JP4200936B2 - Positive radiation sensitive resin composition - Google Patents

Description

  The present invention is particularly suitable for a chemically amplified resist suitable for fine processing using fine ultraviolet rays such as KrF excimer laser or ArF excimer laser as well as deep radiation such as charged particle beam and X-ray. The present invention relates to a radiation resin composition.

In the field of microfabrication represented by the manufacture of integrated circuit elements, in order to obtain a higher degree of integration, the process size in lithography has been miniaturized. In recent years, microfabrication of 0.5 μm or less is reproducible. There is a need for techniques that can be performed well. Therefore, it is necessary to accurately form a pattern of 0.5 μm or less even in a resist used for fine processing, but a conventional method using visible light (wavelength 800 to 400 nm) or near ultraviolet light (wavelength 400 to 300 nm). Then, it is extremely difficult to form a fine pattern of 0.5 μm or less with high accuracy. Therefore, the use of radiation having a shorter wavelength (wavelength of 300 nm or less) has been intensively studied.
Examples of such short-wavelength radiation include charged particles such as far-ultraviolet rays and electron beams typified by an emission line spectrum (wavelength 254 nm) of a mercury lamp, a KrF excimer laser (wavelength 248 nm), or an ArF excimer laser (wavelength 193 nm). X-rays such as X-rays and synchrotron radiation can be mentioned. Among these, lithography using an excimer laser is particularly attracting attention because of its high output and high efficiency characteristics. For this reason, resists used in lithography are also required to be able to form fine patterns of 0.5 μm or less with high sensitivity, high resolution and good reproducibility by excimer laser.

As a resist suitable for far ultraviolet rays such as KrF excimer laser, a radiation sensitive acid generator that generates an acid upon irradiation with radiation (hereinafter referred to as “exposure”) is used, and the sensitivity of the resist by the catalytic action of the acid. A “chemically amplified resist” with improved resistance has been proposed.
As such a chemically amplified resist, for example, Patent Document 1 discloses a combination of a resin protected with a t-butyl group or a t-butoxycarbonyl group and a radiation-sensitive acid generator. Each combination of a silyl group protected resin and a radiation sensitive acid generator is disclosed. In addition, many reports have been made on chemically amplified resists such as a resist containing a resin protected with an acetal group or a ketal group and a radiation-sensitive acid generator (see, for example, Patent Document 3). In particular, a chemically amplified resist using a resin having an acetal group or a ketal group has been a problem in the case of a basic substrate such as silicon nitride or titanium nitride that has been used in the manufacture of integrated circuit elements in recent years. The pull is small and attracts attention (see Non-Patent Document 1, for example).

More recently, a diazodisulfone compound having a structure in which a cyclohexane ring is bonded to a sulfonyl group and two oxygen atoms forming an acyclic or cyclic ketal structure are bonded to a carbon atom at the 3-position of the cyclohexane ring, and the diazo A radiation-sensitive resin composition containing a disulfone compound as a radiation-sensitive acid generator has been proposed, and this radiation-sensitive resin composition has no tail as a chemically amplified resist and is said to have excellent pattern shape. ing. However, the diazodisulfone compound has a broad concept, and the relationship between the structure of the compound, the line edge roughness (that is, the irregularities on the surface of the line pattern), and the focal depth margin has not been studied.

JP 59-45439 A JP-A-60-52845 JP-A-2-25850 Proc.SPIE, Vol.3049, p.314

  However, the development of better chemically amplified resists with smaller line edge roughness and better depth of focus allowance, etc., from the perspective of device design dimensions of sub-half micron and more precise line width control However, in addition to the radiation-sensitive acid generator component that composes it, the functions of the resin component and other additive components are complicatedly related to the function as a chemically amplified resist. In reality, it is still extremely difficult to achieve the function.

  In view of the above-mentioned situation in the prior art, the object of the present invention is to efficiently produce acid with high sensitivity (low exposure energy amount) against various radiations, particularly far ultraviolet rays represented by KrF excimer laser or ArF excimer laser. Contains a diazodisulfone compound that can generate a chemically amplified resist with excellent line edge roughness, depth of focus margin, etc. when used as a radiation sensitive acid generator in chemically amplified resists, especially chemically amplified It is an object of the present invention to provide a positive radiation sensitive resin composition suitable as a resist.

The present invention
(A) a radiation-sensitive acid generator containing a diazodisulfone compound represented by the following formula (1) (hereinafter referred to as “diazodisulfone compound (1)”) as an essential component; and (B) an acid-dissociable group. A positive-type radiation-sensitive resin composition comprising an alkali-insoluble or hardly-alkali-soluble resin having a resin that becomes readily alkali-soluble when the acid-dissociable group is dissociated ,
Consists of.

〔式（１）において、Ｒ¹ 〜Ｒ⁹ は相互に独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシル基または炭素数１〜４のヒドロキシアルキル基を示し、Ａは置換または非置換の炭素数１〜１０の直鎖状もしくは分岐状の２価の炭化水素基を示す。〕

[In Formula (1), R < ¹ > -R < ⁹ > shows a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxyl group, or a C1-C4 hydroxyalkyl group mutually independently, A represents a substituted or non-substituted linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. ]

  The term “alkali-insoluble or alkali-insoluble” as used herein refers to alkali development that is employed when forming a resist pattern from a resist film formed using a radiation-sensitive resin composition containing an acid-dissociable group-containing resin. Under the conditions, when a film using only the resin instead of the resist film is developed, it means that 50% or more of the initial film thickness of the film remains after development.

Hereinafter, the present invention will be described in detail.
Diazodisulfone compound (1)
In the formula (1), the alkyl group having 1 to 4 carbon atoms, the alkoxyl group having 1 to 4 carbon atoms, and the hydroxyalkyl group having 1 to 4 carbon atoms of R ^{1 to} R ⁹ are each linear or branched. be able to.
Preferred examples of R ^{1 to} R ⁹ include hydrogen atom, methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, Methoxy group, ethoxy group, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 2-hydroxy-i-propyl group, 4-hydroxy-n-butyl Examples thereof include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group.

  In formula (1), examples of the substituted or unsubstituted C 1-10 linear or branched divalent hydrocarbon group of A include, for example, two oxygen atoms to which A is bonded, and A group that forms a 5- to 8-membered ring structure with a carbon atom to which two oxygen atoms are bonded is preferable, and a group represented by the following formula (2) is particularly preferable.

〔式（２）において、Ｒ¹⁰〜Ｒ¹³は相互に独立に水素原子、炭素数１〜４のアルキル基、炭素数１〜４のアルコキシル基または炭素数１〜４のヒドロキシアルキル基を示す。〕

[In Formula (2), R < ¹⁰ > -R < ¹³ > shows a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxyl group, or a C1-C4 hydroxyalkyl group mutually independently. ]

In formula (2), the alkyl group having 1 to 4 carbon atoms, the alkoxy group having 1 to 4 carbon atoms, and the hydroxyalkyl group having 1 to 4 carbon atoms in R ^{10 to} R ¹³ are each linear or branched. be able to.
Preferred examples of R ^{10 to} R ¹³ include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, an i-butyl group, a sec-butyl group, a t-butyl group, Methoxy group, ethoxy group, hydroxymethyl group, 2-hydroxyethyl group, 3-hydroxy-n-propyl group, 2-hydroxy-n-propyl group, 2-hydroxy-i-propyl group, 4-hydroxy-n-butyl Examples thereof include a hydrogen atom, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, an n-butyl group, a sec-butyl group, and a t-butyl group.

In the formula (1), examples of the substituent other than the alkoxyl group and the hydroxyl group in the linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms substituted for A include, for example, a halogen atom, a nitro group, A cyano group, an acyl group having 2 to 10 carbon atoms, an alkoxycarbonyloxy group having 2 to 10 carbon atoms, and the like. These acyl groups and alkoxycarbonyloxy groups are linear, branched or cyclic. Can do.
In the formula (1), one or more substituents in the linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms substituted for A may be present.

The diazodisulfone compound (1) can be synthesized, for example, according to the following scheme (I) using t-butylthioalcohol as a reaction raw material. In scheme (I),
Y in Y-SH represents a group represented by the following formula (i).

〔式（ｉ）において、Ｒ¹ 〜Ｒ⁹ およびＡは式（１）におけるそれぞれＲ¹ 〜Ｒ⁹ およびＡと同義である。〕

In [Equation (i), R ¹ to R ⁹ and A have the same meanings as respectively R ¹ to R ⁹ and A in the formula (1). ]

  In the reaction of Scheme (I), t-butylthioalcohol is dissolved in a 1,4-dioxane solution of hydrogen chloride, and reacted by adding paraformaldehyde (p-FAD) to give the chloride shown in (a). Is obtained. Then, the bisthiomethane compound shown to (b) is obtained by making this chloride react with a thiol compound (Y-SH) on basic conditions. Thereafter, the bisthiomethane compound is oxidized by a conventional method to obtain the bissulfonylmethane compound shown in (c). Thereafter, the bissulfonylmethane compound is dissolved in acetonitrile or the like, reacted with p-toluenesulfonyl azide (p-TSAZ) at room temperature under basic conditions, and diazotized, and then purified by column chromatography, By distilling off, the diazodisulfone compound (1) is obtained.

The thiol compound (Y-SH) can be synthesized, for example, according to the following scheme (II) using 2-cyclohexen-1-one or a ring-substituted derivative thereof as a reaction raw material. However, in the scheme (II), the description of the substituents R ^{1 to} R ⁹ on the cyclohexene ring and the cyclohexane ring is omitted.

