JP2002202607A - Positive type photoresist composition for exposure with far ultraviolet ray - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a positive type photoresist composition for exposure with far UV having improved exposure margin and defocus latitude in the resolution of a contact hole pattern. SOLUTION: The positive type photoresist composition contains a compound which generates a perfluoroalkanesulfonic acid when irradiated with active rays or radiation and a resin having a specified structure and a velocity of dissolution in an alkali developing solution increased by the action of the acid.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a positive photoresist composition for deep ultraviolet exposure used in an ultra microlithography process such as the production of an ultra LSI or a high-capacity microchip and other photofabrication processes. It is. More specifically, the present invention relates to a positive photoresist composition for deep ultraviolet exposure which can form a high-definition pattern by using light having a wavelength of not more than 250 nm, particularly a deep ultraviolet region including excimer laser light.

[0002]

2. Description of the Related Art In recent years, the degree of integration of integrated circuits has been increasing more and more, and in the manufacture of semiconductor substrates such as VLSIs, processing of ultrafine patterns having a line width of less than half a micron is required. It has become In order to meet the need, the wavelength used in an exposure apparatus used for photolithography is becoming shorter and shorter, and now it is considered to use excimer laser light (XeCl, KrF, ArF, etc.) having a short wavelength among far ultraviolet rays. Up to now.
A chemically amplified resist is used for forming a pattern in lithography in this wavelength region.

In general, chemically amplified resists can be broadly classified into three types: so-called two-component, 2.5-component and three-component resists. The two-component system combines a compound that generates an acid by photolysis (hereinafter referred to as a photoacid generator) and a binder resin. The binder resin is a resin having in its molecule a group (also referred to as an acid-decomposable group) that decomposes under the action of an acid to increase the solubility of the resin in an alkaline developer. The 2.5-component system further contains a low-molecular compound having an acid-decomposable group in such a two-component system. The three-component system contains a photoacid generator, an alkali-soluble resin, and the above low molecular compound.

The above-mentioned chemically amplified resist is suitable for a photoresist for irradiating ultraviolet rays or far ultraviolet rays, but among them, it is necessary to further meet the required characteristics in use. As a photoresist composition for an ArF light source, a photoresist composition obtained by combining a (meth) acrylic resin having a lower absorption than a partially hydroxylated styrene resin with a compound capable of generating an acid by light is used. Proposed. For example, JP-A-7-199467 and JP-A-7-2523
No. 24 etc. Among them, JP-A-6-289615 discloses a resin in which a tertiary carbon organic group is ester-bonded to oxygen of a carboxyl group of acrylic acid.

Further, Japanese Patent Application Laid-Open No. Hei 7-234511 discloses an acid-decomposable resin having an acrylic ester or a fumaric ester as a repeating structural unit. The fact is that performance has not been obtained.

Since lithography processes for manufacturing devices using 0.18 μm and 0.13 μm design rules often use light having a wavelength of 193 nm as exposure radiation, a resist polymer which does not contain much ethylenic unsaturation is required. Is desired.

As a photoresist composition for an ArF light source, a resin into which an alicyclic hydrocarbon moiety is introduced for the purpose of imparting dry etching resistance has been proposed. Is extremely hydrophobic, so that tetramethylammonium hydroxide (hereinafter referred to as TMA), which has been widely used as a resist developing solution in the past,
H) There are phenomena such as difficulty in developing with an aqueous solution and peeling of the resist from the substrate during development.

JP-A-10-10739 discloses an energy-sensitive resist containing a polymer obtained by polymerizing a monomer having an alicyclic structure such as a norbornene ring in its main chain, maleic anhydride, and a monomer having a carboxyl group. Materials are disclosed. JP-A-10-111569 discloses a radiation-sensitive resin composition containing a resin having an alicyclic skeleton in the main chain and a radiation-sensitive acid generator. JP-A-11-202491 discloses a polymer containing a norbornene derivative, and androstan-17-
A radiation-sensitive resin composition containing a carboxylic acid ester compound is disclosed.

Further, Japanese Patent Application Laid-Open No. 9-73173,
JP-A-90637 and JP-A-10-161313 contain an alkali-soluble group protected by a structure containing an alicyclic group, and a structural unit which is made to be alkali-soluble by the removal of the alkali-soluble group by an acid. A resist material using an acid-sensitive compound is described.

[0010] Japanese Patent Application Laid-Open No. 9-90637 and 10-
JP-A-2070769 and JP-A-10-274852 describe resist compositions containing an acid-decomposable resin having a specific lactone structure. JP-A-10-130340 discloses a chemically amplified resist containing a terpolymer having a specific repeating structural unit having a norbornene structure in a main chain. JP-A-11-30544
No. 4 discloses a resin containing a repeating structural unit having an adamantane structure in a side chain and a resin containing maleic anhydride as a repeating structural unit. EP1048983
A1 is a repeating unit composed of norbornene having a specific acid-decomposable group, a repeating unit composed of anhydride, and a fatty acid for the purpose of improving storage stability, transparency, dry etching property, sensitivity, resolution, pattern shape and the like. A composition comprising a resin having a repeating unit having a cyclic group is disclosed.

However, conventional resist compositions have not been sufficiently improved in exposure margin and defocus latitude in resolving a contact hole pattern. The exposure margin is a phenomenon that the diameter of the contact hole fluctuates with the fluctuation of the exposure amount,
Defocus latitude refers to a phenomenon in which the diameter of a contact hole fluctuates due to defocus.

[0012]

SUMMARY OF THE INVENTION Accordingly, an object of the present invention is to improve the original performance of the above-mentioned microphotofabrication using far ultraviolet light, especially ArF excimer laser light, and to solve the problems of the prior art. In particular, it is an object of the present invention to provide a positive photoresist composition for deep ultraviolet exposure with improved exposure margin and defocus latitude in resolving contact holes.

[0013]

Means for Solving the Problems The present inventors have made intensive studies on the constituent materials of a resist composition in a positive-type chemical amplification system, and as a result, have found that the present invention uses a specific photoacid generator and a specific resin. It has been found that the object of the present invention can be achieved, and the present invention has been achieved. That is, the above object is achieved by the following configuration.

(1) (A) The following general formulas (I ') to (I) which generate sulfonic acids upon irradiation with actinic rays or radiation.
II ′), and (B) a repeating structural unit represented by the following general formula (I), a repeating structural unit represented by the following general formula (II), and a repeating structure represented by the following general formula (III) And a resin whose dissolution rate in an alkali developing solution is increased by the action of an acid.

[0015]

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[0016]

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[0017]

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[0018]

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The above general formula (I ') ~ (III' ) in: R ₅₁ ~
R ₈₇ each independently represents a hydrogen atom, a linear, branched or cyclic alkyl group, a linear, branched or cyclic alkoxy group, a hydroxyl group, a halogen atom, or -SR.
Represents ₈₈ groups. R ₈₈ represents a linear, branched or cyclic alkyl group or aryl group. R _{51 to} R ₆₅ , R ₆₆
Of to R _77, R ₇₈ to R _87, 2 or more are bonded, a single bond, carbon, oxygen, sulfur, and also form a ring containing one or more selected from nitrogen Good. X ^- is,
Represents R ^F SO ₃ ^— . Here, R ^F is a fluorine-substituted linear, branched or cyclic alkyl group having 2 or more carbon atoms.

In the general formula (I), R _{11 to} R ₁₄ are each independently a group capable of decomposing under the action of an acid, a hydrogen atom, a halogen atom, a cyano group, —COOH, —COOR ₁₅ , —C (=
O) —XA—R ₁₆ , or an alkyl group or a cyclic hydrocarbon group, and at least one of R _{11 to} R ₁₄ represents a group decomposed by the action of an acid. Further, at least two members out of R _{11 to} R ₁₄ may combine to form a ring. n is 0
Or represents 1. Here, R ₁₅ represents an alkyl group, a cyclic hydrocarbon group or the following —Y group. X represents an oxygen atom, a sulfur _{atom, -NH -, - NHSO 2 -} , or -NHSO ₂ NH
Represents-. A is a single bond, an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group,
It represents a single or a combination of two or more groups selected from the group consisting of ester groups. R ₁₆ is -COOH, -C
OOR ₁₅ , -CN, hydroxyl group, alkoxy group, -CO-N
HR ₁₇ , -CO-NH-SO ₂ -R ₁₇ or the following -Y
Represents a group. R ₁₇ represents an alkyl group or a cyclic hydrocarbon group. A —Y group;

[0021]

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In the —Y group, R _{21 to} R ₃₀ each independently represent a hydrogen atom or an alkyl group. a and b represent 1 or 2.

In the general formula (II): Z ₂ is -O- or-
N (R ₄₁ )-. Here, R ₄₁ is a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO ₂ —R ₄₂
Represents R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue. In the general formula (III): R ₉₁ represents a hydrogen atom, a lower alkyl group, a halogen atom or —CN. X ₅ is —O—,
-S -, - NR ₉₃ -, or -NR ₉₃ SO ₂ - represents a. R
₉₃ represents a hydrogen atom, a chain or a cyclic alkyl group. B
Represents a single bond or a linking group. R ₉₂ represents a hydrogen atom, a chain or cyclic alkyl group, an alkoxy group, a hydroxyl group, a carboxy group, a cyano group, —COOR ₉₄ , or the following general formula (I
V) represents a group represented by any of (X) to (X). R ₉₄ is
Represents a hydrogen atom, or a chain or cyclic alkyl group.

[0024]

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[0025] _{^{-N + (R 95) (R}} 96) (R 97) · X - (VIII) -R 98 -A 50 -R 99 (IX) -SO 3 R 100 (X)

In the formula (IV), Ra₁, Rb₁, R
c₁, Rd₁, And Re₁Is independently a hydrogen atom or
Represents an alkyl group having 1 to 4 carbon atoms. m and n are each independently
Represents an integer of 0 to 3, and m + n is 2 or more and 6 or less.
In the formulas (V-1) to (V-4), R_1b~ R_5bIs each
Each independently represents a hydrogen atom, an alkyl group, a cycloalkyl group or
Represents an alkenyl group. R_1b~ R_5bTwo of the
To form a ring. In the formula (VII), R_1d~
R_8dRepresents a hydrogen atom or an alkyl group each independently.
R_d0Represents a hydrogen atom, a chain or cyclic alkyl group,
Represents an alkyl group or an aralkyl group. m is an integer of 1 to 10
Represent. In the formula (VIII), R₉₅~ R₉₇Are each independently water
Atom, chain or cyclic alkyl group, alkenyl group,
Represents a reel group or an aralkyl group. Where R₉₅~ R ₉₇
May combine with each other to form a non-aromatic ring or an aromatic ring.
X^-Is R-SO_Three ^-Represents R is an aliphatic hydrocarbon group or
Represents an aromatic hydrocarbon group. In the formula (IX), R₉₈Is simple
Alkylene group, arylene group, or a combination thereof.
Represents a divalent group. A₅₀Is the functional group shown below
Indicates the difference.

[0027]

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R ₉₉ represents a hydrogen atom or an alkyl group. In the formula (X), R ₁₀₀ is a chain or cyclic alkyl group,
Represents an aryl group or an aralkyl group.

(2) The positive photoresist composition for deep ultraviolet exposure according to the above (1), wherein the resin of the component (B) further contains a repeating unit represented by the following formula (XI). object.

[0030]

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[0031] In the general formula _{(XI), R 91 c,} X 5 c and Bc, respectively, R _91, X ₅ in the above general formula (III)
And B. R _92c represents a group represented by the following general formula (XI ′).

[0032]

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In the general formula (XI ′), R ₂ c to R ₄ c
Each independently represents a hydrogen atom or a hydroxyl group. Where R
At least one of ₂ c to R ₄ c represents a hydroxyl group. (3) The positive photoresist composition for deep ultraviolet exposure according to the above (1) or (2), further comprising a fluorine-based and / or silicon-based surfactant. (4) The positive photoresist composition for deep UV exposure according to any one of the above (1) to (3), further comprising an organic basic compound.

Further, the following embodiments are also preferable. (5) X ^- R ^F is CF ₃ (CF ₂₎ of y (where, y is 1 to 1
The positive resist composition according to any one of the above (1) to (4), wherein the positive resist composition is a fluorine-substituted linear alkyl group represented by the following formula: (6) The positive resist composition according to the above (5), wherein y is an integer of 1 to 9. (7) The positive resist composition according to the above (5), wherein y is an integer of 1 to 5.

[0035]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, the compounds used in the present invention will be described in detail.

