, Ltd.). And the minimum irradiation energy at the time of resolving the line | wire of 100 nm line width was calculated | required, and this value was called "sensitivity (mJ / cm <2>)".

(Pattern shape)

The cross-sectional shape of the 100 nm line pattern (line: space = 1: 1) in the irradiation amount which shows the said sensitivity was observed using the scanning electron microscope (S-4800 by Hitachi, Ltd.). Then, the shape was evaluated in two stages of "rectangle" or "taper".

(Roughness characteristic: LER)

The above 100 nm line pattern (line: space = 1: 1) was observed using a scanning electron microscope (S-9260, Hitachi, Ltd.). And the distance between the reference line which should have an edge and an actual edge was measured about 30 points of equal intervals contained in the 50 micrometers of longitudinal directions. Then, the standard deviation of this distance was calculated, and 3σ was calculated. And this 3σ was called "LER (nm)."

These evaluation results are shown in Table 6 below.

As shown in Table 6, the composition of the Example was excellent in all of a sensitivity, a pattern shape, and LER compared with the composition of a comparative example.

Claims (22)

Resin containing the repeating unit represented by following General formula (I);
An actinic ray-sensitive or radiation-sensitive resin composition comprising a compound that generates an acid by irradiation with actinic rays or radiation.

In formula (I),
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 carboxyl group, an alkyloxycarbonyl group, an alkylcarbon A carbonyloxy 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 leaving by the action of an acid.
S ₂ represents a substituent (excluding hydrogen atoms), and in the case of r ≧ 2, the plurality of S ₂ may be the same as or different from each other.
p represents the integer of 1-5.
q represents the integer of 1-5.
r represents the integer of 0-4 which satisfy | fills the relationship which becomes p + r <= 5.] The method of claim 1,
R _<a> is a hydrogen atom or a methyl group, said p = 1 and said q = 1, The actinic-ray-sensitive or radiation-sensitive resin composition characterized by the above-mentioned. 3. The method of claim 2,
The repeating unit is an actinic ray-sensitive or radiation-sensitive resin composition, characterized in that represented by the 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 leaving by the action of an acid.
S ₂ represents a substituent (excluding hydrogen atoms), and in the case of r ≧ 2, the plurality of S ₂ may be the same as or different from each other.
r represents the integer of 0-4.] The method of claim 3, wherein
The actinic ray-sensitive or radiation-sensitive resin composition, wherein r = 0. The method of claim 1,
Y _a represents -O-, -CH ₂ O-, -COO- or -COOCH ₂ -actinic ray-sensitive or radiation-sensitive resin composition, characterized in that. The method of claim 5, wherein
Y _b represents a single bond, -CH ₂ O- or -COOCH ₂ -actinic ray-sensitive or radiation-sensitive resin composition, characterized in that. The method of claim 1,
Ar is an actinic ray-sensitive or radiation-sensitive resin composition, characterized in that a structural unit containing a naphthalene or anthracene ring, or a biphenyl or terphenyl structure. The method of claim 1,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the resin further comprises at least one of a repeating unit represented by the following general formula (A1) and a repeating unit represented by the general formula (A2).

[In the general formula (A1)
m represents the integer of 0-4.
n represents the integer of 1-5 which satisfy | fills the relationship which becomes m + n <= 5.
S ₁ represents a substituent (excluding hydrogen atoms), and in the case of m ≧ 2, a plurality of S ₁ may be the same as or different from each other.
A ₁ represents a group which is released by the action of a hydrogen atom or an acid, and when n ≧ 2, a plurality of the A _{1 's} may be the same as or different from each other.
In the general formula (A2)
X 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, carboxyl group, alkyloxycarbonyl group, alkylcarbon A siloxy group or an aralkyl group is shown.
A ₂ represents a group leaving by the action of an acid.] The method of claim 1,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the compound which generates an acid by irradiation with actinic light or radiation contains an anion represented by the following general formula (SA1) or general formula (SA2).