  2-Cyclohexen-1-one and its ring-substituted derivatives are commercially available as reagents, but those that can be easily obtained as synthesis raw materials for the diazodisulfone compound (1) include 2-cyclohexen-1-one and 2-methyl. -2-cyclohexen-1-one, 4,4-dimethyl-2-cyclohexen-1-one, 2,4,4-trimethyl-2-cyclohexen-1-one, 4,4-di-n-propyl-2 -Cyclohexen-1-one, 2-methoxy-2-cyclohexen-1-one, 5- (2-hydroxy-i-propyl) -2-methyl-2-cyclohexen-1-one, and the like.

In the reaction of Scheme (II), usually 1 to 10 mol, preferably 1 to 3 mol of thioacetic acid is usually 0 to 50 ° C., preferably 10 to 30 ° C. with respect to 1 mol of 2-cyclohexen-1-one. The reaction is usually performed for 2 to 100 hours, preferably 48 to 72 hours, and then purified by distillation to obtain the thioacetate ester shown in (d). Thereafter, the thioacetic acid ester and the diol compound (HO-A-OH) (where A is the same as A in formula (1)) are reacted in the presence of an acid to give (e). The ketal compound shown is obtained. Thereafter, the ketal compound with respect to 1 mole, usually 0.01 to 0.2 mol, preferably in the presence of 0.02 to 0.1 moles of base (e.g., NaOCH _3, KOCH _3, etc.), an organic solvent ( For example, methanol, ethanol, tetrahydrofuran, 1,4-dioxane, etc.) are usually treated at 0-60 ° C., preferably 20-50 ° C., usually for 1-20 hours, preferably 3-5 hours, and then column chromatography. The thiol compound (Y-SH) is obtained by purification by distillation.

  The diazodisulfone compound (1) can generate acid efficiently with high sensitivity (low exposure energy) against various radiations, especially far ultraviolet rays typified by KrF excimer laser or ArF excimer laser, and is stable in storage. It is a compound that can provide a chemically amplified resist with excellent line edge roughness, depth of focus margin, etc. when used as a radiation-sensitive acid generator in chemically amplified resists, especially useful for microfabrication It can be used very suitably as a radiation sensitive acid generator in such chemically amplified resists.

Positive-type radiation-sensitive resin composition The positive-type radiation-sensitive resin composition of the present invention comprises (A) a radiation-sensitive acid generator having (A) a diazodisulfone compound (1) as an essential component and (B) an acid-dissociable group. An alkali-insoluble or hardly-alkali-soluble resin having a resin that is readily alkali-soluble when the acid-dissociable group is dissociated (hereinafter referred to as “acid-dissociable group-containing resin”).

-(A) component-
The amount of the diazodisulfone compound (1) used as the component (A) is usually 0.01 to 50 parts by weight, preferably 0.1 to 30 parts by weight, per 100 parts by weight of the total resin components in the resin composition. Particularly preferred is 0.5 to 25 parts by weight. In this case, if the amount of the diazodisulfone compound (1) used is less than 0.01 parts by weight, the sensitivity and resolution as a resist tend to be reduced. On the other hand, if it exceeds 50 parts by weight, the applicability and heat resistance as a resist. Tends to decrease.
In the present invention, the diazodisulfone compound (1) can be used alone or in admixture of two or more.

In the present invention, a radiation sensitive acid generator (hereinafter referred to as “other acid generator”) other than the diazodisulfone compound (1) may be used in combination as the component (A) in some cases.
Examples of other acid generators include onium salt compounds, sulfone compounds, sulfonic acid ester compounds, and sulfonimide compounds.
Examples of these other acid generators are shown below.

Onium salt compounds:
Examples of the onium salt compound include iodonium salt, sulfonium salt, phosphonium salt, diazonium salt, ammonium salt, pyridinium salt and the like.
Specific examples of the onium salt compound include bis (4-t-butylphenyl) iodonium trifluoromethanesulfonate, bis (4-t-butylphenyl) iodonium nonafluorobutanesulfonate, bis (4-t-butylphenyl) iodonium 2- Trifluoromethylbenzenesulfonate, bis (4-t-butylphenyl) iodonium 10-camphor-sulfonate, bis (4-t-butylphenyl) iodonium p-toluenesulfonate, diphenyliodonium trifluoromethanesulfonate, diphenyliodonium nonafluorobutanesulfonate, Diphenyliodonium 2-trifluoromethylbenzenesulfonate, diphenyliodonium 10-camphor-sulfonate, diphenyliodonium p-tolue Sulfonate, triphenylsulfonium trifluoromethane sulfonate, triphenylsulfonium nonafluorobutanesulfonate, triphenylsulfonium 2-trifluoromethylbenzenesulfonate, triphenylsulfonium 10-camphor - sulfonate, triphenylsulfonium p- toluenesulfonate,

4-t-butylphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butylphenyldiphenylsulfonium nonafluorobutanesulfonate, 4-t-butylphenyldiphenylsulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butylphenyldiphenylsulfonium 10 -Camphor-sulfonate, 4-t-butylphenyldiphenylsulfonium p-toluenesulfonate, 4-t-butoxyphenyldiphenylsulfonium trifluoromethanesulfonate, 4-t-butoxyphenyldiphenylsulfonium nonafluorobutanesulfonate, 4-t-butoxyphenyl diphenyl Sulfonium 2-trifluoromethylbenzenesulfonate, 4-t-butoxyphenyldiphenyls Honiumu 10 camphor - sulfonate, may be mentioned 4-t-butoxyphenyl diphenylsulfonium p- toluenesulfonate and the like.

Sulfone compounds:
Examples of the sulfone compound include β-ketosulfone, β-sulfonylsulfone, and α-diazo compounds thereof.
Specific examples of the sulfone compound include phenacylphenylsulfone, mesitylphenacylsulfone, bis (phenylsulfonyl) methane, 4-trisphenacylsulfone, and the like.
Sulfonic acid ester compounds:
Examples of the sulfonic acid ester compounds include alkyl sulfonic acid esters, haloalkyl sulfonic acid esters, aryl sulfonic acid esters, and imino sulfonates.
Specific examples of the sulfonate compound include benzoin tosylate, pyrogallol tris (trifluoromethanesulfonate), pyrogallol tris (methanesulfonate), nitrobenzyl-9,10-diethoxyanthracene-2-sulfonate, α-methylolbenzointosylate , Α-methylol benzoin n-octane sulfonate, α-methylol benzoin trifluoromethane sulfonate, α-methylol benzoin n-dodecane sulfonate, and the like.
Sulfonimide compounds:
As a sulfonimide compound, the compound represented by following formula (3) can be mentioned, for example.

〔式（３）において、Ｘはアルキレン基、アリーレン基、アルコキシレン基等の２価の基を示し、Ｒ¹⁴はアルキル基、アリール基、ハロゲン置換アルキル基、ハロゲン置換アリール基等の１価の基を示す。）

[In the formula (3), X represents a divalent group such as an alkylene group, an arylene group or an alkoxylene group, and R ¹⁴ represents a monovalent group such as an alkyl group, an aryl group, a halogen-substituted alkyl group or a halogen-substituted aryl group. Indicates a group. )

As a specific example of the sulfonimide compound,
N- (trifluoromethanesulfonyloxy) succinimide, N- (trifluoromethanesulfonyloxy) phthalimide, N- (trifluoromethanesulfonyloxy) diphenylmaleimide, N- (trifluoromethanesulfonyloxy) bicyclo [2.2.1] hept-5 -Ene-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (trifluoromethane Sulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (trifluoromethanesulfonyloxy) naphthylimide,
N- (10-camphorsulfonyloxy) succinimide, N- (10-camphorsulfonyloxy) phthalimide, N- (10-camphorsulfonyloxy) diphenylmaleimide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (10-camphorsulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (10-camphorsulfonyloxy) naphthylimide,

N- (4-methylbenzenesulfonyloxy) succinimide, N- (4-methylbenzenesulfonyloxy) phthalimide, N- (4-methylbenzenesulfonyloxy) diphenylmaleimide, N- (4-methylbenzenesulfonyloxy) bicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (4-methylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (4-methylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-methylbenzenesulfonyloxy) naphthyl Imide,
N- (2-trifluoromethylbenzenesulfonyloxy) succinimide, N- (2-trifluoromethylbenzenesulfonyloxy) phthalimide, N- (2-trifluoromethylbenzenesulfonyloxy) diphenylmaleimide, N- (2-trifluoro Methylbenzenesulfonyloxy) bicyclo [2.2.1] hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) -7-oxabicyclo [2.2.1 ] Hept-5-ene-2,3-dicarboximide, N- (2-trifluoromethylbenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide N- (2-trifluoromethylbenzenesulfonyloxy) naphthylimide,

N- (4-fluorobenzenesulfonyloxy) succinimide, N- (4-fluorobenzenesulfonyloxy) phthalimide, N- (4-fluorobenzenesulfonyloxy) diphenylmaleimide, N- (4-fluorobenzenesulfonyloxy) bicyclo [2 2.1] hept-5-ene-2,3-dicarboximide, N- (4-fluorobenzenesulfonyloxy) -7-oxabicyclo [2.2.1] hept-5-ene-2,3 -Dicarboximide, N- (4-fluorobenzenesulfonyloxy) bicyclo [2.2.1] heptane-5,6-oxy-2,3-dicarboximide, N- (4-fluorobenzenesulfonyloxy) naphthyl An imide etc. can be mentioned.