[1] Photoacid Generator In the present invention, as the photoacid generator, (A) a sulfonic acid which is generated by irradiation with an actinic ray or radiation; The compounds represented are used.

In the general formulas (I ′) to (III ′), R ₅₁
To R ₈₈ linear, as the branched alkyl group may have a substituent, a methyl group, an ethyl group, a propyl group, n-
Examples thereof include those having 1 to 5 carbon atoms such as a butyl group, a sec-butyl group, a t-butyl group and a t-amyl group. Examples of the cyclic alkyl group include those having 3 to 8 carbon atoms which may have a substituent, such as a cyclopropyl group, a cyclopentyl group and a cyclohexyl group. Examples of the linear or branched alkoxy group represented by R _{51 to} R ₈₇ include a methoxy group, an ethoxy group, a hydroxyethoxy group, a propoxy group, an n-butoxy group, an isobutoxy group, a sec-butoxy group and a t-butoxy group. Such a C1-C4 thing is mentioned.

Examples of the cyclic alkoxy group include a cyclopentyloxy group and a cyclohexyloxy group. Examples of the halogen atom for R _{51 to} R ₈₇ include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. Examples of the aryl group for R ₈₈ include a phenyl group,
Those having 6 to 14 carbon atoms which may have a substituent such as a tolyl group, a methoxyphenyl group and a naphthyl group are exemplified. As these substituents, an alkoxy group having 1 to 4 carbon atoms, a halogen atom (for example, a fluorine atom,
A chlorine atom, an iodine atom), an aryl group having 6 to 10 carbon atoms, an alkenyl group having 2 to 6 carbon atoms, a cyano group, a hydroxy group, a carboxy group, an alkoxycarbonyl group, and a nitro group.

R _{51 to} R ₆₅ , R _{66 to} R ₇₇ , R _{78 to} R
₈₇ or one or more selected from the group consisting of a single bond, carbon, oxygen, sulfur, and nitrogen, formed by bonding two or more of them;
Examples of the ring containing more than one kind include a furan ring, a dihydrofuran ring, a pyran ring, a trihydropyran ring, a thiophene ring, a pyrrole ring, and the like.

In the general formulas (I ') to (III'), X
^-Is R^FSO_Three ^-Is an anion represented by Where R^F
Has 2 or more carbon atoms, preferably 2 to 10 carbon atoms,
Preferably it has 2 to 8 carbon atoms, more preferably 2 to 5 carbon atoms.
Fluorine-substituted linear, branched or cyclic alkyl
Group. Preferred R^FAs CF_Three(CF_Two) y
Wherein y is an integer of 1 to 15,
A alkyl group, more preferably y is an integer of 1 to 9,
More preferably, y is an integer of 1 to 5 and
Is a alkyl group. These fluorine-substituted linear alkyl groups
[CF_Three(CF_Two) y], sensitivity and resolution
Excellent balance between exposure and post-heating.
However, the performance change is small. R^FAs a specific
Is CF_ThreeCF_Two-, CF_Three(CF_Two)_Two-, CF_Three(C
F_Two)_Three-, CF_Three(CF_Two)_Four-, CF_Three(CF_Two)_Five-, C
F_Three(CF_Two)₇-, CF_Three(CF_Two)₉-, CF_Three(CF_Two)
₁₁-, CF_Three(CF_Two)₁₃-, CF_Three(CF_Two)₁₅-
And preferably CF_ThreeCF_Two-, CF_Three(CF_Two)_Two-, C
F_Three(CF_Two)_Three-, CF _Three(CF_Two)_Four-, CF_Three(CF_Two)
_Five-, CF_Three(CF_Two)₇-, CF_Three(CF_Two)₉-
More preferably CF_ThreeCF_Two-, CF_Three(CF_Two)_Two-, C
F_Three(CF_Two)_Three-, CF_Three(CF_Two)_Four-, CF_Three(CF_Two)
_Five-. Particularly preferably CF_Three(CF_Two) _Three-.

Particularly preferred photoacid generators have the general formula
(I ′) and X^-Is CF_Three(CF_Two) _ThreeSO_Three ^-In
Compound.

The compounds represented by the general formulas (I ') to (III') in which such an anion portion is constituted by a sulfonate anion having a fluorine-substituted alkyl group are used as a photoacid generator, and When combined with the resin (B) having the specific structure, the positive resist composition of the present invention has sufficient sensitivity and resolution for exposure to far ultraviolet light, particularly ArF excimer laser light (wavelength: 193 nm), and Excellent margin improvement effect.

As specific examples of the photoacid generators represented by the general formulas (I ') to (III'), the following compounds (I-1) to (I)
-32), (II-1) to (II-11), (III-1) to
(III-22).

[0044]

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[0045]

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[0046]

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[0047]

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[0048]

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[0049]

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[0050]

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[0051]

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[0052]

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[0053]

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The amount of the photoacid generators represented by the above general formulas (I ′) to (III ′) is usually in the range of 0.001 to 20% by weight based on the solid content in the composition. And preferably 0.01 to 15% by weight, more preferably 0.1 to 15% by weight.
It is used in the range of 10 to 10% by weight. If the amount of the photoacid generator is less than 0.001% by weight, the sensitivity becomes low. If the amount is more than 20% by weight, the light absorption of the resist becomes too high, and the profile deteriorates and the process (especially baking) ) The margin is undesirably narrow. Note that the use of a sulfonium salt is slightly preferable in terms of defocus latitude.

The compounds represented by the general formulas (I ') and (II') are obtained by reacting an aryl Grignard reagent such as arylmagnesium bromide with a substituted or unsubstituted phenyl sulfoxide to obtain a triaryl compound. It can be synthesized by salt exchange of a sulfonium halide with a corresponding sulfonic acid. Further, a substituted or unsubstituted phenyl sulfoxide and an aromatic compound corresponding to
It can be synthesized by a method of condensation and salt exchange using an acid catalyst such as diphosphorus pentoxide or aluminum chloride, and a method of condensation and salt exchange between a diaryliodonium salt and a diarylsulfide using a catalyst such as copper acetate. The salt exchange can be performed by a method of once converting to a halide salt and then converting it to a sulfonate using a silver reagent such as silver oxide, or by using an ion exchange resin. The sulfonic acid or sulfonic acid salt used for the salt exchange may be a commercially available one, or may be obtained by hydrolysis of a commercially available sulfonic acid halide. General formula (II
The compound represented by I ') can be synthesized by reacting an aromatic compound with periodate and subjecting the obtained iodonium salt to salt exchange with the corresponding sulfonic acid.

In the positive resist composition of the present invention, a photoacid generator other than the compounds represented by formulas (I ') to (III') can be used in combination. The amount of the photoacid generator that may be used in combination is 1000% by weight or less, preferably 700% by weight or less based on the photoacid generators represented by the above general formulas (I ′) to (III ′). And more preferably 50
0% by weight or less. Known photoacid generators that can be used in combination include photoinitiators for photocationic polymerization, photoinitiators for photoradical polymerization, photodecolorants for dyes, photochromic agents, and microresists. Light (400 ~
200 nm ultraviolet light, far ultraviolet light, particularly preferably g
Line, h line, i line, KrF excimer laser light), ArF
A compound capable of generating an acid by excimer laser light, electron beam, X-ray, molecular beam or ion beam and a mixture thereof can be appropriately selected and used.

Other photoacid generators which can be used in combination in the present invention include, for example, onium salts such as diazonium salts, ammonium salts, phosphonium salts, iodonium salts, sulfonium salts, selenonium salts, arsonium salts, and the like, and organic halides. Compounds, organometallic / organic halides, photoacid generators having an o-nitrobenzyl-type protecting group, compounds that generate sulfonic acid upon photolysis represented by iminosulfonate, disulfone compounds, diazoketosulfones, diazo Disulfone compounds and the like can be mentioned. Further, a group in which an acid is generated by such light or a compound in which a compound is introduced into a main chain or a side chain of a polymer can be used.

Further, VNRPillai, Synthesis, (1), 1 (198
0), A. Abad etal, Tetrahedron Lett., (47) 4555 (1971),
Compounds that generate an acid by light described in DHR Barton et al., J. Chem. Soc., (C), 329 (1970), U.S. Pat. No. 3,779,778, and EP 126,712 can also be used.

Among the above-mentioned compounds capable of generating an acid which can be used in combination, those which are particularly effectively used are described below. (1) The following general formula (PAG) substituted with a trihalomethyl group
The oxazole derivative represented by 1) or the general formula (PAG)
An S-triazine derivative represented by 2).

[0060]

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In the formula, R ²⁰¹ is a substituted or unsubstituted aryl group or alkenyl group, and R ²⁰² is a substituted or unsubstituted aryl group, alkenyl group, alkyl group, —C (Y) ₃
Show Y represents a chlorine atom or a bromine atom. Specific examples include the following compounds, but the present invention is not limited thereto.

[0062]

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(2) An iodonium salt represented by the following formula (PAG3) or a sulfonium salt represented by the following formula (PAG4).

[0064]

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Here, the formulas Ar ¹ and Ar ² each independently represent a substituted or unsubstituted aryl group. R ²⁰³ , R ²⁰⁴ ,
R ²⁰⁵ each independently represents a substituted or unsubstituted alkyl group or aryl group.

Z ^- represents a counter anion, for example, B
F ₄ ⁻ , AsF ₆ ⁻ , PF ₆ ⁻ , SbF ₆ ⁻ , SiF ₆ ²⁻ , Cl
Condensed polynuclear aromatic sulfonic acid anions such as O ₄ ⁻ , CF ₃ SO ₃ ⁻ , pentafluorobenzene sulfonic acid anion, naphthalene-1-sulfonic acid anion, anthraquinone sulfonic acid anion, and sulfonic acid group-containing dyes. Is not limited to these.

Further, two of R ²⁰³ , R ²⁰⁴ and R ²⁰⁵ and Ar ¹ and Ar ² may be bonded through a single bond or a substituent.

Specific examples include the following compounds, but are not limited thereto.

[0069]

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[0070]

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[0071]

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[0072]

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[0073]

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[0074]

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[0075]

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[0076]

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[0077]

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In the above, Ph represents a phenyl group.
The onium salts represented by the general formulas (PAG3) and (PAG4) are known and can be synthesized, for example, by the methods described in U.S. Pat. Nos. 2,807,648 and 4,247,473 and JP-A-53-101,331. .

(3) Disulfone derivatives represented by the following formula (PAG5) or iminosulfonate derivatives represented by the following formula (PAG6).

[0080]

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In the formula, Ar ³ and Ar ⁴ each independently represent a substituted or unsubstituted aryl group. R ²⁰⁶ represents a substituted or unsubstituted alkyl group or aryl group. A represents a substituted or unsubstituted alkylene group, alkenylene group, or arylene group. Specific examples include the following compounds, but are not limited thereto.

[0082]

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[0083]

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[0084]

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[0085]

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[0086]

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(4) A diazodisulfone derivative represented by the following general formula (PAG7).

[0088]

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Here, R represents a linear, branched or cyclic alkyl group or an optionally substituted aryl group. Specific examples include the following compounds, but are not limited thereto.

[0090]

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[0091]

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[2] Resin (component (B)) Next, (B) a repeating unit represented by the above general formula (I), a repeating unit represented by the above general formula (II), An acid-decomposable resin having a repeating unit represented by (III) (hereinafter, abbreviated as “acid-decomposable resin according to the present invention”) will be described.

In the above general formula (I), R₁₁~ R
₁₄Are each independently a group that decomposes under the action of an acid,
, Halogen atom, cyano group, -COOH, -COOR
₁₅, -C (= O) -XA-R₁₆Or an alkyl group
Represents a cyclic hydrocarbon group, and R ₁₁~ R₁₄At least
One is a group decomposed by the action of an acid (acid-decomposable group).
You. Also, R₁₁~ R₁₄At least two of
A ring may be formed. n represents 0 or 1. Where R
₁₅Represents an alkyl group, a cyclic hydrocarbon group or the above-described -Y group.
Represent. X represents an oxygen atom, a sulfur atom, -NH-, -NHS
O_Two-Or-NHSO_TwoRepresents NH-. A is a single bond,
Alkylene group, cycloalkylene group, ether group, thio
From the group consisting of ether, carbonyl, and ester groups
Displays the selected single or combination of two or more groups.
You. R₁₆Are -COOH, -COOR ₁₅, -CN, hydroxyl
Group, alkoxy group, -CO-NH-R₁₇, -CO-NH
-SO _Two-R₁₇Alternatively, it represents the above-described -Y group. R₁₇Is al
Represents a kill group or a cyclic hydrocarbon group. In the above -Y group
And R_{twenty one}~ R₃₀Is each independently a hydrogen atom or an alkyl
Represents a group. a and b represent 1 or 2.