[In formula (SA1),
Ar ₁ represents an aryl group.
n represents an integer of 1 or more.
D represents a single bond or a divalent linking group.
B represents a hydrocarbon group.
In formula (SA2),
Each Xf independently represents a fluorine atom or an alkyl group in which at least one hydrogen atom is substituted with a fluorine atom.
R ₁ and R ₂ each independently represent a hydrogen atom, a fluorine atom, an alkyl group or an alkyl group in which one or more hydrogen atoms are substituted with fluorine atoms, and when y ≧ ₂ , each of the plurality of R ₁ and R ₂ may be the same as each other; Good or different.
L represents a single bond or a divalent linking group, and in the case of z ≧ 2, a plurality of the L's may be the same as or different from each other.
E represents a group having a cyclic structure.
x represents an integer of 1 to 20, y represents an integer of 0 to 10, and z represents an integer of 0 to 10.] A repeating unit (A) represented by the following general formula (I);
An actinic ray-sensitive or radiation-sensitive resin composition comprising a resin having a repeating unit (B) which generates an acid by irradiation with actinic light or radiation.

In formula (I),
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 carboxyl group, an alkyloxycarbonyl group, an alkylcarbon A carbonyloxy 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 leaving by the action of an acid.
S ₂ represents a substituent (excluding hydrogen atoms), and in the case of r ≧ 2, the plurality of S ₂ may be the same as or different from each other.
p represents the integer of 1-5.
q represents the integer of 1-5.
r represents the integer of 0-4 which satisfy | fills the relationship which becomes p + r <= 5.] 11. The method of claim 10,
R _a is a hydrogen atom or a methyl group, p = 1 and q = 1, the actinic ray-sensitive or radiation-sensitive resin composition. The method of claim 11,
The repeating unit (A) is an actinic ray-sensitive or radiation-sensitive resin composition, characterized 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 leaving by the action of an acid.
S ₂ represents a substituent (excluding hydrogen atoms), and in the case of r ≧ 2, the plurality of S ₂ may be the same as or different from each other.
r represents the integer of 0-4.] 13. The method of claim 12,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein r = 0. 11. The method of claim 10,
Y _a represents -O-, -CH ₂ O-, -COO- or -COOCH ₂ -actinic ray-sensitive or radiation-sensitive resin composition, characterized in that. 15. The method of claim 14,
Y _b represents a single bond, -CH ₂ O- or -COOCH ₂ -actinic ray-sensitive or radiation-sensitive resin composition, characterized in that. 11. The method of claim 10,
Ar is an actinic ray-sensitive or radiation-sensitive resin composition, characterized in that a structural unit containing a naphthalene or anthracene ring, or a biphenyl or terphenyl structure. 11. The method of claim 10,
At least part of the repeating unit (B) is an actinic ray-sensitive or radiation-sensitive resin composition, characterized in that represented by one or more selected from the group consisting of the following general formula (B1), (B2) and (B3) .

[Wherein,
A represents a structural site that is decomposed by actinic radiation or radiation to generate an acid anion.
R ₀₄ , R ₀₅ and R ₀₇ to R ₀₉ each independently represent 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 carboxyl 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 a nitrogen atom. R ₂₆ and R ₂₇ each independently represent 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 of a plurality thereof; Shows a coupling 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 method of claim 17,
A is an actinic ray-sensitive or radiation-sensitive resin composition, characterized in that the structural portion having a sulfonium salt structure or an iodonium salt structure. The method of claim 17,
A is an actinic ray-sensitive or radiation-sensitive resin composition, characterized in that the structural site is converted into an acid anion by irradiation of actinic light or radiation. 11. The method of claim 10,
The actinic ray-sensitive or radiation-sensitive resin composition, wherein the resin further comprises at least one of a repeating unit represented by the following general formula (A1) and a repeating unit represented by the general formula (A2).

[In the general formula (A1)
m represents the integer of 0-4.
n represents the integer of 1-5 which satisfy | fills the relationship which becomes m + n <= 5.
S ₁ represents a substituent (excluding hydrogen atoms), and in the case of m ≧ 2, a plurality of S ₁ may be the same as or different from each other.
A ₁ represents a group which is released by the action of a hydrogen atom or an acid, and when n ≧ 2, a plurality of the A _{1 's} may be the same as or different from each other.
In the general formula (A2)
X 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, carboxyl group, alkyloxycarbonyl group, alkylcarbon A siloxy group or an aralkyl group is shown.
A ₂ represents a group leaving by the action of an acid.] The resist film formed using the actinic-ray-sensitive or radiation-sensitive resin composition in any one of Claims 1-20. Forming a film | membrane using the actinic-ray-sensitive or radiation-sensitive resin composition in any one of Claims 1-20;
Exposing the film;
And developing the exposed film.