These other acid generators can be used alone or in admixture of two or more.
The amount of the other acid generator used is preferably 100% by weight or less, particularly preferably 50% by weight or less, based on the diazodisulfone compound (1). In this case, if the amount of the other acid generator used exceeds 100% by weight, the resist pattern formed on the basic substrate tends to be skirted and the pattern shape tends to deteriorate.

-(B) component-
As the acid dissociable group-containing resin constituting the component (B) in the present invention, for example, a hydrogen atom of the acidic functional group in an alkali-soluble resin having one or more acidic functional groups such as a phenolic hydroxyl group and a carboxyl group, A resin having a structure substituted with one or more acid dissociable groups that can be dissociated in the presence of an acid can be given.

  The acid-dissociable group-containing resin in the present invention includes a repeating unit represented by the following formula (4) (hereinafter referred to as “repeating unit (4)”) and a repeating unit represented by the following formula (5) (hereinafter referred to as “repeating unit”). And a resin having a repeating unit (hereinafter referred to as “resin (B1)”).

〔式（４）において、Ｒ¹⁵は水素原子またはメチル基を示す。〕

In [Equation (4), R ¹⁵ represents a hydrogen atom or a methyl group. ]

〔式（５）において、Ｒ¹⁶およびＲ¹⁷は相互に独立に水素原子またはメチル基を示し、
Ｒ¹⁸は炭素数１〜４のアルキル基を示し、Ｒ¹⁹は炭素数１〜６のアルキル基を示す。〕

[In the formula (5), R ¹⁶ and R ¹⁷ each independently represent a hydrogen atom or a methyl group,
R ¹⁸ represents an alkyl group having 1 to 4 carbon atoms, and R ¹⁹ represents an alkyl group having 1 to 6 carbon atoms. ]

In the resin (B1), the repeating unit (4), the repeating unit (5) and other repeating units may be present alone or in combination of two or more.
Further, the resin (B1) can also have a structure partially crosslinked with an appropriate crosslinking group (for example, a crosslinking group having a diethylene glycol skeleton).

In the formula (5), the alkyl group having 1 to 4 carbon atoms of R ¹⁸ may be linear or branched, and examples thereof include a methyl group, an ethyl group, an n-propyl group, and an i-propyl group. , N-butyl group, i-butyl group, sec-butyl group and t-butyl group, and the alkyl group having 1 to 6 carbon atoms of R ¹⁹ is linear, branched or cyclic. Examples thereof include methyl group, ethyl group, n-propyl group, i-propyl group, n-butyl group, i-butyl group, sec-butyl group, t-butyl group, n-pentyl group, neopentyl group. Group, n-hexyl group, cyclopentyl group, cyclohexyl group and the like.

As a specific example of the repeating unit (5),
4- (1-methoxyethoxy) styrene, 4- (1-ethoxyethoxy) styrene, 4- (1-n-propoxyethoxy) styrene, 4- (1-i-propoxyethoxy) styrene, 4- (1-n -Butoxyethoxy) styrene, 4- (1-t-butoxyethoxy) styrene, 4- (1-n-pentyloxyethoxy) styrene, 4- (1-n-hexyloxyethoxy) styrene, 4- (1-cyclopentyl) Oxyethoxy) styrene, 4- (1-cyclohexyloxyethoxy) styrene,
4- (1-methoxypropoxy) styrene, 4- (1-ethoxypropoxy) styrene, 4- (1-n-propoxypropoxy) styrene, 4- (1-i-propoxypropoxy) styrene, 4- (1-n -Butoxypropoxy) styrene, 4- (1-t-butoxypropoxy) styrene, 4- (1-n-pentyloxypropoxy) styrene, 4- (1-n-hexyloxypropoxy) styrene, 4- (1-cyclopentyl) Oxypropoxy) styrene, 4- (1-cyclohexyloxypropoxy) styrene,

4- (1-methoxybutoxy) styrene, 4- (1-ethoxybutoxy) styrene, 4- (1-n-propoxybutoxy) styrene, 4- (1-i-propoxybutoxy) styrene, 4- (1-n -Butoxybutoxy) styrene, 4- (1-t-butoxybutoxy) styrene, 4- (1-n-pentyloxybutoxy) styrene, 4- (1-n-hexyloxybutoxy) styrene, 4- (1-cyclopentyl) Oxybutoxy) styrene, 4- (1-cyclohexyloxybutoxy) styrene,
4- (1-methoxy-2-methylpropoxy) styrene, 4- (1-ethoxy-2-methylpropoxy) styrene, 4- (1-n-propoxy-2-methylpropoxy) styrene, 4- (1-i -Propoxy-2-methylpropoxy) styrene, 4- (1-n-butoxy-2-methylpropoxy) styrene, 4- (1-t-butoxy-2-methylpropoxy) styrene, 4- (1-n-pentyl) Oxy-2-methylpropoxy) styrene, 4- (1-n-hexyloxy-2-methylpropoxy) styrene, 4- (1-cyclopentyloxy-2-methylpropoxy) styrene, 4- (1-cyclohexyloxy-2) -Methylpropoxy) styrene,

4- (1-methoxypentyloxy) styrene, 4- (1-ethoxypentyloxy) styrene, 4- (1-n-propoxypentyloxy) styrene, 4- (1-i-propoxypentyloxy) styrene, 4- (1-n-butoxypentyloxy) styrene, 4- (1-t-butoxypentyloxy) styrene, 4- (1-n-pentyloxypentyloxy) styrene, 4- (1-n-hexyloxypentyloxy) Styrene, 4- (1-cyclopentyloxypentyloxy) styrene, 4- (1-cyclohexyloxypentyloxy) styrene,
4- (1-methoxy-2,2-dimethylpropoxy) styrene, 4- (1-ethoxy-2,2-dimethylpropoxy) styrene, 4- (1-n-propoxy-2,2-dimethylpropoxy) styrene, 4- (1-i-propoxy-2,2-dimethylpropoxy) styrene, 4- (1-n-butoxy-2,2-dimethylpropoxy) styrene, 4- (1-t-butoxy-2,2-dimethyl) Propoxy) styrene, 4- (1-n-pentyloxy-2,2-dimethylpropoxy) styrene, 4- (1-n-hexyloxy-2,2-dimethylpropoxy) styrene, 4- (1-cyclopentyloxy-) 2,2-dimethylpropoxy) styrene, 4- (1-cyclohexyloxy-2,2-dimethylpropoxy) styrene,

4- (1-methoxyethoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) -α-methylstyrene, 4- (1-n-propoxyethoxy) -α-methylstyrene, 4- (1-i -Propoxyethoxy) -α-methylstyrene, 4- (1-n-butoxyethoxy) -α-methylstyrene, 4- (1-t-butoxyethoxy) -α-methylstyrene, 4- (1-n-pentyl) Oxyethoxy) -α-methylstyrene, 4- (1-n-hexyloxyethoxy) -α-methylstyrene, 4- (1-cyclopentyloxyethoxy) -α-methylstyrene, 4- (1-cyclohexyloxyethoxy) -Α-methylstyrene,
4- (1-methoxypropoxy) -α-methylstyrene, 4- (1-ethoxypropoxy) -α-methylstyrene, 4- (1-n-propoxypropoxy) -α-methylstyrene, 4- (1-i -Propoxypropoxy) -α-methylstyrene, 4- (1-n-butoxypropoxy) -α-methylstyrene, 4- (1-t-butoxypropoxy) -α-methylstyrene, 4- (1-n-pentyl) Oxypropoxy) -α-methylstyrene, 4- (1-n-hexyloxypropoxy) -α-methylstyrene, 4- (1-cyclopentyloxypropoxy) -α-methylstyrene, 4- (1-cyclohexyloxypropoxy) -Α-methylstyrene,

4- (1-methoxybutoxy) -α-methylstyrene, 4- (1-ethoxybutoxy) -α-methylstyrene, 4- (1-n-propoxybutoxy) -α-methylstyrene, 4- (1-i -Propoxybutoxy) -α-methylstyrene, 4- (1-n-butoxybutoxy) -α-methylstyrene, 4- (1-t-butoxybutoxy) -α-methylstyrene, 4- (1-n-pentyl) Oxybutoxy) -α-methylstyrene, 4- (1-n-hexyloxybutoxy) -α-methylstyrene, 4- (1-cyclopentyloxybutoxy) -α-methylstyrene, 4- (1-cyclohexyloxybutoxy) -Α-methylstyrene,
4- (1-methoxy-2′-methylpropoxy) -α-methylstyrene, 4- (1-ethoxy-2-methylpropoxy) -α-methylstyrene, 4- (1-n-propoxy-2-methylpropoxy) ) -Α-methylstyrene, 4- (1-i-propoxy-2-methylpropoxy) -α-methylstyrene, 4- (1-n-butoxy-2-methylpropoxy) -α-methylstyrene, 4- ( 1-t-butoxy-2-methylpropoxy) -α-methylstyrene, 4- (1-n-pentyloxy-2-methylpropoxy) -α-methylstyrene, 4- (1-n-hexyloxy-2-) Methylpropoxy) -α-methylstyrene, 4- (1-cyclopentyloxy-2-methylpropoxy) -α-methylstyrene, 4- (1-cyclohexyloxy-2-methylpropyl) (Ropoxy) -α-methylstyrene,