The structure of the group decomposed by the action of an acid is represented by —C (＝ O) —X ₁ —R _p . Where R _p
A tertiary alkyl group such as a t-butyl group and a t-amyl group, an isobornyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, and a 1-cyclohexyloxyethyl group. -An alkoxyethyl group,
1-methoxymethyl group, 1-ethoxymethyl group and other alkoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3-oxocyclohexyl ester group, 2-methyl-2 -Adamantyl group, mevalonic lactone residue, 2- (γ-butyrolactonyloxycarbonyl) -2-propyl group and the like. X ₁
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.

Examples of the halogen atom in R _{11 to} R ₁₄ include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom. As the alkyl group for R _{11 to} R _{14, a} linear or branched alkyl group having 1 to 10 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable. More preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group,
t-butyl group. Examples of the cyclic hydrocarbon group for R _{11 to} R ₁₄ include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, and norbornyl. Group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group,
Nobornane epoxy group, menthyl group, isomenthyl group,
Examples include a neomenthyl group and a tetracyclododecanyl group.

The ring formed by bonding at least two members out of R _{11 to} R ₁₄ is preferably a ring having 5 carbon atoms such as cyclopentene, cyclohexene, cycloheptane and cyclooctane.
To 12 rings. Examples of the alkoxy group for R ₁₆ include a methoxy group, an ethoxy group, a propoxy group,
Examples thereof include those having 1 to 4 carbon atoms such as a butoxy group. The alkyl group, cyclic hydrocarbon group, and alkoxy group may further have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, and a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom). , An iodine atom, etc.), an alkoxy group (preferably having 1 to 4 carbon atoms, such as methoxy group, ethoxy group, propoxy group, butoxy group, etc.), an acyl group (eg, formyl group, acetyl group, etc.), an acyloxy group (eg, acetoxy group) And the like).

Examples of the alkylene group in the above A include groups represented by the following formula. -[C (R _b ) (R _c )] _r-wherein R _b and R _c represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms). Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

In the above -Y group, R _{21 to} R ₃₀ each independently represent a hydrogen atom or an alkyl group. a and b are 1
Or 2 is represented. Examples of the alkyl group for R _{21 to} R ₃₀ include a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group. R _{21 to} R
The alkyl group as ₃₀ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group,
Cyano group, halogen atom (for example, chlorine atom, bromine atom, fluorine atom, iodine atom), alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), acyl group (Preferably having 2 to 5 carbon atoms, for example, formyl group, acetyl group, etc.), acyloxy group (preferably having 2 to 5 carbon atoms, for example, acetoxy group), aryl group (preferably having 6 to 14 carbon atoms, for example, phenyl group) And the like.

The following are specific examples of the repeating unit represented by the above general formula (I), but the present invention is not limited to these specific examples.

[0100]

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[0101]

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In the general formula (II), Z ₂ represents-
Represents O- or -N ( _R41 )-. Here, R ₄₁ represents a hydrogen atom, a hydroxyl group, an alkyl group, a haloalkyl group, or —OSO
Representing a ₂ -R _42. R ₄₂ represents an alkyl group, a haloalkyl group, a cycloalkyl group or a camphor residue.

The alkyl group for R ₄₁ and R ₄₂ is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably methyl, ethyl, propyl, isopropyl, n-
A butyl group, an isobutyl group, a sec-butyl group and a t-butyl group. Examples of the haloalkyl group for R ₄₁ and R ₄₂ include a trifluoromethyl group, a nanofluorobutyl group, a pentadecafluorooctyl group, and a trichloromethyl group. Examples of the cycloalkyl group for R ₄₂ include a cyclopentyl group, a cyclohexyl group, and a cyclooctyl group.

The alkyl group, haloalkyl group as R ₄₁ and R ₄₂ , the cycloalkyl group as R ₄₂ or the camphor residue may have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (for example, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom), and an alkoxy group (preferably having 1 to 1 carbon atoms).
4, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., an acyl group (preferably having 2 to 5 carbon atoms, for example, a formyl group, an acetyl group, etc.), an acyloxy group (preferably having 2 to 5 carbon atoms, for example, An acetoxy group) and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group).

Specific examples of the repeating unit represented by the general formula (II) include the following [I'-1] to [I'-7], but the present invention is limited to these specific examples. Not something.

[0106]

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[0107]

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Next, the repeating unit represented by formula (III) will be described. In the formula (III), R ₉₁ is
Represents a hydrogen atom, a lower alkyl group, a halogen atom, or a cyano group. As the lower alkyl group for R ₉₁ ,
5 are preferable, and examples thereof include a methyl group, an ethyl group, a propyl group, a butyl group, and a pentyl group. This lower alkyl group may further have a substituent. Examples of such a substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom) and an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy group). Group, ethoxy group,
A propoxy group, a butoxy group and the like), an acyl group (preferably having 2 to 5 carbon atoms, such as a formyl group and an acetyl group),
An acyloxy group (preferably having 2 to 5 carbon atoms, for example, an acetoxy group), an aryl group (preferably having 6 to 14 carbon atoms,
For example, a phenyl group).

[0109] X ₅ is, -O -, - S -, - NR 93 -, or -NR ₉₃ SO ₂ - it represents a. R ₉₃ represents a hydrogen atom, a chain or a cyclic alkyl group. The chain alkyl group for R ₉₃ is a lower alkyl group, preferably having 1 to 5 carbon atoms, and includes a methyl group, an ethyl group, a propyl group, a butyl group, a pentyl group and the like. Examples of the cyclic alkyl group include those having 3 to 12 carbon atoms. These may further have a substituent, as a substituent,
For example, a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, Butoxy group), an acyl group (preferably having 2 to 5 carbon atoms, for example,
Examples thereof include a formyl group, an acetyl group and the like, an acyloxy group (preferably having 2 to 5 carbon atoms, for example, an acetoxy group), and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group).

B represents a single bond or a linking group. Examples of the linking group of B include a single or a combination of two or more groups selected from the group consisting of an alkylene group, a cycloalkylene group, an ether group, a thioether group, a carbonyl group, and an ester group. As the cycloalkylene group for B, those having 3 to 10 carbon atoms are preferable, and examples thereof include a cyclopentylene group, a cyclohexylene group, and a cyclooctylene group.

Examples of the alkylene group represented by B include groups represented by the following formula. -[C (R _x ) ( _RY )] _Z -R _{x and} R _y are each independently a hydrogen atom, a hydroxyl group, a halogen atom, a linear or cyclic alkyl group, an alkoxy group which may have a substituent. , An alkenyl group, an aryl group, or an aralkyl group. However, Rx and Ry may combine with each other to form a cyclic alkyl ring.

Examples of the linear alkyl group for Rx or Ry include a linear or branched alkyl group, which may have a substituent. As the linear or branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable. , More preferably methyl, ethyl, propyl, isopropyl, n-
Butyl, isobutyl, sec-butyl, pentyl, neopentyl, hexyl, heptyl, octyl, nonyl, and decyl. Examples of the cyclic alkyl group include those having 3 to 30 carbon atoms, and may include a hetero atom such as an oxygen atom or a nitrogen atom. Specifically, a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, a tricyclodecanyl group, a dicyclopentenyl group,
Nobornane epoxy group, menthyl group, isomenthyl group,
Examples include a neomenthyl group, a tetracyclododecanyl group, a steroid residue, a tetrahydropyranyl group, and a morpholino group.

Examples of the alkoxy group include those having 1 to 12 carbon atoms, preferably 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.
An ethoxy group, a propoxy group, a butoxy group and the like can be mentioned. Examples of the alkenyl group include an alkenyl group having 2 to 6 carbon atoms, which may have a substituent. Specifically, a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopentenyl group, a cyclohexenyl group, a 3-oxocyclohexenyl group, a 3-oxocyclopentenyl group, a 3-oxoindenyl group, and the like. No. Among these, the cyclic alkenyl group may contain an oxygen atom. The aryl group includes those having 6 to 10 carbon atoms, and may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group, and a mesitylmethyl group.

Examples of the substituent which the chain or cyclic alkyl group, alkoxy group, alkenyl group, aryl group or aralkyl group may have include, for example, a carboxyl group, a cyano group, a hydroxyl group, a halogen atom (a chlorine atom , A bromine atom, a fluorine atom, an iodine atom, etc.), an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group,
Propoxy group, butoxy group), acetylamide group, alkoxycarbonyl group, acyl group (preferably having 2 to 2 carbon atoms)
10, for example, a formyl group, an acetyl group, a propionyl group), an acyloxy group (preferably having 2 to 10 carbon atoms, for example, an acetoxy group), and an aryl group (preferably having 6 carbon atoms)
To 14, for example, a phenyl group). Rx or Ry
The aryl group or the aralkyl group as the substituent, further includes an alkyl group (preferably having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group) Etc.). The alkyl group as the substituent may further have a substituent such as a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group). . Z is an integer of 1 to 10, preferably 1 to 4.

R ₉₂ represents a hydrogen atom, a chain or cyclic alkyl group, an alkoxy group, a hydroxyl group, a carboxy group, a cyano group,
—COOR ₉₄ or a group represented by any of the above formulas (IV) to (X). _Examples of the chain alkyl group as R ₉₂ and R ₉₄ generally include those having 1 to 30 carbon atoms, preferably 6 to 20 carbon atoms. For example, a methyl group,
Ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group, hexyl group, heptyl group, octyl group,
Nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nonadecyl, eicosyl and the like can be mentioned. R ₉₂ and R
The cyclic alkyl group as ₉₄ generally has 3 carbon atoms.
To 40, preferably 6 to 20. For example, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl Group, steroid residue, tetrahydropyranyl group, morpholino group and the like.

The chain alkyl group as R ₉₂ and R ₉₄ may have a substituent. Examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom),
An alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), an alkoxycarbonyl group, an acyl group (preferably having 2 carbon atoms)
To 5, for example, a formyl group, an acetyl group, etc.), an acyloxy group (preferably, having 2 to 5 carbon atoms, for example, an acetoxy group), an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group), and an acetylamide group. Can be mentioned. Here, examples of the alkoxy group in the alkoxycarbonyl group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. The cyclic alkyl group as R ₉₂ and R ₉₄ is
As a substituent, a carboxyl group, a cyano group, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, an iodine atom),
An alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy group, ethoxy group, propoxy group, butoxy group, etc.), an alkoxycarbonyl group, an acyl group (preferably having 2 carbon atoms)
To 5, for example, a formyl group, an acetyl group and the like), an acyloxy group (preferably having 2 to 5 carbon atoms, for example, an acetoxy group), an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group), and an acetylamide group. It may be.
Here, examples of the alkoxy group in the alkoxycarbonyl group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

As the repeating unit represented by the above formula (III) wherein R ₉₂ is a cyclic alkyl group, a repeating unit represented by the following formula (IIIa) or (IIIb) is preferable.

[0118]

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The formula (IIIa) and the formula (III)
In b), R ₀ represents a hydrogen atom, a lower alkyl group, a halogen atom, or a cyano group. R ₆₁ and R ₆₂ represent a lower alkyl group. R _{63 to} R ₆₈ each independently represent a hydrogen atom, a lower alkyl group, a lower alkoxy group or a halogen atom.
R ₆₃ and R ₆₄ or R ₆₅ and R ₆₆ may together form a carbonyl group. R ₆₃ and R ₆₅ may be linked to form an alkylene chain. k and l are integers of 2 to 5.

The above general formulas (IIIa) and (IIIb)
In the repeating unit represented by, acid-decomposability is exhibited by the presence of a tertiary carbon atom to which _R61 is bonded. R ₀ is preferably a hydrogen atom. The lower alkyl group represented by R ₀ and R _{61 to} R ₆₈ has 1 to 6 carbon atoms, and preferably has 1 to 4 carbon atoms. Specific examples include, for example, a methyl group, an ethyl group, a linear or branched propyl group, and a linear or branched butyl group. The lower alkoxy group represented by R _{63 to} R ₆₈ has 1 to 6 carbon atoms, preferably 1 carbon atom.
~ 4. Specific examples include a methoxy group, an ethoxy group, a linear or branched propoxy group, and a linear or branched butoxy group. The lower alkyl groups as R ₀ and R _{61 to} R ₆₈ and the lower alkoxy groups as R _{63 to} R ₆₈ may have a substituent. As the substituent,
Examples thereof include a halogen atom such as a chlorine atom and a bromine atom, and an alkoxy group (preferably having 1 to 3 carbon atoms) such as a methoxy group and an ethoxy group.