4- (1-methoxypentyloxy) -α-methylstyrene, 4- (1-ethoxypentyloxy) -α-methylstyrene, 4- (1-n-propoxypentyloxy) -α-methylstyrene, 4- ( 1-i-propoxypentyloxy) -α-methylstyrene, 4- (1-n-butoxypentyloxy) -α-methylstyrene, 4- (1-t-butoxypentyloxy) -α-methylstyrene, 4- (1-n-pentyloxypentyloxy) -α-methylstyrene, 4- (1-n-hexyloxypentyloxy) -α-methylstyrene, 4- (1-cyclopentyloxypentyloxy) -α-methylstyrene, 4- (1-cyclohexyloxypentyloxy) -α-methylstyrene,
4- (1-methoxy-2,2-dimethylpropoxy) -α-methylstyrene, 4- (1-ethoxy-2,2-dimethylpropoxy) -α-methylstyrene, 4- (1-n-propoxy-2) , 2-dimethylpropoxy) -α-methylstyrene, 4- (1-i-propoxy-2,2-dimethylpropoxy) -α-methylstyrene, 4- (1-n-butoxy-2,2-dimethylpropoxy) -Α-methylstyrene, 4- (1-t-butoxy-2,2-dimethylpropoxy) -α-methylstyrene, 4- (1-n-pentyloxy-2,2-dimethylpropoxy) -α-methylstyrene 4- (1-n-hexyloxy-2,2-dimethylpropoxy) -α-methylstyrene, 4- (1-cyclopentyloxy-2,2-dimethylpropoxy) -α-methyl Styrene, 4- (1-cyclohexyl-2,2-dimethyl propoxy)-.alpha.-methyl styrene,

4- (1-methyl-1-methoxyethoxy) styrene, 4- (1-methyl-1-ethoxyethoxy) styrene, 4- (1-methyl-1-n-propoxyethoxy) styrene, 4- (1-methyl -1-i-propoxyethoxy) styrene, 4- (1-methyl-1-n-butoxyethoxy) styrene, 4- (1-methyl-1-t-butoxyethoxy) styrene, 4- (1-methyl-1) -N-pentyloxyethoxy) styrene, 4- (1-methyl-1-n-hexyloxyethoxy) styrene, 4- (1-methyl-1-cyclopentyloxyethoxy) styrene, 4- (1-methyl-1- (Cyclohexyloxyethoxy) styrene,
4- (1-methyl-1-methoxypropoxy) styrene, 4- (1-methyl-1-ethoxypropoxy) styrene, 4- (1-methyl-1-n-propoxypropoxy) styrene, 4- (1-methyl -1-i-propoxypropoxy) styrene, 4- (1-methyl-1-n-butoxypropoxy) styrene, 4- (1-methyl-1-t-butoxypropoxy) styrene, 4- (1-methyl-1) -N-pentyloxypropoxy) styrene, 4- (1-methyl-1-n-hexyloxypropoxy) styrene, 4- (1-methyl-1-cyclopentyloxypropoxy) styrene, 4- (1-methyl-1- (Cyclohexyloxypropoxy) styrene,

4- (1-methyl-1-methoxybutoxy) styrene, 4- (1-methyl-1-ethoxybutoxy) styrene, 4- (1-methyl-1-n-propoxybutoxy) styrene, 4- (1-methyl -1-i-propoxybutoxy) styrene, 4- (1-methyl-1-n-butoxybutoxy) styrene, 4- (1-methyl-1-t-butoxybutoxy) styrene, 4- (1-methyl-1) -N-pentyloxybutoxy) styrene, 4- (1-methyl-1-n-hexyloxybutoxy) styrene, 4- (1-methyl-1-cyclopentyloxybutoxy) styrene, 4- (1-methyl-1- (Cyclohexyloxybutoxy) styrene,
4- (1,2-dimethyl-1-methoxypropoxy) styrene, 4- (1,2-dimethyl-1-ethoxypropoxy) styrene, 4- (1,2-dimethyl-1-n-propoxypropoxy) styrene, 4- (1,2-dimethyl-1-i-propoxypropoxy) styrene, 4- (1,2-dimethyl-1-n-butoxypropoxy) styrene, 4- (1,2-dimethyl-1-t-butoxy) Propoxy) styrene, 4- (1,2-dimethyl-1-n-pentyloxypropoxy) styrene, 4- (1,2-dimethyl-1-n-hexyloxypropoxy) styrene, 4- (1,2-dimethyl) -1-cyclopentyloxypropoxy) styrene, 4- (1,2-dimethyl-1-cyclohexyloxypropoxy) styrene,

4- (1-methyl-1-methoxypentyloxy) styrene, 4- (1-methyl-1-ethoxypentyloxy) styrene, 4- (1-methyl-1-n-propoxypentyloxy) styrene, 4- ( 1-methyl-1-i-propoxypentyloxy) styrene, 4- (1-methyl-1-n-butoxypentyloxy) styrene, 4- (1-methyl-1-t-butoxypentyloxy) styrene, 4- (1-methyl-1-n-pentyloxypentyloxy) styrene, 4- (1-methyl-1-n-hexyloxypentyloxy) styrene, 4- (1-methyl-1-cyclopentyloxypentyloxy) styrene, 4- (1-methyl-1-cyclohexyloxypentyloxy) styrene,
4- (1,2,2-trimethyl-1-methoxypropoxy) styrene, 4- (1,2,2-trimethyl-1-ethoxypropoxy) styrene, 4- (1,2,2-trimethyl-1-n -Propoxypropoxy) styrene, 4- (1,2,2-trimethyl-1-i-propoxypropoxy) styrene, 4- (1,2,2-trimethyl-1-n-butoxypropoxy) styrene, 4- (1 , 2,2-Trimethyl-1-t-butoxypropoxy) styrene, 4- (1,2,2-trimethyl-1-n-pentyloxypropoxy) styrene, 4- (1,2,2-trimethyl-1- n-hexyloxypropoxy) styrene, 4- (1,2,2-trimethyl-1-cyclopentyloxypropoxy) styrene, 4- (1,2,2-trimethyl-1-cycline) Hexyloxy propoxy) styrene,

4- (1-methyl-1-methoxyethoxy) -α-methylstyrene, 4- (1-methyl-1-ethoxyethoxy) -α-methylstyrene, 4- (1-methyl-1-n-propoxyethoxy) -Α-methylstyrene, 4- (1-methyl-1-i-propoxyethoxy) -α-methylstyrene, 4- (1-methyl-1-n-butoxyethoxy) -α-methylstyrene, 4- (1 -Methyl-1-t-butoxyethoxy) -α-methylstyrene, 4- (1-methyl-1-n-pentyloxyethoxy) -α-methylstyrene, 4- (1-methyl-1-n-hexyloxy) Ethoxy) -α-methylstyrene, 4- (1-methyl-1-cyclopentyloxyethoxy) -α-methylstyrene, 4- (1-methyl-1-cyclohexyloxyethoxy) -α-methyl Styrene,
4- (1-methyl-1-methoxypropoxy) -α-methylstyrene, 4- (1-methyl-1-ethoxypropoxy) -α-methylstyrene, 4- (1-methyl-1-n-propoxypropoxy) -Α-methylstyrene, 4- (1-methyl-1-i-propoxypropoxy) -α-methylstyrene, 4- (1-methyl-1-n-butoxypropoxy) -α-methylstyrene, 4- (1 -Methyl-1-t-butoxypropoxy) -α-methylstyrene, 4- (1-methyl-1-n-pentyloxypropoxy) -α-methylstyrene, 4- (1-methyl-1-n-hexyloxy) Propoxy) -α-methylstyrene, 4- (1-methyl-1-cyclopentyloxypropoxy) -α-methylstyrene, 4- (1-methyl-1-cyclohexyloxyp) Epoxy)-.alpha.-methyl styrene,

4- (1-methyl-1-methoxybutoxy) -α-methylstyrene, 4- (1-methyl-1-ethoxybutoxy) -α-methylstyrene, 4- (1-methyl-1-n-propoxybutoxy) -Α-methylstyrene, 4- (1-methyl-1-i-propoxybutoxy) -α-methylstyrene, 4- (1-methyl-1-n-butoxybutoxy) -α-methylstyrene, 4- (1 -Methyl-1-t-butoxybutoxy) -α-methylstyrene, 4- (1-methyl-1-n-pentyloxybutoxy) -α-methylstyrene, 4- (1-methyl-1-n-hexyloxy) Butoxy) -α-methylstyrene, 4- (1-methyl-1-cyclopentyloxybutoxy) -α-methylstyrene, 4- (1-methyl-1-cyclohexyloxybutoxy) -α-methyl Styrene,
4- (1,2-dimethyl-1-methoxypropoxy) -α-methylstyrene, 4- (1,2-dimethyl-1-ethoxypropoxy) -α-methylstyrene, 4- (1,2-dimethyl-1 -N-propoxypropoxy) -α-methylstyrene, 4- (1,2-dimethyl-1-i-propoxypropoxy) -α-methylstyrene, 4- (1,2-dimethyl-1-n-butoxypropoxy) -Α-methylstyrene, 4- (1,2-dimethyl-1-t-butoxypropoxy) -α-methylstyrene, 4- (1,2-dimethyl-1-n-pentyloxypropoxy) -α-methylstyrene 4- (1,2-dimethyl-1-n-hexyloxypropoxy) -α-methylstyrene, 4- (1,2-dimethyl-1-cyclopentyloxypropoxy) -α-methyl Styrene, 4- (1,2-dimethyl-1-cyclohexyloxy propoxy)-.alpha.-methyl styrene,

4- (1-methyl-1-methoxypentyloxy) -α-methylstyrene, 4- (1-methyl-1-ethoxypentyloxy) -α-methylstyrene, 4- (1-methyl-1-n-propoxy) Pentyloxy) -α-methylstyrene, 4- (1-methyl-1-i-propoxypentyloxy) -α-methylstyrene, 4- (1-methyl-1-n-butoxypentyloxy) -α-methylstyrene 4- (1-methyl-1-t-butoxypentyloxy) -α-methylstyrene, 4- (1-methyl-1-n-pentyloxypentyloxy) -α-methylstyrene, 4- (1-methyl -1-n-hexyloxypentyloxy) -α-methylstyrene, 4- (1-methyl-1-cyclopentyloxypentyloxy) -α-methylstyrene, 4- (1 Methyl-1-cyclohexyloxy pentyloxy)-.alpha.-methyl styrene,
4- (1,2,2-trimethyl-1-methoxypropoxy) -α-methylstyrene, 4- (1,2,2-trimethyl-1-ethoxypropoxy) -α-methylstyrene, 4- (1,2 , 2-Trimethyl-1-n-propoxypropoxy) -α-methylstyrene, 4- (1,2,2-trimethyl-1-i-propoxypropoxy) -α-methylstyrene, 4- (1,2,2 -Trimethyl-1-n-butoxypropoxy) -α-methylstyrene, 4- (1,2,2-trimethyl-1-t-butoxypropoxy) -α-methylstyrene, 4- (1,2,2-trimethyl) -1-n-pentyloxypropoxy) -α-methylstyrene, 4- (1,2,2-trimethyl-1-n-hexyloxypropoxy) -α-methylstyrene, 4- (1,2,2-trime Mention may be made of units in which a polymerizable unsaturated bond is cleaved, such as til-1-cyclopentyloxypropoxy) -α-methylstyrene, 4- (1,2,2-trimethyl-1-cyclohexyloxypropoxy) styrene.

  Of these repeating units (5), 4- (1-methoxyethoxy) styrene, 4- (1-ethoxyethoxy) styrene, 4- (1-methyl-1-methoxyethoxy) styrene, 4- (1-methoxy) Propoxy) styrene, 4- (1-ethoxypropoxy) styrene, 4- (1-methoxyethoxy) -α-methylstyrene, 4- (1-ethoxyethoxy) -α-methylstyrene, 4- (1-methyl-1) -Methoxyethoxy) -α-methylstyrene, 4- (1-methoxypropoxy) -α-methylstyrene, 4- (1-ethoxypropoxy) -α-methylstyrene and the like units having a polymerizable unsaturated bond cleaved are preferred. .

Moreover, as another repeating unit, for example,
Styrene, α-methylstyrene, 2-methylstyrene, 3-methylstyrene, 4-methylstyrene, 2-methoxystyrene, 3-methoxystyrene, 4-methoxystyrene, 4-t-butoxystyrene, 4-t-butoxycarbonyl Vinyl aromatic compounds such as oxystyrene, 4-t-butoxycarbonylmethoxystyrene, 4- (2-t-butoxycarbonylethoxy) styrene, 4-tetrahydrofuranyloxystyrene, 4-tetrahydropyranyloxystyrene; (meth) acrylic Methyl methacrylate, ethyl (meth) acrylate, n-propyl (meth) acrylate, i-propyl (meth) acrylate, n-butyl (meth) acrylate, i-butyl (meth) acrylate, (meth) acrylic Sec-butyl acid, t-butyl (meth) acrylate, (me ) N-pentyl acrylate, neopentyl (meth) acrylate, n-hexyl (meth) acrylate, 2-ethylhexyl (meth) acrylate, 2-hydroxyethyl (meth) acrylate, 2-hydroxy (meth) acrylate Propyl, 3-hydroxypropyl (meth) acrylate, cyclopentyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, cyclohexyl (meth) acrylate, (meth) acrylic 1-methylcyclohexyl acid, 1-ethylcyclohexyl (meth) acrylate, norbornyl (meth) acrylate, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, dicyclopentenyl (meth) acrylate, ( Amethanyl acrylate (Meth) acrylic acid adamantyl methyl, (meth) acrylic acid tetrahydrofuranyl, (meth) acrylic acid tetrahydropyranyl, (meth) acrylic acid phenyl, (meth) acrylic acid benzyl, (meth) acrylic acid phenethyl (meta) ) Acrylic esters;

Unsaturated carboxylic acids such as (meth) acrylic acid, crotonic acid, maleic acid, fumaric acid, cinnamic acid;
Carboxyalkyl esters of unsaturated carboxylic acids such as 2-carboxyethyl (meth) acrylate, 2-carboxypropyl (meth) acrylate, 3-carboxypropyl (meth) acrylate;
Unsaturated nitrile compounds such as (meth) acrylonitrile, α-chloroacrylonitrile, crotonnitrile, maleinnitrile, fumaronitrile;
Unsaturated amide compounds such as (meth) acrylamide, N, N-dimethyl (meth) acrylamide, crotonamide, maleinamide, fumaramide;
Unsaturated imide compounds such as maleimide, N-phenylmaleimide, N-cyclohexylmaleimide;
N-vinyl-ε-caprolactam, N-vinyl pyrrolidone, 2-vinyl pyridine, 3-vinyl pyridine, 4-vinyl pyridine, 2-vinyl imidazole, other nitrogen-containing vinyl compounds such as 4-vinyl imidazole, etc. Examples include units in which a saturated bond is cleaved.

  Among these other repeating units, styrene, α-methylstyrene, 4-t-butoxystyrene, 4-t-butoxycarbonyloxystyrene, 4-t-butoxycarbonylmethoxystyrene, 4- (2′-t-butoxy) Carbonylethoxy) styrene, t-butyl (meth) acrylate, 1-methylcyclopentyl (meth) acrylate, 1-ethylcyclopentyl (meth) acrylate, 1-methylcyclohexyl (meth) acrylate, (meth) acrylic acid 1 -Units in which a polymerizable unsaturated bond is cleaved, such as ethylcyclohexyl, isobornyl (meth) acrylate, tricyclodecanyl (meth) acrylate, are preferred.

The ratio of the number of repeating units (5) to the total number of repeating units (4) and repeating units (5) in the resin (B1) cannot be generally specified, but is preferably 5 to 90%, more preferably 10 ~ 80%.
Moreover, the content rate of the other repeating unit in resin (B1) is 50 mol% or less normally with respect to all the repeating units, Preferably it is 30 mol% or less.
The polystyrene-reduced weight molecular weight (hereinafter referred to as “Mw”) of the resin (B1) measured by gel permeation chromatography is preferably 1,000 to 500,000, more preferably 3,000 to 300,000. .

The resin (B1) is, for example,
(I) A portion of the phenolic hydroxyl group in the (co) polymer of 4-hydroxystyrene and / or 4-hydroxy-α-methylstyrene is subjected to weakly acidic conditions with ethyl vinyl ether, ethylene glycol n-butyl vinyl ether, A method of reacting with a vinyl ether compound such as ethylene glycol cyclohexyl vinyl ether,
(B) A portion of the phenolic hydroxyl group in 4-hydroxystyrene or 4-hydroxy-α-methylstyrene is subjected to weakly acidic conditions such as ethyl vinyl ether, ethylene glycol n-butyl vinyl ether, ethylene glycol cyclohexyl vinyl ether, etc. A monomer corresponding to the repeating unit (5) is synthesized by reacting with a vinyl ether compound, and this can be produced by a method of copolymerizing with a monomer corresponding to the repeating unit (4) by a conventional method. .
The structure partially crosslinked by a crosslinking group having a diethylene glycol skeleton in the resin (B1) is introduced by reacting, for example, an appropriate amount of diethylene glycol divinyl ether simultaneously with the vinyl ether compound in the method (a). can do.

As the resin (B1), in particular, a resin having a structure in which a part of hydrogen atoms of a phenolic hydroxyl group in poly (4-hydroxystyrene) is substituted with a group —C (R ¹⁷ ) (R ¹⁸ ) OR ¹⁹ 4 -Hydroxystyrene and / or 4-hydroxy-α-methylstyrene is copolymerized with styrene or a styrene derivative thereof, a part of the hydrogen atom of the phenolic hydroxyl group is a group -C (R ¹⁷ ) (R ¹⁸ ) A resin having a structure substituted with OR ¹⁹ and comprising each repeating unit represented by the following formula (6) is preferred.

[In the formula (6), R ¹⁵ has the same meaning as R ¹⁵ in formula (4), R ¹⁶ has the same meaning as R ¹⁶ in formula ^{(5), R 17, R} 18 and R ¹⁹ has the formula (5) Each having the same meaning as R ¹⁷ , R ¹⁸ and R ¹⁹ , R ²⁰ and R ²² each independently represent a hydrogen atom or a methyl group, and R ²¹ is a hydrogen atom or a linear or branched group having 1 to 4 carbon atoms. An alkyl group, a linear or branched alkoxyl group having 1 to 4 carbon atoms, a t-butoxycarbonyloxy group, a t-butoxycarbonylmethoxy group, or a 2-t-butoxycarbonylethoxy group, and R ²³ represents carbon. A linear, branched or cyclic alkyl group having a number of 1 to 10 is shown, p and q are 0 or 1, and (p + q) ≠ 0. ]
In this invention, resin (B1) can be used individually or in mixture of 2 or more types.