R ₆₃ and R ₆₄ , or R ₆₅ and R ₆₆ may together form a carbonyl group. k and l are preferably 2 to 4, more preferably 2 or 3. The alkylene chain which may be formed by linking R ₆₃ and R ₆₅ preferably has 3 or less carbon atoms, such as a methylene chain, an ethylene chain and a propylene chain.

The alkoxy group represented by R ₉₂ generally has 1 to 30, preferably 3 to 20, more preferably 4 to 15 carbon atoms. Examples thereof include methoxy, ethoxy, propoxy and butoxy. And the like. The alkoxy group for R ₉₂ may further have a substituent. Examples of the substituent are the same as those described as the substituent for the chain or cyclic alkyl group as R ₉₂ .

In the following, R ₉₂ is an alkyl group, an alkoxy group,
A repeating unit represented by the general formula (III), which is a hydrogen atom,
And specific examples of the repeating unit represented by general formula (IIIa) and general formula (IIIb), but are not limited thereto.

[0124]

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[0125]

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[0126]

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[0127]

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[0128]

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[0129]

[Of 60]

*) Units differing in the number of groups in parentheses are a mixture of units, and have an average of 1.4 groups in parentheses.

Further, a repeating structural unit in which R ₉₂ in the formula (III) is a structure represented by the following general formula (IV) will be described.

[0132]

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Ra ₁ , Rb ₁ , Rc ₁ , Rd ₁ , and Re ₁ each independently represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms. m and n each independently represent an integer of 0 to 3;
Is 2 or more and 6 or less. Ra _{1 to} Re ₁ having 1 to 4 carbon atoms
Examples of the alkyl group include methyl, ethyl, propyl, isopropyl, n-butyl, isobutyl, and s.
Examples thereof include an ec-butyl group and a t-butyl group. These alkyl groups may be substituted with a substituent such as an alkoxy group (preferably having 1 to 4 carbon atoms).

Hereinafter, specific examples of the repeating structural unit having the structure of the general formula (IV) will be shown, but it should not be construed that the invention is limited thereto.

[0135]

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[0136]

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[0137]

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In the specific examples of the repeating unit having the structure of the general formula (IV), (IV-17) to (IV-36) are preferable in that the exposure margin becomes better. Further, as the structure of the general formula (IV), a structure having an acrylate structure is preferable from the viewpoint that edge roughness is improved.

The repeating unit structure in which R ₉₂ in the formula (III) has a group represented by any of the following formulas (V-1) to (V-4) will be described.

[0140]

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In the general formulas (V-1) to (V-4),
R _{1b to} R _5b each independently represent a hydrogen atom, an alkyl group, a cycloalkyl group or an alkenyl group. Two of R _{1b to} R _5b may combine to form a ring.

In the general formulas (V-1) to (V-4),
Examples of the alkyl group for R _{1b to} R _5b include a linear or branched alkyl group. As the linear or branched alkyl group, a linear or branched alkyl group having 1 to 12 carbon atoms is preferable, and more preferably a linear or branched alkyl group having 1 to 12 carbon atoms.
0 linear or branched alkyl groups, more preferably methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, Hexyl group, heptyl group, octyl group, nonyl group and decyl group. R _{1b to} R
The cycloalkyl group in _5b is preferably a cycloalkyl group having 3 to 8 carbon atoms such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, and a cyclooctyl group. As the alkenyl group for R _{1b to} R _5b ,
For example, those having 2 to 6 carbon atoms such as a vinyl group, a propenyl group, a butenyl group and a hexenyl group are preferred. Also, R _1b
Examples of the ring formed by combining two of R to _R5b include a 3- to 8-membered ring such as a cyclopropane ring, a cyclobutane ring, a cyclopentane ring, a cyclohexane ring, and a cyclooctane ring.

[0143] The alkyl group as R _1b to R _5b, cycloalkyl group, of the alkenyl group, and R _1b to R _5b 2
The rings formed by the bonding may each have a substituent. Preferred substituents include a hydroxyl group, a carboxy group, a nitro group, a cyano group, a halogen atom (a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom), and having 1 to 4 carbon atoms.
And C2 to C5 alkoxycarbonyl groups, C2 to C5 acyl groups, and C2 to C5 acyloxy groups. Note that R _{1b to} R _5b in the general formulas (V-1) to (V-4) may be connected to any of the carbon atoms constituting the cyclic skeleton.

Preferred as a repeating unit having a group represented by any of formulas (V-1) to (V-4) is a repeating unit represented by the following formula (AI).

[0145]

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In the general formula (AI), R _b0 represents a hydrogen atom, a halogen atom, or a substituted or unsubstituted alkyl group having 1 to 4 carbon atoms. Preferred substituents which the alkyl group of _Rb0 may have are those represented by the general formulas (V-1) to (V-1).
Preferred examples of the substituent which may be possessed by the alkyl group as R _1b in (V-4) include those exemplified above. Examples of the halogen atom for R _b0 include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. R
_b0 is preferably a hydrogen atom. B ₂ is represented by the general formula (V-1)
And represents a group represented by any of (V-4). A '
Is the same as defined for B in formula (III). In A ′, examples of the combined divalent group include those represented by the following formula.

[0147]

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In the above formula, Rab and Rbb represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group having 1 to 4 carbon atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r
1 represents an integer of 1 to 10, preferably an integer of 1 to 4.
m represents an integer of 1 to 3, preferably 1 or 2.

Hereinafter, specific examples of the repeating unit represented by the formula (AI) will be shown, but the present invention is not limited thereto.

[0150]

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[0151]

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[0152]

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[0153]

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[0154]

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[0155]

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[0156]

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Next, a repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following general formula (VI) will be described.

[0158]

[Of 75]

The bridged alicyclic ring containing Z may have a substituent. Examples of the substituent include a carboxyl group, a hydroxyl group, a halogen atom, an alkyl group (preferably having 1 to 4 carbon atoms), and an alkoxy group (preferably having 1 to 4 carbon atoms).
4), an alkoxycarbonyl group (preferably having 2 to 2 carbon atoms)
5), acyl groups (eg, formyl group, benzoyl group), acyloxy groups (eg, propylcarbonyloxy group, benzoyloxy group), and alkylsulfonylsulfamoyl groups (—CONHSO ₂ CH _{3 and the} like). In addition, the alkyl group as a substituent further includes a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms).
And so on.

In the general formula (III), B represents the general formula (V
It may be bonded at any position of the carbon atom constituting the bridged alicyclic structure containing Z in I).

Hereinafter, specific examples of the repeating unit having the structure represented by formula (VI) will be shown, but the invention is not limited thereto.

[0162]

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[0163]

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Further, a repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following general formula (VII) will be described.

[0165]

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In the general formula (VII), R _{1d to} R _8d are
Each independently represents a hydrogen atom or a chain alkyl group. R
_d0 represents a hydrogen atom, a chain or cyclic alkyl group, an aryl group or an aralkyl group. m represents an integer of 1 to 10.

R _{1d to} R _8d and R _d0 in the general formula (VII)
Examples of the chain alkyl group include a linear, branched or cyclic alkyl group, which may have a substituent. The linear or branched alkyl group has 1 to 1 carbon atoms.
Twelve linear or branched alkyl groups are preferred,
More preferably, it is a linear or branched alkyl group having 1 to 10 carbon atoms, and still more preferably, a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, and t -Butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group,
Decyl group. _Examples of the cyclic alkyl group for R _d0 include those having 3 to 30 carbon atoms, and specific examples thereof include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, and a tricyclodecanyl. Group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, steroid residue and the like.

The aryl group represented by R _d0 has 6 to 2 carbon atoms.
Zero thing is mentioned, and it may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. The aralkyl group for R _d0 includes those having 7 to 20 carbon atoms, and may have a substituent. Examples thereof include a benzyl group, a phenethyl group, and a cumyl group. In the present invention, R _{1d to} R _8d are preferably a hydrogen atom or a methyl group. As R _d0 , a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable. m is preferably 1 to 6.

The above-mentioned chain or cyclic alkyl group, aryl group, aralkyl group, alkylene group, cyclic alkylene group,
Further substituents in the arylene group include a carboxyl group, a cyano group, a hydroxyl group, a halogen atom (eg, a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc.), an alkyl group, a substituted alkyl group, an alkoxy group (preferably having 1-4, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., an alkoxycarbonyl group, an acyl group, an acyloxy group (for example, an acetoxy group), and an acetylamide group. Here, examples of the alkyl group include lower alkyl groups such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, and a cyclopentyl group. Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom,
An alkoxy group (preferably having 1 to 4 carbon atoms) can be mentioned.

Specific examples of the repeating unit having the structure represented by formula (VII) are shown below, but it should not be construed that the invention is limited thereto.

[0171]

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[0172]

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[0173]

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[0174]

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[0175]

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[0176]

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Next, a description will be given of a repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following formula (VIII). −N ⁺ (R ₉₅ ) (R ₉₆ ) (R ₉₇ ) · X ⁻ (VIII)

In the general formula (VIII): R₉₅~ R₉₇Are each
Independently, a hydrogen atom, an alkyl group which may have a substituent,
Lucenyl group, aryl group, aralkyl group, cyclic alkyl
Represents a group. Where R₉₅~ R ₉₇Are non-aromatic
A ring or an aromatic ring may be formed.

R _{95 to} R ₉₇ each independently represent a hydrogen atom, a chain or cyclic alkyl group, an alkenyl group, an aryl group,
Or an aralkyl group. However, R ₉₅ to R _97, taken together non-aromatic ring, may form an aromatic ring. Examples of the chain alkyl group include a linear or branched alkyl group, which may have a substituent. A linear or branched alkyl group having 1 to 12 carbon atoms is preferable, a linear or branched alkyl group having 1 to 10 carbon atoms is more preferable, and a methyl group, an ethyl group, and a propyl group are more preferable. , Isopropyl group, n-butyl group, isobutyl group, sec-butyl group, pentyl group, neopentyl group,
Hexyl group, heptyl group, octyl group, nonyl group and decyl group.

The cyclic alkyl group may have 3 to 3 carbon atoms.
Zero atoms are mentioned, and they may contain a hetero atom such as an oxygen atom or a nitrogen atom. Specifically, cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, norbornyl group, boronyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group,
Menthyl, isomenthyl, neomenthyl, tetracyclododecanyl, steroid residues, tetrahydropyranyl, morpholino and the like can be mentioned.

Examples of the alkenyl group include alkenyl groups having 2 to 6 carbon atoms, which may have a substituent.
Specifically, a vinyl group, a propenyl group, an allyl group, a butenyl group, a pentenyl group, a hexenyl group, a cyclopentenyl group, a cyclohexenyl group, a 3-oxocyclohexenyl group, a 3-oxocyclopentenyl group, a 3-oxoindenyl group, and the like. No. Among these, the cyclic alkenyl group may contain an oxygen atom. The aryl group includes those having 6 to 10 carbon atoms, and may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group.

Examples of the aralkyl group include a benzyl group, a phenethyl group, a naphthylmethyl group, a naphthylethyl group and a mesitylmethyl group.

[0183] chain or cyclic alkyl group as R ₉₅ to R _97, an alkenyl group, an aryl group, or an aralkyl group, and R ₉₅ to R ₉₇ are bonded may form a non-aromatic ring, the aromatic ring is Yes Examples of the optionally substituted substituent include a carboxyl group, a cyano group, a hydroxyl group, a halogen atom (a chlorine atom, a bromine atom, a fluorine atom, an iodine atom, etc.) and an alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy Group, ethoxy group, propoxy group, butoxy group), acetylamide group, alkoxycarbonyl group, acyl group (preferably having 2 to 10 carbon atoms, for example, formyl group, acetyl group, propionyl group), acyloxy group (preferably having 2 carbon atoms) Two
10, for example, an acetoxy group) and an aryl group (preferably having 6 to 14 carbon atoms, for example, a phenyl group). R
_{95 to} R ₉₇ as an aryl group or an aralkyl group and R ₉₅
To R ₉₇ are combined to form non-aromatic ring may be, for the aromatic ring, as a substituent, an alkyl group (preferably having from 1 to 5 carbon atoms, such as methyl group, ethyl group, propyl group, isopropyl group, butyl Group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, etc.). The alkyl group as the substituent may further have a substituent such as a hydroxyl group, a halogen atom, an alkoxy group (preferably having 1 to 4 carbon atoms, for example, a methoxy group, an ethoxy group, a propoxy group, a butoxy group). .

X ^- has a specific structure R-SO ₃ as described above.
^- with a. As the aliphatic hydrocarbon group for R, preferably a linear or branched alkyl group or a cyclic alkyl group having 1 to 20 carbon atoms which may have a substituent can be exemplified. The aromatic hydrocarbon group for R is preferably an aromatic group having 6 to 14 carbon atoms which may have a substituent.

Examples of the alkyl group represented by R include a methyl group, an ethyl group, a propyl group and an n-
Butyl group, n-pentyl group, n-hexyl group, n-octyl group, 2-ethylhexyl group, decyl group, dodecyl group and the like, and as the cyclic alkyl group, a cyclopentyl group which may have a substituent , Cyclohexyl, cyclooctyl, cyclododecyl, adamantyl, norbornyl, camphor, tricyclodecanyl, menthyl and the like. Examples of the aromatic group include a phenyl group and a naphthyl group which may have a substituent.

Examples of the substituent which the aliphatic hydrocarbon group and the aromatic hydrocarbon group may have include, for example, a halogen atom, a hydroxyl group, an alkoxy group, an alkoxycarbonyl group,
Examples include a camphor group, and specifically, methyl, t-butyl, methoxy, ethoxy, t-butoxy, fluorine, chlorine, bromine, cyano, hydroxyl, methoxycarbonyl, ethoxy Examples include a carbonyl group, a t-butoxycarbonyl group, a t-amyloxycarbonyl group, and the like. Further, an aryl group (preferably having 6 to 14 carbon atoms) can be cited as a substituent for an aliphatic hydrocarbon group, and an alkyl group (1 to 15 carbon atoms) can be cited as a substituent for an aromatic hydrocarbon group.

Hereinafter, specific examples of the repeating unit having the structure represented by formula (VIII) will be shown. However, the content of the present invention is not limited to these.

[0188]

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[0189]

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[0190]

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[0191]

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[0192]

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Further, a repeating structural unit in which R ₉₂ in the formula (III) has a structure represented by the following formula (IX) or (X) will be described. -R ₉₈ -A ₅₀ -R ₉₉ (IX) -SO ₃ R ₁₀₀ (X)

In the general formula (IX), R ₉₈ represents a single bond, an alkylene group, an arylene group, or a combination thereof.
Represents a valence group. The arylene group has 6 to 10 carbon atoms.
And may have a substituent. Specific examples include a phenylene group, a tolylene group, and a naphthylene group.

Examples of the alkylene group include the following groups. -[C (Rf) (Rg)] r- wherein Rf and Rg represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, or an alkoxy group, and they may be the same or different; The group is preferably a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group and a butyl group, and more preferably represents a substituent selected from the group consisting of a methyl group, an ethyl group, a propyl group and an isopropyl group. . Examples of the substituent of the substituted alkyl group include a hydroxyl group, a halogen atom, and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. r represents an integer of 1 to 10. In the above, examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom.

A ₅₀ represents any of the following functional groups.

[0197]

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R ₉₉ represents a hydrogen atom or an alkyl group. The chain alkyl group for R ₉₉ may be linear or branched, and may have a substituent. The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably has 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, Preferable examples include n-butyl group, isobutyl group, sec-butyl group, t-butyl group, pentyl group, hexyl group, heptyl group, octyl group, nonyl group, and decyl group.

R ₁₀₀ in the general formula (X) represents a linear or cyclic alkyl group, aryl group or aralkyl group which may have a substituent. The chain alkyl group of R ₁₀₀ may be linear or branched, and may have a substituent. The linear or branched alkyl group preferably has 1 to 12 carbon atoms, more preferably has 1 to 10 carbon atoms, and specifically includes a methyl group, an ethyl group, a propyl group, an isopropyl group, n-butyl group,
Preferred examples include an isobutyl group, a sec-butyl group, a t-butyl group, a pentyl group, a hexyl group, a heptyl group, an octyl group, a nonyl group, and a decyl group. Examples of the cyclic alkyl group represented by R ₁₀₀ include those having 3 to 30 carbon atoms, and specifically include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a norbornyl group, a boronyl group, and a tricyclodecanyl group. , Dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group, steroid residue and the like.

The aryl group represented by R ₁₀₀ has 6 to 6 carbon atoms.
20, and may have a substituent. Specific examples include a phenyl group, a tolyl group, and a naphthyl group. The aralkyl group for R ₁₀₀ has 7 to 20 carbon atoms.
And may have a substituent. Specific examples include a benzyl group, a phenethyl group, and a cumyl group.

Examples of the substituent which the chain alkyl group of R ₉₉ and the chain or cyclic alkyl group, alkoxy group, aryl group or aralkyl group of R ₁₀₀ may have include, for example, carboxyl group, cyano group, Hydroxyl group, halogen atom (chlorine atom, bromine atom, fluorine atom, iodine atom, etc.), alkoxy group (preferably having 1 to 4 carbon atoms, for example, methoxy group, ethoxy group, propoxy group, butoxy group), acetylamide group, alkoxycarbonyl Group, acyl group (preferably having 2 to 10 carbon atoms, for example, formyl group, acetyl group, propionyl group), acyloxy group (preferably having 2 to 10 carbon atoms, for example, acetoxy group), aryl group (preferably having 6 to 10 carbon atoms) 14, for example, a phenyl group). As for the aryl group or the aralkyl group as R _100, as a substituent, an alkyl group (preferably having 1 to 5 carbon atoms, for example, a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a cyclopropyl group, a cyclobutyl group, A cyclopentyl group). The alkyl group as the substituent further includes a hydroxyl group, a halogen atom, and an alkoxy group (preferably having 1 to 4 carbon atoms, such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group).
And the like.

[0202] Hereinafter, -NH-SO ₂ - formula containing
Specific examples (2) to (5) of the monomer corresponding to the repeating unit represented by (III), and specific examples (6) of the monomer corresponding to the repeating structural unit having the structure represented by the general formula (IX) To (15), but are not limited thereto.

[0203]

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[0204]

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[0205]

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Hereinafter, specific examples of the monomer corresponding to the repeating structural unit having the structure represented by formula (X) will be shown, but the invention is not limited thereto.

[0207]

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[0208]

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[0209]

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The acid-decomposable resin used in the present invention may further contain a repeating unit represented by the following formula (XI).

[0211]

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With respect to the general formula (XI), R ₉₁ c, X ₅ c,
R ₉₃ c and B c are the same as R ₉₁ , X ₅ , R ₉₃ and B in the formula (III), respectively. R _92c represents a group represented by the following general formula (XI ′).

[0213]

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In the general formula (XI ′), R ₂ c to R ₄ c
Each independently represents a hydrogen atom or a hydroxyl group. Where R
At least one of ₂ c to R ₄ c represents a hydroxyl group.

The structure represented by formula (XI) is preferably a dihydroxy form or a monohydroxy form, more preferably a dihydroxy form.

Specific examples of the repeating unit having the structure represented by formula (XI) are shown below, but it should not be construed that the invention is limited thereto.

[0219]

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[0218]

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The acid-decomposable resin of the present invention may further contain a repeating unit represented by the following formula (XI-A) or (XI-B).

[0220]

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In the above formula (XI-A), R _{13h to} R _16h
Is independently a hydrogen atom, a halogen atom, a cyano group,
-COOH, -COOR _17h , -C (= O) -X _h -A _h
-R represents a _{1 8h,} or may have a substituent alkyl or cyclic hydrocarbon group. Further, at least two members out of R _{13h to} R _16h may combine to form a ring. n represents 0 or 1. However, none of R _{13h to} R _16h has a group that can be decomposed by an acid. R _17h represents an alkyl group, a cyclic hydrocarbon group or the above-mentioned -Y which may have a substituent.
Represents a group. X _h is an oxygen atom, a sulfur atom, -NH-,-
Represents NHSO ₂ — or —NHSO ₂ NH—. A _h represents a single bond or a divalent linking group. R _18h represents -COOH,-
COOR _17h , -CN, a hydroxyl group, an optionally substituted alkoxy group, -CO-NH-R _19h , -CO-N
Represents an H-SO ₂ -R _19h or said -Y groups. R _19h is
Represents an alkyl group or a cyclic hydrocarbon group which may have a substituent.

Examples of the halogen atom in R _{13h to} R _16h include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

The alkyl group for R _{13h to} R _16h is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably methyl, ethyl, propyl, isopropyl, n-
A butyl group, an isobutyl group, a sec-butyl group and a t-butyl group.

Examples of the cyclic hydrocarbon group for R _{13h to} R _16h include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, and a 2-methyl-2-adamantyl. Group, norbornyl group, boronyl group, isobornyl group,
Examples include a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. The ring formed by combining at least two of the above R _{13h to} R _16h is a ring having 5 to 5 carbon atoms such as cyclopentene, cyclohexene, cycloheptane and cyclooctane.
Twelve rings.

Examples of the alkoxy group for R _18h include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Further substituents in the above alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. As the halogen atom, a chlorine atom, a bromine atom, a fluorine atom,
And iodine atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

Examples of the divalent linking group for A _h include a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group,
A single one selected from the group consisting of a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups is exemplified.

[0228] Alkylene groups represented by A _h, as the substituted alkylene group include a group represented by the following formula. -[C (R _bh ) (R _ch )] _r-wherein R _bh and R _ch represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

In the general formula (XI-B), R _{13i to} R _16i are
Each independently represents a hydrogen atom, a halogen atom, a cyano group, -C
OOH, -COOR _17i , a group decomposed by the action of an acid,
—C (＝ O) —X _i —A _i —R _18i , or an alkyl group or a cyclic hydrocarbon group which may have a substituent.
In addition, at least two members out of R _{13i to} R _16i may combine to form a ring. n represents 0 or 1. R _17i represents an _optionally substituted alkyl group, cyclic hydrocarbon group or the above-mentioned —Y group. X _i represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-. A _i represents a single bond or a divalent linking group. R _18i is
-COOH, -COOR _17i , -CN, a hydroxyl group, an optionally substituted alkoxy group, -CO-NH-R
_19i, represents a -CO-NH-SO ₂ -R _19i or said -Y groups. R _19i represents an alkyl group or a cyclic hydrocarbon group which may have a substituent. In the above-mentioned -Y group, R _{21 to} R
Each ₃₀ independently represents a hydrogen atom or an alkyl group which may have a substituent. a and b represent 1 or 2.

The structure of the group decomposed by the action of an acid is represented by -C (= O) -X _1i -R _pi . _Where R _pi
A tertiary alkyl group such as a t-butyl group and a t-amyl group, an isobornyl group, a 1-ethoxyethyl group, a 1-butoxyethyl group, a 1-isobutoxyethyl group, and a 1-cyclohexyloxyethyl group. -An alkoxyethyl group,
1-methoxymethyl group, 1-ethoxymethyl group and other alkoxymethyl group, 3-oxoalkyl group, tetrahydropyranyl group, tetrahydrofuranyl group, trialkylsilyl ester group, 3-oxocyclohexyl ester group, 2-methyl-2 -Adamantyl group, mevalonic lactone residue, 2- (γ-butyrolactonyloxycarbonyl) -2-propyl group and the like. X _1i
It represents an oxygen atom, a sulfur atom, -NH -, - NHSO ₂ - or an -NHSO ₂ NH-.

Examples of the halogen atom for R _{13i to} R _16i include a chlorine atom, a bromine atom, a fluorine atom and an iodine atom.

The alkyl group for R _{13i to} R _16i is preferably a linear or branched alkyl group having 1 to 10 carbon atoms, more preferably a linear or branched alkyl group having 1 to 6 carbon atoms. And more preferably methyl, ethyl, propyl, isopropyl, n-
A butyl group, an isobutyl group, a sec-butyl group and a t-butyl group.

Examples of the cyclic hydrocarbon group for R _{13i to} R _16i include a cyclic alkyl group and a bridged hydrocarbon group, such as cyclopropyl group, cyclopentyl group, cyclohexyl group, adamantyl group, 2-methyl-2-adamantyl. Group, norbornyl group, boronyl group, isobornyl group,
Examples include a tricyclodecanyl group, a dicyclopentenyl group, a nobornane epoxy group, a menthyl group, an isomenthyl group, a neomenthyl group, and a tetracyclododecanyl group. The ring formed by combining at least two of the above R _{13i to} R _16i is a ring having 5 to 5 carbon atoms such as cyclopentene, cyclohexene, cycloheptane, cyclooctane and the like.
Twelve rings.