Furthermore, in the present invention, an acid-dissociable group-containing resin other than the resin (B1) (hereinafter referred to as “another acid-dissociable group-containing resin”) can also be used.
As other acid-dissociable group-containing resins, for example, a phenolic hydroxyl group or a hydrogen atom of a carboxyl group in an alkali-soluble resin having one or more repeating units represented by the following formulas (7) to (10), A resin substituted with one or more acid dissociable groups that can be dissociated in the presence of an acid, as such, includes an alkali-insoluble or hardly alkali-soluble resin (hereinafter referred to as “resin (B2)”). be able to.

〔式（７）において、Ｒ²⁴は水素原子またはメチル基を示し、Ｒ²⁵はハロゲン原子または炭素数１〜６の１価の有機基を示し、ｒは０〜３の整数であり、複数存在するＲ²⁵は相互に同一でも異なってもよい。〕

[In the formula (7), R ²⁴ represents a hydrogen atom or a methyl group, R ²⁵ represents a halogen atom or a monovalent organic group having 1 to 6 carbon atoms, r is an integer of 0 to 3, R ²⁵ may be the same as or different from each other. ]

〔式（８）において、Ｒ²⁶は水素原子またはメチル基を示す。〕

[In Formula (8), R ²⁶ represents a hydrogen atom or a methyl group. ]

〔式（１０）において、Ｒ²⁷〜Ｒ³¹は相互に独立に水素原子または炭素数１〜４の直鎖状もしくは分岐状のアルキル基を示す。〕

[In Formula (10), R < ²⁷ > -R < ³¹ > shows a hydrogen atom or a C1-C4 linear or branched alkyl group mutually independently. ]

Examples of the acid dissociable group in the resin (B2) include a substituted methyl group, a 1-substituted ethyl group, a 1-substituted propyl group, a 1-branched alkyl group, a silyl group, a germyl group, an alkoxycarbonyl group, an acyl group, and a ring. Formula acid dissociable groups and the like can be mentioned.
Examples of the substituted methyl group include methoxymethyl group, methylthiomethyl group, ethoxymethyl group, ethylthiomethyl group, methoxyethoxymethyl group, benzyloxymethyl group, benzylthiomethyl group, phenacyl group, bromophenacyl group, and methoxyphenacyl. Group, methylthiophenacyl group, α-methylphenacyl group, cyclopropylmethyl group, benzyl group, diphenylmethyl group, triphenylmethyl group, bromobenzyl group, nitrobenzyl group, methoxybenzyl group, methylthiobenzyl group, ethoxybenzyl group , Ethylthiobenzyl group, piperonyl group, methoxycarbonylmethyl group, ethoxycarbonylmethyl group, n-propoxycarbonylmethyl group, i-propoxycarbonylmethyl group, n-butoxycarbonylmethyl group, t-butoxy Rubonirumechiru group, and the like can be mentioned.

Examples of the 1-substituted ethyl group include 1-methoxyethyl group, 1-methylthioethyl group, 1,1-dimethoxyethyl group, 1-ethoxyethyl group, 1-ethylthioethyl group, 1,1- Diethoxyethyl group, 1-phenoxyethyl group, 1-phenylthioethyl group, 1,1-diphenoxyethyl group, 1-benzyloxyethyl group, 1-benzylthioethyl group, 1-cyclopropylethyl group, 1- Phenylethyl group, 1,1-diphenylethyl group, 1-methoxycarbonylethyl group, 1-ethoxycarbonylethyl group, 1-n-propoxycarbonylethyl group, 1-i-propoxycarbonylethyl group, 1-n-butoxycarbonyl Examples thereof include an ethyl group and a 1-t-butoxycarbonylethyl group. Examples of the 1-branched alkyl group include i-propyl group, sec-butyl group, t-butyl group, 1,1-dimethylpropyl group, 1-methylbutyl group, 1,1-dimethylbutyl group and the like. Can be mentioned.
Examples of the 1-substituted propyl group include 1-methoxypropyl group and 1-ethoxypropyl group.

Examples of the silyl group include trimethylsilyl group, ethyldimethylsilyl group, methyldiethylsilyl group, triethylsilyl group, i-propyldimethylsilyl group, methyldi-i-propylsilyl group, tri-i-propylsilyl group, Examples thereof include a t-butyldimethylsilyl group, a methyldi-t-butylsilyl group, a tri-t-butylsilyl group, a phenyldimethylsilyl group, a methyldiphenylsilyl group, and a triphenylsilyl group.
Examples of the germyl group include a trimethylgermyl group, an ethyldimethylgermyl group, a methyldiethylgermyl group, a triethylgermyl group, an i-propyldimethylgermyl group, a methyldi-i-propylgermyl group, and a trimethylgermyl group. -I-propylgermyl group, t-butyldimethylgermyl group, methyldi-t-butylgermyl group, tri-t-butylgermyl group, phenyldimethylgermyl group, methyldiphenylgermyl group, triphenylgermyl group, etc. be able to.
Examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, an i-propoxycarbonyl group, and a t-butoxycarbonyl group.

Examples of the acyl group include acetyl group, propionyl group, butyryl group, heptanoyl group, hexanoyl group, valeryl group, pivaloyl group, isovaleryl group, laurylyl group, myristoyl group, palmitoyl group, stearoyl group, oxalyl group, malonyl group, Succinyl group, glutaryl group, adipoyl group, piperoyl group, suberoyl group, azelaoil group, sebacoyl group, acryloyl group, propioloyl group, methacryloyl group, crotonoyl group, oleoyl group, maleoyl group, fumaroyl group, mesaconoyl group, canphoroyl group, benzoyl Group, phthaloyl group, isophthaloyl group, terephthaloyl group, naphthoyl group, toluoyl group, hydroatropoyl group, atropoyl group, cinnamoyl group, furoyl group, thenoyl group, nicotinoyl group, iso Kochinoiru group, p- toluenesulfonyl group, and mesyl group.
Further, examples of the cyclic acid dissociable group include a cyclopropyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexenyl group, a 4-methoxycyclohexyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, a tetrahydrothiopyranyl group, and a tetrahydro group. A thiofuranyl group, 3-bromotetrahydropyranyl group, 4-methoxytetrahydropyranyl group, 4-methoxytetrahydrothiopyranyl group, 3-tetrahydrothiophene-1,1-dioxide group and the like can be mentioned.

  Among these acid dissociable groups, t-butyl group, 1-methoxymethyl group, 1-methoxyethyl group, 1-ethoxyethyl group, 1-ethoxypropyl group, 1-propoxyethyl group, trimethylsilyl group, t-butoxy group A carbonyl group, t-butoxycarbonylmethyl group, tetrahydropyranyl group, tetrahydrofuranyl group and the like are preferable.

The rate of introduction of the acid dissociable group in the resin (B2) (the ratio of the number of acid dissociable groups to the total number of acidic functional groups and acid dissociable groups in the resin (B2)) Although it cannot unconditionally be defined depending on the type of the alkali-soluble resin into which the group is introduced, it is preferably 10 to 100%, more preferably 15 to 100%.
The Mw of the resin (B2) is preferably 1,000 to 150,000, more preferably 3,000 to 100,000.

The resin (B2) can be produced, for example, by introducing one or more acid-dissociable groups into an alkali-soluble resin produced in advance, and one or more monomers having an acid-dissociable group ( It can be produced by (co) polymerization, (co) polycondensation of one or more polycondensation components having an acid dissociable group, and the like.
In this invention, resin (B2) can be used individually or in mixture of 2 or more types.
In the present invention, the resin (B2) can be used alone, but it is also preferred to use it together with the resin (B1).

-Additives-
Various additives, such as an acid diffusion control agent, surfactant, and a sensitizer, can be mix | blended with the positive radiation sensitive resin composition of this invention as needed.
The acid diffusion control agent controls the diffusion phenomenon in the resist film of the acid generated from the radiation sensitive acid generator such as diazodisulfone compound (1) by exposure, and suppresses undesired chemical reaction in the unexposed area. It has a function to perform. By using such an acid diffusion control agent, the storage stability of the composition is improved, and as a resist, the resolution is improved, and due to fluctuations in the holding time (PED) from exposure to development. Changes in the line width of the resist pattern can be suppressed, and the process stability is extremely excellent.
As the acid diffusion controller, a nitrogen-containing compound whose basicity does not change by exposure or baking is preferable, and an example thereof is a compound represented by the following formula (11) (hereinafter referred to as “nitrogen-containing compound (α)”). ), A diamino compound having two nitrogen atoms in the same molecule (hereinafter referred to as “nitrogen-containing compound (β)”), and a polymer having three or more nitrogen atoms (hereinafter referred to as “nitrogen-containing compound (γ)”). ), Amide group-containing compounds, urea compounds, nitrogen-containing heterocyclic compounds, and the like.