Examples of the alkoxy group for R _18i include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group.

Further substituents in the above alkyl group, cyclic hydrocarbon group and alkoxy group include a hydroxyl group, a halogen atom, a carboxyl group, an alkoxy group, an acyl group, a cyano group and an acyloxy group. As the halogen atom, a chlorine atom, a bromine atom, a fluorine atom,
And iodine atoms. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group, and a butoxy group. Examples of the acyl group include a formyl group and an acetyl group. Examples thereof include an acetoxy group.

Examples of the divalent linking group for A _i include a single bond, an alkylene group, a substituted alkylene group, an ether group, a thioether group, a carbonyl group, an ester group, an amide group,
A single one selected from the group consisting of a sulfonamide group, a urethane group, and a urea group, or a combination of two or more groups is exemplified.

[0237] Alkylene groups represented by A _i, as the substituted alkylene group include a group represented by the following formula. -[C (R _bi ) (R _ci )] _r-wherein R _bi and R _ci represent a hydrogen atom, an alkyl group, a substituted alkyl group, a halogen atom, a hydroxyl group, an alkoxy group,
Both may be the same or different. As the alkyl group, a lower alkyl group such as a methyl group, an ethyl group, a propyl group, an isopropyl group, and a butyl group is preferable, and a methyl group, an ethyl group, a propyl group, and an isopropyl group are more preferable. As the substituent of the substituted alkyl group,
Examples include a hydroxyl group, a halogen atom and an alkoxy group. Examples of the alkoxy group include those having 1 to 4 carbon atoms such as a methoxy group, an ethoxy group, a propoxy group and a butoxy group. Examples of the halogen atom include a chlorine atom, a bromine atom, a fluorine atom, and an iodine atom. r represents an integer of 1 to 10.

Specific examples of the repeating unit represented by the general formula (XI-A) or (XI-B) include the following, but the present invention is limited to these specific examples. Not something.

[0239]

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[0240]

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As preferred copolymer components which may be further contained in the acid-decomposable resin according to the present invention, the following general formula (XII-
A) or a repeating unit represented by (XII-B).

[0242]

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In the formula, Z_jIs an oxygen atom, -NH-,
-N (-R_50j)-, -N (-OSO _TwoR_50j)-
Then R_50jIs (substituted) alkyl group, (substituted) cyclic hydrocarbon
Has a meaning.

As the alkyl group for R _50j ,
A linear or branched alkyl group having 1 to 10 carbon atoms is preferable, a linear or branched alkyl group having 1 to 6 carbon atoms is more preferable, and a methyl group, an ethyl group, and a propyl group are more preferable. Isopropyl group, n-butyl group, isobutyl group, sec-butyl group and t-butyl group.

Examples of the cyclic hydrocarbon group for R _50j include a cyclic alkyl group and a bridged hydrocarbon group, such as a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, an adamantyl group, a 2-methyl-2-adamantyl group, and a norbornyl group. Group, boronyl group, isobornyl group, tricyclodecanyl group, dicyclopentenyl group, nobornane epoxy group, menthyl group, isomenthyl group, neomenthyl group, tetracyclododecanyl group and the like. As specific examples of the repeating unit represented by formula (XII-A) or (XII-B), the following [XII-A-9]
To [XII-A-16], [XII-B-9] to [XII-B]
-16], but is not limited to these specific examples.

[0246]

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[0247]

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In the acid-decomposable resin according to the present invention, the following monomers are further copolymerized so as to give a repeating unit constituting the resin within a range where the effects of the present invention can be effectively obtained. However, the present invention is not limited to the following monomers. Thereby, the performance required for the resin, particularly (1) solubility in a coating solvent, (2) film forming property (glass transition point), (3) alkali developability, and (4) film loss (hydrophobicity, alkali (Selection of a soluble group), (5) adhesion of the unexposed portion to the substrate, and (6) dry etching resistance can be finely adjusted. Examples of such a comonomer include acrylates, methacrylates,
Examples thereof include compounds having one addition-polymerizable unsaturated bond selected from acrylamides, methacrylamides, allyl compounds, vinyl ethers, vinyl esters, and the like.

Specifically, for example, acrylic esters such as alkyl (the alkyl group has 1 to 1 carbon atoms)
Acrylates (for example, methyl acrylate, ethyl acrylate, propyl acrylate, amyl acrylate, cyclohexyl acrylate, ethylhexyl acrylate, octyl acrylate, acrylate-
t-octyl, chloroethyl acrylate, 2-hydroxyethyl acrylate 2,2-dimethylhydroxypropyl acrylate, 5-hydroxypentyl acrylate, trimethylolpropane monoacrylate, pentaerythritol monoacrylate, benzyl acrylate, methoxybenzyl acrylate, furfuryl acrylate, Tetrahydrofurfuryl acrylate, etc.);

Methacrylic esters, for example, alkyl (alkyl having preferably 1 to 10 carbon atoms) methacrylate (for example, methyl methacrylate,
Ethyl methacrylate, propyl methacrylate, isopropyl methacrylate, amyl methacrylate, hexyl methacrylate, cyclohexyl methacrylate,
Benzyl methacrylate, chlorobenzyl methacrylate, octyl methacrylate, 2-hydroxyethyl methacrylate, 4-hydroxybutyl methacrylate,
5-hydroxypentyl methacrylate, 2,2-dimethyl-3-hydroxypropyl methacrylate, trimethylolpropane monomethacrylate, pentaerythritol monomethacrylate, furfuryl methacrylate, tetrahydrofurfuryl methacrylate, etc.);

Acrylamides, for example, acrylamide, N-alkylacrylamide, (where the alkyl group has 1 to 10 carbon atoms, for example, methyl, ethyl, propyl, butyl, t-butyl, heptyl, octyl Group, cyclohexyl group, hydroxyethyl group, etc.), N, N-dialkylacrylamide (alkyl group having 1 to 10 carbon atoms, for example, methyl group, ethyl group, butyl group, isobutyl group, ethylhexyl group, A cyclohexyl group, etc.), N-
Hydroxyethyl-N-methylacrylamide, N-2
-Acetamidoethyl-N-acetylacrylamide and the like;

Methacrylamides, for example, methacrylamide, N-alkyl methacrylamide (alkyl having 1 to 10 carbon atoms, for example, methyl, ethyl, t-butyl, ethylhexyl, hydroxyethyl, cyclohexyl) Groups, etc.), N, N-dialkylmethacrylamide (an alkyl group includes an ethyl group, a propyl group, a butyl group, etc.), N-hydroxyethyl-N-methylmethacrylamide and the like;

Allyl compounds such as allyl esters (eg, allyl acetate, allyl caproate, allyl caprylate, allyl laurate, allyl palmitate, allyl stearate, allyl benzoate, allyl acetoacetate, allyl lactate), allyloxy Ethanol, etc .;

Vinyl ethers such as alkyl vinyl ethers (eg, hexyl vinyl ether, octyl vinyl ether, decyl vinyl ether, ethylhexyl vinyl ether, methoxyethyl vinyl ether, ethoxyethyl vinyl ether, chloroethyl vinyl ether, 1-methyl-2,2-dimethylpropyl vinyl ether, 2-ethyl Butyl vinyl ether, hydroxyethyl vinyl ether, diethylene glycol vinyl ether, dimethylaminoethyl vinyl ether, diethylaminoethyl vinyl ether, butylaminoethyl vinyl ether, benzyl vinyl ether, tetrahydrofurfuryl vinyl ether, etc.);

Vinyl esters such as vinyl butyrate, vinyl isobutyrate, vinyl trimethyl acetate, vinyl diethyl acetate, vinyl valate, vinyl caproate, vinyl chloroacetate, vinyl dichloroacetate, vinyl methoxy acetate, vinyl butoxy acetate, Vinyl acetoacetate, vinyl lactate, vinyl-β-phenylbutyrate, vinylcyclohexylcarboxylate and the like;

Dialkyl itaconates (eg, dimethyl itaconate, diethyl itaconate, dibutyl itaconate, etc.); acrylic acid, methacrylic acid, crotonic acid, itaconic acid, acrylonitrile, methacrylonitrile and the like.

The proportion of each repeating unit depends on the desired dry etching resistance of the resist, sensitivity, prevention of pattern cracking, substrate adhesion, resist profile, and resolution, heat resistance, etc. which are necessary requirements of general resists. It can be set appropriately in consideration of the situation.

The content of the repeating structural unit represented by the general formula (I) in the acid-decomposable resin is as follows:
It is preferably from 10 to 60 mol%, more preferably from 15 to 5 mol%.
It is 5 mol%, more preferably 20 to 50 mol%. In the acid-decomposable resin, the content of the repeating structural unit represented by the general formula (II) is 10 to 70 mol% in all the repeating structural units.
Is more preferable, more preferably 15 to 60 mol%, and still more preferably 20 to 50 mol%. In the acid-decomposable resin, the content of the repeating structural unit represented by the general formula (III) is
It is preferably 1 to 80 mol%, more preferably 2 to 75 mol%, and still more preferably 5 to 70 mol% in all the repeating structural units.
Mol%.

In the acid-decomposable resin, the compounds represented by the general formulas (I) and (II)
The total of the repeating units having an acid-decomposable group such as the repeating structural unit represented by I) is preferably from 15 to 90 mol%, more preferably from 15 to 85 mol%, even more preferably from 20 to 80 mol%. is there.

Further, the content of the repeating structural unit based on the monomer of the further copolymerization component other than the repeating structural unit represented by the above (I), (II) or (III) in the resin may be adjusted to a desired value. Although it can be appropriately set according to the performance of the above, generally, other additional units are added to the total number of moles of the repeating structural units represented by the general formulas (I), (II) and (III). The total number of repeating structural units is preferably 99 mol% or less, more preferably 90 mol% or less, and still more preferably 80 mol% or less. When the composition of the present invention is used for ArF exposure, the acid-decomposable resin preferably does not contain an aromatic ring from the viewpoint of transparency to ArF light.

The acid-decomposable resin used in the present invention can be synthesized according to a conventional method (for example, radical polymerization). For example, as a general synthesis method, monomer species are charged into a reaction vessel at once or in the middle of a reaction, and if necessary, a reaction solvent such as tetrahydrofuran, 1,4-dioxane, ethers such as diisopropyl ether and methyl ethyl ketone, Ketones such as methyl isobutyl ketone, ester solvents such as ethyl acetate, and further dissolved in a solvent that dissolves the composition of the present invention such as propylene glycol monomethyl ether acetate described below, and then homogenized. Under an inert gas atmosphere, if necessary, heating is performed, and polymerization is started using a commercially available radical initiator (such as an azo initiator or a peroxide).
If desired, an initiator is added or added in portions, and after completion of the reaction, the mixture is poured into a solvent and a desired polymer is recovered by a method such as powder or solid recovery. Reaction concentration is 20% by weight
It is preferably at least 30% by weight, more preferably at least 40% by weight. Reaction temperature is 10 ° C. to 150
° C, preferably from 30 ° C to 120 ° C, more preferably from 50 to 100 ° C.

The weight-average molecular weight of the acid-decomposable resin according to the present invention is preferably from 1,000 to 200,000 in terms of polystyrene by the GPC method. When the weight average molecular weight is less than 1,000, heat resistance and dry etching resistance are deteriorated, so that it is not preferable.
If it exceeds 00, the development property is deteriorated and the viscosity becomes extremely high, so that a film formation property is deteriorated.

In the positive photoresist composition for deep ultraviolet exposure according to the present invention, the compounding amount of the acid-decomposable resin according to the present invention in the whole composition is 40 to 9 in the total solid content of the resist.
9.99% by weight is preferable, and more preferably 50 to 9% by weight.
9.97% by weight.

The solid content of (A) the photoacid generator or (B) the resin is added to the above solvent in a solid concentration of 3 to 25% by weight.
It is preferably dissolved, more preferably 5 to 22% by weight, and still more preferably 7 to 20% by weight.

[3] Surfactant The positive photoresist composition for deep ultraviolet exposure according to the present invention preferably contains a fluorine-based and / or silicon-based surfactant. The fluorine-based and / or silicon-based surfactant is at least one of a fluorine-based surfactant, a silicon-based surfactant, and a surfactant containing both a fluorine atom and a silicon atom. The positive photoresist composition for deep ultraviolet exposure of the present invention contains the acid-decomposable resin and the surfactant,
When an exposure light source of 50 nm or less, particularly 220 nm or less is used, a resist pattern having excellent sensitivity, resolution, substrate adhesion, and dry etching resistance, and having less development defects and scum can be obtained. As these surfactants, for example, JP-A-62-36663, JP-A-61-226746, JP-A-61-226745
No., JP-A-62-170950, JP-A-63-34540, JP-A-7-2
No. 30165, JP-A-8-62834, JP-A-9-54432, JP-A-9
No.-5988, U.S. Pat.Nos. 5,405,720, 5,306,692, 5,529,881
Nos. 5296330, 5436098, 5576143, 52945
Nos. 11 and 5824451, and the following commercially available surfactants can be used as they are. As commercially available surfactants that can be used, for example, F-top EF301, EF303, (manufactured by Shin-Akita Chemical Co., Ltd.), Florad FC
430, 431 (Sumitomo 3M Limited), Mega Fuck F171,
F173, F176, F189, R08 (Dainippon Ink Chemical Industry Co., Ltd.)
Manufactured), Surflon S-382, SC101, 102, 103, 104, 10
5, 106 (manufactured by Asahi Glass Co., Ltd.) or a fluorine-based surfactant or a silicon-based surfactant. In addition, polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.)
Can also be used as a silicon-based surfactant.

The amount of the surfactant is usually 0.001% by weight to 2% by weight, preferably 0.01% by weight to 1% by weight, based on the solid content in the composition of the present invention. These surfactants can be used alone or in combination of two or more.

Examples of the other surfactants include polyoxyethylene alkyl ethers such as polyoxyethylene lauryl ether, polyoxyethylene stearyl ether, polyoxyethylene cetyl ether, and polyoxyethylene oleyl ether; Polyoxyethylene alkyl allyl ethers such as oxyethylene octyl phenol ether, polyoxyethylene nonyl phenol ether, polyoxyethylene / polyoxypropylene block copolymers, sorbitan monolaurate, sorbitan monopalmitate, sorbitan monostearate, sorbitan monooleate Fatty acid esters such as sorbitan trioleate, sorbitan tristearate, polyoxyethylene sorbitan monolaurate Nonionic surfactants such as polyoxyethylene sorbitan monopalmitate, polyoxyethylene sorbitan monostearate, polyoxyethylene sorbitan trioleate, polyoxyethylene sorbitan fatty acid esters such as polyoxyethylene sorbitan tristearate, etc. Can be mentioned. The amount of these surfactants is usually 2 parts by weight or less, preferably 1 part by weight or less, per 100 parts by weight of the solids in the composition of the present invention. These surfactants may be added alone or in some combination.

[4] Organic Basic Compound A preferable organic basic compound that can be used in the present invention is a compound that is more basic than phenol. Among them, a nitrogen-containing basic compound is preferable.

[0269]

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Here, R ²⁵⁰ , R ²⁵¹ and R ²⁵² are the same or different and each represent a hydrogen atom, an alkyl group having 1 to 6 carbon atoms, an aminoalkyl group having 1 to 6 carbon atoms, or a hydroxyalkyl having 1 to 6 carbon atoms. Or a substituted or unsubstituted aryl group having 6 to 20 carbon atoms, wherein R ²⁵¹ and R ²⁵² may be bonded to each other to form a ring.

[0271]

Embedded image

Wherein R ²⁵³ , R ²⁵⁴ , R ²⁵⁵ and R ²⁵⁶
Are the same or different and represent an alkyl group having 1 to 6 carbon atoms.) Further preferred compounds are nitrogen-containing basic compounds having two or more nitrogen atoms having different chemical environments in one molecule,
Particularly preferred are compounds containing both a substituted or unsubstituted amino group and a ring structure containing a nitrogen atom, or compounds having an alkylamino group. Preferred specific examples include substituted or unsubstituted guanidine, substituted or unsubstituted aminopyridine, substituted or unsubstituted aminoalkylpyridine, substituted or unsubstituted aminopyrrolidine, substituted or unsubstituted indazol, substituted or unsubstituted Pyrazole, substituted or unsubstituted pyrazine,
Substituted or unsubstituted pyrimidine, substituted or unsubstituted purine, substituted or unsubstituted imidazoline, substituted or unsubstituted pyrazoline, substituted or unsubstituted piperazine, substituted or unsubstituted aminomorpholine, substituted or unsubstituted amino And alkyl morpholine. Preferred substituents are an amino group, an aminoalkyl group, an alkylamino group, an aminoaryl group, an arylamino group, an alkyl group, an alkoxy group, an acyl group, an acyloxy group, an aryl group, an aryloxy group, a nitro group,
A hydroxyl group and a cyano group.

Preferred specific compounds are guanidine, 1,1-dimethylguanidine, 1,1,3,3,-
Tetramethylguanidine, 2-aminopyridine, 3-aminopyridine, 4-aminopyridine, 2-dimethylaminopyridine, 4-dimethylaminopyridine, 2-diethylaminopyridine, 2- (aminomethyl) pyridine,
-Amino-3-methylpyridine, 2-amino-4-methylpyridine, 2-amino-5-methylpyridine, 2-amino-6-methylpyridine, 3-aminoethylpyridine, 4-aminoethylpyridine, 3-amino Pyrrolidine, piperazine, N- (2-aminoethyl) piperazine, N- (2-aminoethyl) piperidine, 4-amino-2,2,6,6-tetramethylpiperidine, 4-piperidinopiperidine, 2-imino Piperidine, 1- (2-
Aminoethyl) pyrrolidine, pyrazole, 3-amino-
5-methylpyrazole, 5-amino-3-methyl-1-
p-tolylpyrazole, pyrazine, 2- (aminomethyl) -5-methylpyrazine, pyrimidine, 2,4-diaminopyrimidine, 4,6-dihydroxypyrimidine,
-Pyrazoline, 3-pyrazoline, N-aminomorpholine, N- (2-aminoethyl) morpholine, 1,5-
Diazabicyclo [4,3,0] non-5-ene, 1,8
-Diazabicyclo [5,4,0] undec-7-ene,
3,4,5-triphenylimidazole, N-methylmorpholine, N-ethylmorpholine, N-hydroxyethylmorpholine, N-benzylmorpholine, cyclohexylmorpholinoethylthiourea (CHMETU)
Grade morpholine derivatives, hindered amines described in JP-A-11-52575 (for example, [0005]
), But is not limited thereto.

Particularly preferred specific examples are 1,5-diazabicyclo [4.3.0] -5-nonene, 1,8-diazabicyclo [5.4.0] -7-undecene, 1,4-diazabicyclo [2 .2.2] octane, 4-dimethylaminopyridine,
Hexamethylenetetramine, 4,4-dimethylimidazoline, pyrroles, pyrazoles, imidazoles, pyridazines, pyrimidines, tertiary morpholines such as CHMETU, bis (1,2,2,6,6-pentamethyl-
Hindered amines such as (4-piperidyl) sebagate and the like can be mentioned. By using these, the density dependency becomes excellent.

Among them, 1,5-diazabicyclo [4,
3,0] non-5-ene, 1,8-diazabicyclo [5,4,0] undec-7-ene, 1,4-diazabicyclo [2,2,2] octane, 4-dimethylaminopyridine, hexamethylene Preferred are tetramine, CHMETU, and bis (1,2,2,6,6-pentamethyl-4-piperidyl) sebacate.

These nitrogen-containing basic compounds are used alone or in combination of two or more. The amount of the nitrogen-containing basic compound to be used is generally 0.001 to 10% by weight, preferably 0.01 to 5% by weight, based on the solid content of the entire photosensitive resin composition. If the amount is less than 0.001% by weight, the effect of the addition of the nitrogen-containing basic compound cannot be obtained. On the other hand, if it exceeds 10% by weight, the sensitivity tends to decrease and the developability of the unexposed portion tends to deteriorate.

[5] Other Additives The positive photoresist composition of the present invention may further enhance the solubility in an acid-decomposable dissolution inhibiting compound, a dye, a plasticizer, a sensitizer and a developer, if necessary. And the like can be contained.

The positive resist composition of the present invention is applied to a support by dissolving the above components in a solvent capable of dissolving the above components. As the solvent used here, ethylene dichloride, cyclohexanone, cyclopentanone, 2-heptanone,
γ-butyrolactone, methyl ethyl ketone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, 2-methoxyethyl acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, toluene, ethyl acetate, methyl lactate, lactic acid Ethyl, methyl methoxypropionate, ethyl ethoxypropionate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, N, N-
Dimethylformamide, dimethylsulfoxide, N-methylpyrrolidone, tetrahydrofuran and the like are preferable, and these solvents are used alone or in combination.

Of the above, preferred solvents are propylene glycol monomethyl ether acetate, 2-
Heptanone, γ-butyrolactone, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether, propylene glycol monoethyl ether, methyl lactate, ethyl lactate, methyl methoxypropionate, ethyl ethoxypropionate , N-methylpyrrolidone and tetrahydrofuran.

Such a positive photoresist composition of the present invention is applied on a substrate to form a thin film. The thickness of this coating film is preferably from 0.2 to 1.2 μm. In the present invention, if necessary, a commercially available inorganic or organic antireflection film can be used.

As the antireflection film, an inorganic film type such as titanium, titanium dioxide, titanium nitride, chromium oxide, carbon and α-silicon, and an organic film type made of a light absorbing agent and a polymer material can be used. The former requires equipment such as a vacuum deposition apparatus, a CVD apparatus, and a sputtering apparatus for film formation. As the organic antireflection film, for example, Japanese Patent Publication No. 7-69
611, a condensate of a formaldehyde-modified melamine resin with a diphenylamine derivative, an alkali-soluble resin,
A light absorbing agent or a reaction product of a maleic anhydride copolymer and a diamine type light absorbing agent described in US Pat. No. 5,294,680;
JP-A-6-118631, containing a resin binder and a methylolmelamine-based thermal crosslinking agent;
Acrylic resin type antireflection film having a carboxylic acid group, an epoxy group and a light absorbing group in the same molecule described in 18656, a film comprising a methylolmelamine and a benzophenone-based light absorbing agent described in JP-A-8-87115, and a method described in JP-A-8-179509 Examples thereof include those obtained by adding a low-molecular-weight light absorbing agent to a polyvinyl alcohol resin. Also, as an organic anti-reflection film,
DUV30 series manufactured by Brewer Science,
DUV-40 series, Shipley's AC-2, AC
-3 can also be used.

The above-mentioned resist solution is coated on a substrate (eg, a silicon / silicon dioxide coating) used for the production of precision integrated circuit devices (on a substrate provided with the above antireflection film if necessary), a spinner, a coater, and the like. After coating by an appropriate coating method such as that described above, exposure through a predetermined mask, baking and development can provide a good resist pattern. Here, the exposure light is preferably 150
It is light having a wavelength of nm to 250 nm. Specifically, Kr
F excimer laser (248 nm), ArF excimer laser (193 nm), F ₂ excimer laser (157
nm), X-rays, electron beams and the like.

Examples of the developing solution include inorganic alkalis such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate and aqueous ammonia;
Primary amines such as ethylamine and n-propylamine;
Secondary amines such as diethylamine and di-n-butylamine, tertiary amines such as triethylamine and methyldiethylamine, alcoholamines such as dimethylethanolamine and triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide and the like An alkaline aqueous solution such as a quaternary ammonium salt, a cyclic amine such as pyrrole, or pyrhelidine can be used. Further, an appropriate amount of an alcohol or a surfactant may be added to the above alkaline aqueous solution.

[0284]

EXAMPLES Hereinafter, the present invention will be described more specifically with reference to examples, but the present invention is not limited to the following examples.

[Synthesis of Acid-Decomposable Resin] A reaction vessel was charged with t-butyl norbornene carboxylate, maleic anhydride, 2-methyl-2-adamantyl acrylate and norbornene lactone acrylate in a molar ratio of 20/20/35/25. , Methyl ethyl ketone / tetrahydrofuran = 1/1 solvent to prepare a solution having a solid content of 60%. This was heated at 65 ° C. under a stream of nitrogen. When the reaction temperature becomes stable, radical initiator V-60 manufactured by Wako Pure Chemical Industries, Ltd.
1 was added at 3 mol% to start the reaction. After heating for 12 hours, the reaction mixture was poured into 5 times the amount of hexane to precipitate a white powder. The precipitated powder was dissolved again in a solvent of methyl ethyl ketone / tetrahydrofuran = 1/1 and poured into a 5-fold amount of hexane / methyl tBu ether to precipitate a white powder, which was filtered and taken out. This operation was repeated again, and drying was performed to obtain the target resin (1). When molecular weight analysis (RI analysis) of the obtained resin (1) by GPC was attempted, 11600 (weight average) in terms of polystyrene,
The amount of residual monomer was 0.4%. From the NMR spectrum, the composition of the resin (1) was 18/23/34/25 in molar ratio of norbornene / maleic anhydride / 2-methyl-2-adamantyl acrylate and norbornene lactone acrylate of the present invention. Hereinafter, resins (2) to (25) were synthesized in the same manner. The structures of the acid-decomposable resins (1) to (25) are shown below.