〔式（１１）において、Ｒ³²、Ｒ³³およびＲ³⁴は相互に独立に水素原子、置換もしくは非置換のアルキル基、置換もしくは非置換のアリール基または置換もしくは非置換のアラルキル基を示す。〕

[In the formula (11), R ³² , R ³³ and R ³⁴ each independently represent a hydrogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a substituted or unsubstituted aralkyl group. ]

  Examples of the nitrogen-containing compound (α) include monoalkylamines such as n-hexylamine, n-heptylamine, n-octylamine, n-nonylamine, n-decylamine and n-dodecylamine; di-n-butylamine Dialkyl such as di-n-pentylamine, di-n-hexylamine, di-n-heptylamine, di-n-octylamine, di-n-nonylamine, di-n-decylamine, di-n-dodecylamine Amines; triethylamine, tri-n-propylamine, tri-n-butylamine, tri-n-pentylamine, tri-n-hexylamine, tri-n-heptylamine, tri-n-octylamine, tri-n- Nonylamine, tri-n-decylamine, tri-n-dodecylamine, n-dodecyldimethylamine, methyldi trialkylamines such as n-dodecylamine; alkanolamines such as monoethanolamine, diethanolamine, triethanolamine; aniline, N-methylaniline, N, N-dimethylaniline, 2-methylaniline, 3-methylaniline, Aromatic amines such as 4-methylaniline, 4-nitroaniline, diphenylamine, triphenylamine, and naphthylamine can be exemplified.

  Examples of the nitrogen-containing compound (β) include ethylenediamine, N, N, N ′, N′-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4′-diaminodiphenylmethane, and 4,4′-diaminodiphenyl ether. 4,4′-diaminobenzophenone, 4,4′-diaminodiphenylamine, N, N, N ′, N′-tetrakis (2-hydroxyethyl) ethylenediamine, N, N, N ′, N′-tetrakis (2- Hydroxypropyl) ethylenediamine, 2,2-bis (4-aminophenyl) propane, 2- (3-aminophenyl) -2- (4-aminophenyl) propane, 2- (4-aminophenyl) -2- (3 -Hydroxyphenyl) propane, 2- (4-aminophenyl) -2- (4-hydroxyphenyl) Examples include propane, 1,4-bis [1- (4-aminophenyl) -1-methylethyl] benzene, 1,3-bis [1- (4-aminophenyl) -1-methylethyl] benzene, and the like. it can.

Examples of the nitrogen-containing compound (γ) include polymers of polyethyleneimine, polyallylamine, dimethylaminoethylacrylamide, and the like.
Examples of the amide group-containing compound include formamide, N-methylformamide, N, N-dimethylformamide, acetamide, N-methylacetamide, N, N-dimethylacetamide, propionamide, benzamide, pyrrolidone, N-methylpyrrolidone and the like. Can be mentioned.
Examples of the urea compound include urea, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, tri-n-butyl. Examples include thiourea.

  Examples of the nitrogen-containing heterocyclic compound include imidazoles such as imidazole, benzimidazole, 4-methylimidazole, 2-phenylimidazole, 4-methyl-2-phenylimidazole and 1-benzylimidazole; pyridine, 2-methylpyridine 4-methylpyridine, 2-ethylpyridine, 4-ethylpyridine, 2-phenylpyridine, 4-phenylpyridine, N-methyl-4-phenylpyridine, 2-benzylpyridine, 4-benzylpyridine, 2,6-di In addition to pyridines such as methanol pyridine, nicotine, nicotinic acid, nicotinamide, quinoline, 8-oxyquinoline and acridine, pyrazine, pyrazole, pyridazine, quinosaline, purine, pyrrolidine, piperidine, morpholine, 4-methylmorpholine, pipepe Jin, 1,4-dimethylpiperazine, and 1,4-diazabicyclo [2.2.2] octane.

Of these nitrogen-containing organic compounds, nitrogen-containing compounds (α) and nitrogen-containing heterocyclic compounds are preferred, and among the nitrogen-containing compounds (α), trialkylamines are particularly preferred. Among them, imidazoles and pyridines are particularly preferable.
The acid diffusion controller can be used alone or in admixture of two or more.
The amount of the acid diffusion controller to be used varies depending on the type thereof, the type of diazodisulfone compound (1) and other acid generators, etc., but is usually 10% per 100 parts by weight of the total resin components in the resin composition. Part or less, preferably 5 parts by weight or less. In this case, when the usage-amount of an acid diffusion control agent exceeds 10 weight part, there exists a tendency for the sensitivity as a resist and the developability of an exposure part to fall.

The surfactant exhibits an effect of improving the coating property, striation, developability, etc. of the radiation sensitive resin composition.
As such a surfactant, any of anionic, cationic, nonionic or amphoteric can be used, but a preferred surfactant is a nonionic surfactant.
Examples of nonionic surfactants include polyoxyethylene higher alkyl ethers, polyoxyethylene higher alkyl phenyl ethers, polyethylene glycol higher fatty acid diesters, and the following trade names: KP (manufactured by Shin-Etsu Chemical) , Polyflow (manufactured by Kyoeisha Yushi Chemical Co., Ltd.), F Top (manufactured by Tokemu Products), Mega Fuck (manufactured by Dainippon Ink & Chemicals), Florard (manufactured by Sumitomo 3M), Asahi Guard, Surflon (manufactured by Asahi Glass) Can be mentioned.
These surfactants can be used alone or in admixture of two or more.
The compounding amount of the surfactant is usually 2 parts by weight or less as an active ingredient of the surfactant per 100 parts by weight of the total resin components in the resin composition.

The sensitizer absorbs radiation energy and transmits the energy to a radiation-sensitive acid generator such as the diazodisulfone compound (1), thereby increasing the amount of acid produced. It has the effect of improving the apparent sensitivity of the radiation sensitive resin composition. Examples of such sensitizers include acetophenones, benzophenones, naphthalene, biacetyl, eosin, rose bengal, pyrenes, anthracenes, phenothiazines and the like.
These sensitizers can be used alone or in admixture of two or more.
The blending amount of the sensitizer is usually 50 parts by weight or less, preferably 30 parts by weight or less, per 100 parts by weight of the total resin components in the resin composition.
In addition, by blending a dye or pigment, the latent image of the exposed area can be visualized, and the influence of halation during exposure can be alleviated. By blending an adhesion aid, adhesion to the substrate can be improved. it can.
Furthermore, examples of other additives include an antihalation agent, a storage stabilizer, an antifoaming agent, a shape improving agent, and the like, specifically 4-hydroxy-4′-methylchalcone.

Composition solution The positive-tone radiation-sensitive resin composition of the present invention, upon its use, usually, after dissolved in a solvent so that the solids concentration is, for example, 1 to 50 wt%, e.g., about pore size 0.2μm filter The solution is prepared as a composition solution.
Specific examples of the solvent include ethers, esters, ether esters, ketones, ketone esters, amides, amide esters, lactams, lactones, (halogenated) hydrocarbons, and the like. Are ethylene glycol monoalkyl ethers, diethylene glycol dialkyl ethers, propylene glycol monoalkyl ethers, propylene glycol dialkyl ethers, ethylene glycol monoalkyl ether acetates, propylene glycol monoalkyl ether acetates, acetates, hydroxyacetates , Lactate esters, alkoxyacetate esters, acetoacetate esters, pyruvate esters, propionate esters, butyrate esters, 2-hydroxy-2-methyl ester Pionic acid esters, 3-alkoxypropionic acid esters, 2-hydroxy-3-methylbutyric acid esters, acyclic or cyclic ketones, N, N-dialkylformamides, N, N-dialkylacetamides, Examples thereof include N-alkylpyrrolidones, γ-lactones, (halogenated) aliphatic hydrocarbons, and (halogenated) aromatic hydrocarbons.

Specific examples of such solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol mono-n-propyl ether, ethylene glycol mono-n-butyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol di-n- Propyl ether, diethylene glycol di-n-butyl ether, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate, propylene glycol mono-n-propyl ether acetate, isopropenyl propio Nate, ethyl acetate, n acetate Propyl, i-propenyl acetate, n-butyl acetate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, ethyl hydroxyacetate, ethyl lactate, ethyl ethoxyacetate, methyl acetoacetate, ethyl acetoacetate, 3-methyl -3-methoxybutyl propionate, 3-methyl-3-methoxybutyl butyrate, ethyl 2-hydroxy-2-methylpropionate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, 3-ethoxypropionic acid Methyl, ethyl 3-ethoxypropionate, methyl 2-hydroxy-3-methylbutyrate, methyl ethyl ketone, cyclohexanone, 2-heptanone, 3-heptanone, 4-heptanone, N, N-dimethylformamide, N, N-dimethylacetamide, N -Methyl Pyrrolidone, toluene, xylene and the like.
Of these solvents, propylene glycol monoalkyl ether acetates, lactic acid esters, 3-alkoxypropionic acid esters, acyclic or cyclic ketones and the like are preferable.
The said solvent can be used individually or in mixture of 2 or more types.

  Further, the solvent may be benzyl ethyl ether, di-n-hexyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, acetonyl acetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-octanol, if necessary. One or more high-boiling solvents such as nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, ethylene glycol monophenyl ether acetate can be added. .