[0286]

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[0287]

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[0288]

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[0289]

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[0290]

Embedded image

The acid-decomposable resins (1) to (25)
Table 1 shows the molar ratio and the weight average molecular weight of each repeating unit.

[0292]

[Table 1]

Examples 1 to 30 and Comparative Example 1 (Preparation and Evaluation of Positive Photoresist Composition) As shown in Table 2, 1.4 g of the acid-decomposable resin synthesized in the above synthesis example and shown in Table 1, An acid generator (the amount of addition is shown in Table 2), 5 mg of an organic basic compound (amine), and 10 mg of a surfactant, if necessary, were dissolved in a solvent at a solid content of 14% by weight. After filtration through a 1 μm microfilter, positive photoresist compositions of Examples 1 to 30 shown in Table 2 were prepared. Further, as Comparative Example 1, a positive photoresist composition shown in Table 2 was prepared in the same manner as in Examples 1 to 30, except that the following resin (R) and the following photoacid generator were used.

Each compound in Table 2 is as follows. [Solvent] S1: Propylene glycol monomethyl ether acetate S2: Ethyl lactate S3: Butyl acetate S4: 2-Heptanone S5: Propylene glycol monomethyl ether S6: Ethyl ethoxypropionate S7: γ-butyrolactone S8: Ethylene carbonate S9: Propylene carbonate S10: Propylene glycol monoethyl ether acetate

[Surfactant] W-1: Megafac F176 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine) W-2: Megafac R08 (manufactured by Dainippon Ink and Chemicals, Inc.) (fluorine) W-3: Polysiloxane polymer KP-341 (manufactured by Shin-Etsu Chemical Co., Ltd.) W-4: Polyoxyethylene nonyl phenyl ether W-5: Troysol S-366 (Troy Chemical Co., Ltd.)
Made)

[Organic basic compound] 1: DBU (1,8-diazabicyclo [5.4.0]-
7-undecene) 2: 4-DMAP (4-dimethylaminopyridine) 3: TPI (2,4,5-triphenylimidazole) 4: 2,6-diisopropylaniline 5: antipyrine 6: 1- (2′-hydroxy Ethyl) piperazine

[Resin used in Comparative Example] Resin R: a resin having the following structure used in Example 3 of EP1048983A1

[0298]

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[0299]

[Table 2]

[0300]

[Table 3]

(Evaluation Test) First, Brewer Sc
ARC-25 manufactured by ICE Co., Ltd. was coated on a silicon wafer by using a spin coater at a thickness of 30 nm, dried, and then coated with the obtained positive photoresist composition.
After drying at 140 ° C. for 90 seconds, a positive photoresist film having a thickness of about 0.4 μm was formed. Exposure was performed while changing the exposure amount and focus according to (mask size 0.16 μm). 145 heat treatment after exposure
Performed at 90 ° C. for 90 seconds, developed with a 2.38 wt% aqueous solution of tetramethylammonium hydroxide, and rinsed with distilled water to obtain a resist pattern profile. The resist pattern on the silicon wafer thus obtained was observed with a scanning microscope, and the resist was evaluated as follows.

[Exposure Margin]: For each resist, the minimum exposure amount for reproducing a contact hole pattern having a diameter of 0.16 μm was varied by ± 5% to obtain a diameter of 0.16 μm.
Variation of the diameter of the contact hole pattern obtained when exposing and developing a contact hole pattern of μm
[(Variation width / 0.16) × 100] (%) was used as an index of the exposure margin. The smaller this value is, the better. [Defocus latitude]: The defocus latitude is represented by an allowable focus width in a range of ± 10% of the dimension of the 0.16 μm contact hole mask pattern. Table 3 shows the evaluation results.

[0303]

[Table 4]

[0304]

[Table 5]

As is clear from Table 3, the positive photoresist composition for ultraviolet exposure according to the present invention has improved exposure margin and defocus latitude in resolving a contact hole pattern.

[0306]

According to the present invention, it is possible to provide a positive photoresist composition for deep ultraviolet exposure, which has improved exposure margin and defocus latitude in resolving a contact hole pattern.

──────────────────────────────────────────────────続 き Continued on the front page (51) Int.Cl. ⁷ Identification symbol FI Theme coat ゛ (Reference) C08K 5/16 C08K 5/16 5/42 5/42 C08L 33/00 C08L 33/00 35/00 35 / 00 45/00 45/00 G03F 7/004 501 G03F 7/004 501 7/033 7/033 H01L 21/027 H01L 21/30 502R F term (reference) 2H025 AA02 AA04 AB16 AC04 AC08 AD03 BE07 BE10 BG00 CB08 CB10 CB14 CB41 CB42 CB45 CB48 CC04 CC20 FA17 4J002 BG071 BG121 BH021 BK001 ER028 EU028 EU048 EU078 EU098 EU108 EU118 EU128 EU138 EU238 EV236 EV256 FD206 FD208 FD317 GP03 4J100 AJ02R AK32Q AL03R AL04 AM03 AR03 AM03 AR03P BA11Q BA11R BA12R BA15P BA15R BA16R BA28R BA32R BA34R BA37R BA38R BA40R BA55Q BA55R BA58R BA59R BB01R BB07Q BB18Q BC02R BC03P BC03R B C04P BC04R BC08P BC08Q BC08R BC09P BC09R BC09S BC12R BC23R BC43R BC48R BC53P BC53R BC58R CA03 CA05 JA38

Claims (4)

[Claims] (1) A method comprising the steps of:
The following general formulas (I ') to (III') which generate sulfonic acid
And (B) a compound represented by the following general formula (I)
Repeating unit represented by general formula (II)
And a repeating unit represented by the general formula (III).
Incorporated in the alkaline developer by the action of acid
Characterized by containing a resin that increases the dissolution rate
A positive photoresist composition for UV exposure. Embedded imageEmbedded imageEmbedded imageEmbedded imageIn the above general formulas (I ′) to (III ′): R₅₁~ R₈₇Are each
Independently hydrogen, linear, branched or cyclic alkyl
Group, linear, branched or cyclic alkoxy group, hydr
Roxyl group, halogen atom, or -SR₈₈Represents a group.
R₈₈Represents a linear, branched or cyclic alkyl group or
Represents a reel group. Also, R₅₁~ R₆₅, R₆₆~ R₇₇, R₇₈
~ R₈₇Two or more of which combine to form a single bond, carbon, acid
One or more selected from nitrogen, sulfur, and nitrogen
May be formed. X^-Is R^FSO_Three ^-The table
You. Where R^FIs a fluorine-substituted straight-chain having 2 or more carbon atoms
It is a chain, branched or cyclic alkyl group. In the general formula (I): R₁₁~ R₁₄Is, independently of each other, the action of an acid
Groups decomposed by hydrogen atom, halogen atom, cyano
Group, -COOH, -COOR₁₅, -C (= O) -XA
-R₁₆Or represents an alkyl group or a cyclic hydrocarbon group,
And R₁₁~ R₁₄At least one of them is separated by the action of an acid.
Represents a group to be understood. Also, R₁₁~ R₁₄At least two of
Two may combine to form a ring. n represents 0 or 1
You. Where R₁₅Is an alkyl group, a cyclic hydrocarbon group or
Represents the following -Y group. X represents an oxygen atom, a sulfur atom, -N
H-, -NHSO_Two-Or-NHSO_TwoRepresents NH-.
A is a single bond, an alkylene group, a cycloalkylene group,
-Tel group, thioether group, carbonyl group, ester group
A single or a group of two or more groups selected from the group consisting of
Indicates a combination. R₁₆Are -COOH, -COOR₁₅,
-CN, hydroxyl group, alkoxy group, -CO-NH-R₁₇,
-CO-NH-SO_Two-R₁₇Alternatively, it represents the following -Y group.
R₁₇Represents an alkyl group or a cyclic hydrocarbon group. —Y group;In the -Y group, R_{twenty one}~ R₃₀Are each independently a hydrogen atom or
Represents a alkyl group. a and b represent 1 or 2. In the general formula (II): Z_TwoIs -O- or -N (R₄₁)-
Represents Where R₄₁Represents a hydrogen atom, a hydroxyl group, an alkyl
Group, haloalkyl group or -OSO_Two-R₄₂Represents R₄₂
Represents an alkyl group, a haloalkyl group, a cycloalkyl group or
Represents a camphor residue. In the general formula (III): R₉₁Is a hydrogen atom, lower alkyl
Represents a group, a halogen atom or -CN. X_FiveIs -O-,
-S-, -NR₉₃-Or -NR₉₃SO_TwoRepresents-. R
₉₃Represents a hydrogen atom, a chain or a cyclic alkyl group. B
Represents a single bond or a linking group. R₉₂Is a hydrogen atom, a chain
Or cyclic alkyl group, alkoxy group, hydroxyl group, carbo
Xy group, cyano group, -COOR₉₄Or the following general formula (I
V) represents a group represented by any of (X) to (X). R₉₄Is
Represents a hydrogen atom, or a chain or cyclic alkyl group. Embedded image-N⁺(R₉₅) (R₉₆) (R₉₇) ・ X^- (VIII) -R₉₈-A₅₀-R₉₉ (IX) -SO_ThreeR₁₀₀ (X) In the formula (IV), Ra₁, Rb₁, Rc₁, Rd₁,
And Re₁Are each independently a hydrogen atom or a group having 1 to 4 carbon atoms.
Represents an alkyl group. m and n each independently represent an integer of 0 to 3
M + n is 2 or more and 6 or less. Formula (V-1)
In (V-4), R_1b~ R_5bIs, independently of each other, hydrogen
Atom, alkyl group, cycloalkyl group or alkenyl group
Represents R_1b~ R_5bTwo of which combine to form a ring
You may. In the formula (VII), R_1d~ R_8dIs German
In addition, it represents a hydrogen atom or an alkyl group. R_d0Is a hydrogen source
Child, chain or cyclic alkyl group, aryl group or aral
Represents a kill group. m represents an integer of 1 to 10. Equation (VII
I) Medium, R₉₅~ R₉₇Are each independently a hydrogen atom or a chain
Or a cyclic alkyl group, an alkenyl group, an aryl group, or
Represents an aralkyl group. Where R₉₅~ R ₉₇Are connected to each other
To form a non-aromatic ring or an aromatic ring. X^-Is R-S
O_Three ^-Represents R is an aliphatic hydrocarbon group or an aromatic hydrocarbon
Represents a group. In the formula (IX), R₉₈Is a single bond, alkylene
Group, arylene group, or divalent group combining these
Represents A₅₀Represents any of the functional groups shown below. Embedded imageR₉₉Represents a hydrogen atom or an alkyl group. Formula (X)
Medium, R₁₀₀Is a chain or cyclic alkyl group, aryl group or
Represents an aralkyl group. 2. The resin of component (B) further comprises the following formula (XI)
The positive photoresist composition for deep ultraviolet exposure according to claim 1, comprising a repeating unit represented by the following formula: Embedded image In the general formula (XI), R ₉₁ c represents a hydrogen atom, a lower alkyl group, a halogen atom or —CN. X ₅ c is —O—,
-S -, - NR ₉₃ c-, or -NR ₉₃ CSO ₂ - represents a.
R _93c represents a hydrogen atom, a chain or a cyclic alkyl group.
Bc represents a single bond or a linking group. R _92c represents a group represented by the following general formula (XI ′). Embedded image In the general formula _{(XI '), R 2 c~R} 4 c represents a hydrogen atom or a hydroxyl group independently. Provided that at least one of R ₂ c to R ₄ c represents a hydroxyl group. 3. The positive photoresist composition for deep ultraviolet exposure according to claim 1, further comprising a fluorine-based and / or silicon-based surfactant. 4. The positive photoresist composition for deep UV exposure according to claim 1, further comprising an organic basic compound.