Formation of Resist Pattern The positive-type radiation-sensitive resin composition of the present invention contains an acid-dissociable group-containing resin and is caused by the action of an acid generated from a radiation-sensitive acid generator such as a diazodisulfone compound (1) by exposure. The acid-dissociable group in the resin is dissociated to form an acidic functional group, whereby the resin becomes alkali-soluble, thereby forming a positive resist pattern.
When forming a resist pattern from the positive radiation sensitive resin composition of the present invention, the composition solution prepared as described above is applied by means such as spin coating, cast coating, roll coating, etc. A resist film is formed by coating on a substrate such as a silicon wafer or a wafer coated with aluminum, and then a heat treatment (hereinafter referred to as “PB”) is performed, and then the resist is formed through a predetermined mask pattern. Expose the coating.
The radiation that can be used in this case is preferably a far ultraviolet ray such as an emission line spectrum of a mercury lamp (wavelength 254 nm), a KrF excimer laser (wavelength 248 nm), an ArF excimer laser (wavelength 193 nm), but other types of acid generators. Depending on the case, charged particle beams such as electron beams, X-rays such as synchrotron radiation, and normal ultraviolet rays such as i-rays (wavelength 365 nm) can also be used.
The exposure conditions such as the radiation dose are appropriately selected according to the composition of the resin composition, the type of additive, and the like.

After the exposure, in order to improve the apparent sensitivity of the resist, it is preferable to perform a heat treatment (hereinafter referred to as “PEB”). The heating conditions vary depending on the composition of the resin composition, the type of additive, and the like, but are usually 30 to 200 ° C, preferably 50 to 150 ° C.
Then, a predetermined resist pattern is formed by developing with an alkaline developer.
Examples of the alkali developer include alkali metal hydroxides, aqueous ammonia, alkylamines, alkanolamines, heterocyclic amines, tetraalkylammonium hydroxides, choline, 1,8-diazabicyclo [5.4. 0] -7-undecene, 1,5-diazabicyclo [4.3.0] -5-nonene and other alkaline compounds in a concentration of usually 5 to 10% by weight, preferably 2 to 5% by weight An alkaline aqueous solution dissolved so as to be used is used. A particularly preferred alkaline developer is an aqueous solution of tetraalkylammonium hydroxides.
In addition, an appropriate amount of a water-soluble organic solvent such as methanol or ethanol, a surfactant, or the like can be added to the developer composed of the alkaline aqueous solution.
When a developer composed of an alkaline aqueous solution is used as described above, it is generally washed with water after development.

The diazodisulfone compound (1) can generate an acid efficiently with high sensitivity (low exposure energy amount), especially with respect to far ultraviolet rays represented by KrF excimer laser or ArF excimer laser, etc., and has excellent storage stability. Therefore, it can be used very suitably as a radiation sensitive acid generator in a chemically amplified resist.
The positive-type radiation-sensitive resin composition of the present invention containing the diazodisulfone compound (1) as a radiation-sensitive acid generator is excellent in sensitivity, line edge roughness, depth of focus margin, etc. It is extremely useful as a chemically amplified resist for the production of integrated circuit elements, which is expected to be advanced.

Hereinafter, the embodiment of the present invention will be described more specifically with reference to examples. However, the present invention is not limited to these examples.
Synthesis example 1
After 90.2 g (1.0 mol) of 2-methylpropane-2-thiol and 30.1 g (1.0 mol) of paraformaldehyde were mixed at room temperature, the temperature of the reaction solution was maintained at 5 ° C. or lower, Hydrogen gas 54.7g (1.5mol) was blown in over about 2 hours. Thereafter, the reaction solution was cooled to 0 ° C., 25.0 g (0.23 mol) of anhydrous calcium chloride was added, and the mixture was stirred for 1 hour. Thereafter, insoluble matters were removed by filtration, and the filtrate was distilled under reduced pressure under a pressure of 1.3 to 2.6 kPa to obtain a chloride (hereinafter referred to as “compound (a)” shown in (a) of scheme (I). 61.0 g (0.44 mol) was obtained as a colorless transparent liquid.

Synthesis example 2
Compound (a) 50.0 g (0.36 mol) obtained in Synthesis Example 1, 1,4-dioxaspiro [4.5] decane-7-thiol 62.8 g (0.36 mol), and tetra-n-butyl Ammonium bromide (3.5 g, 0.01 mol) was mixed at room temperature, cooled to 10 ° C., and 252 g (1.3 mol) of a 20 wt% aqueous sodium hydroxide solution was added dropwise over 30 minutes. Thereafter, the reaction solution is stirred at the same temperature for 2 hours, and then separated to discard the aqueous layer. The organic layer is washed with 200 g of a 7.5 wt% ammonium chloride aqueous solution, and is represented by the following formula (b1). 69.7 g (0.25 mol) of a crude product of the compound (hereinafter referred to as “compound (b1)”) was obtained as an ocher liquid.

Synthesis example 3
After dissolving 69.7 g (0.25 mol) of the crude product of compound (b1) obtained in Synthesis Example 2 and 33.8 g (0.13 mol) of ammonium acetate in 557.6 g of ethanol at room temperature, sodium tungstate 1.8 g (5.5 mmol) of dihydrate was added. Thereafter, 110.2 g (1.1 mol) of 35 wt% hydrogen peroxide water was added dropwise at room temperature over 15 minutes, and then the temperature of the reaction solution was gradually raised to 65 ° C. and stirred at the same temperature for 2 hours. . Thereafter, the reaction solution was once cooled to 35 ° C., and 55.1 g (0.57 mol) of 35 wt% hydrogen peroxide solution was dropped again over 10 minutes, and then the temperature was gradually raised to 65 ° C. at the same temperature. The operation of stirring for 2 hours was repeated until no reaction intermediate was detected by thin layer chromatography (TLC) and the reaction was complete. After completion of the reaction, 446 g of water was added, and the solvent was distilled under reduced pressure by an amount corresponding to 557.6 g of ethanol added first. Thereafter, the reaction solution was cooled to 5 ° C., and the precipitated crystals were filtered off and washed with a small amount of cold ethanol to obtain pale yellowish white crystals. Thereafter, the crystals were purified by suspension in i-propanol under reflux to obtain 56.7 g (0.17 mol) of a compound represented by the following formula (c1) (hereinafter referred to as “compound (c1)”). Obtained as white crystals.

Synthesis example 4
43.0 g (0.13 mol) of the compound (c1) obtained in Synthesis Example 3, 79.7 g (0.40 mol) tosyl azide, and 336.3 g of acetonitrile were mixed at room temperature, cooled to 10 ° C., , 8-diazabicyclo [5.4.0] -7-undecene 3.2 g (21 mmol) was added. Then, after stirring at the same temperature for 2 hours and concentrating under reduced pressure to remove the solvent, 172 g of methanol was added. Thereafter, the reaction solution was cooled to 0 ° C., and the precipitated crystals were separated by filtration and washed with 86 g of cold methanol to obtain red-white crystals. Thereafter, this crystal was recrystallized from methanol 0 to obtain 30.1 g (82 mmol) of a diazodisulfone compound (1) represented by the following formula (12) as a white crystal.

Chemical shift (ppm) of the obtained diazodisulfone compound (1) by ¹ H-NMR analysis (measurement solvent: 6 deuterated acetone) is 1.5 (9H, s, methyl group × 3), 1.5 1.7 (4H, m, methylene group x 2), 1.9 (2H, m, methylene group x 1), 2.1 (2H, m, methylene group x 1), 3.9 (1H, m , —SO ₂ —CH = group), 4.0 (4H, dd, —O—CH ₂ —CH ₂ —O— group), and the mass analysis value by FAB (fast atom bombardment method) is m / z. = 367 (M ⁺ ).

Examples 1-10 and Comparative Examples 1-2
Each component shown in Table 1 (where parts are based on weight) was mixed to obtain a uniform solution, and then filtered through a membrane filter having a pore size of 0.2 μm to prepare a composition solution.
Next, each composition solution was spin-coated on a silicon wafer, and then PB was performed at the temperature and time shown in Table 2 to form a resist film having a thickness of 1.0 μm. After that, each resist film was exposed using a KrF excimer laser irradiation apparatus (trade name: NSR-2005 EX8A) manufactured by Nikon Corporation with a KrF excimer laser (wavelength: 248 nm) through a mask pattern, changing the exposure amount. PEB was performed at the temperature and time shown in FIG.
Next, using a 2.38 wt% tetramethylammonium hydroxide aqueous solution, development was performed at 23 ° C. for 60 seconds, followed by washing with water for 30 seconds and drying to form a resist pattern.

Here, each resist was evaluated in the following manner. The evaluation results are shown in Table 3.
The resist film formed on the sensitive silicon wafer was exposed to light with a different exposure amount, immediately post-exposure baked, then alkali developed, then washed with water and dried to form a resist pattern. The exposure amount for forming a 15 μm line-and-space pattern (1L1S) with a one-to-one line width was taken as the optimum exposure amount, and this optimum exposure amount was taken as the sensitivity.
Line edge roughness (LER)
Each line pattern of a line-and-space pattern (1L1S) having a design line width of 0.15 μm is observed with a scanning electron microscope, as shown in FIG. 1 (however, the unevenness is exaggerated more than it actually is). The difference ΔCD between the line width at the most conspicuous unevenness generated along the lateral surface of the line pattern and the designed line width 0.15 μm is measured, and the case where the 3σ of the ΔCD is less than 10 nm is indicated by “◯”. 10 nm or more was evaluated as "x". 1A is a plan view, and FIG. 1B is a cross-sectional view.
Depth of focus margin (DOF)
When the focus is changed in the range from −1.0 μm to +1.0 nm at the optimum exposure amount, the width of the focus within the range of “0.135 to 0.165 μm” is defined as the focus depth margin. did.

Each component used in Examples 1 to 10 and Comparative Examples 1 and 2 is as follows.
Diazodisulfone compound A-1: Diazodisulfone compound (1) represented by the formula (12)
a-1: Bis (cyclohexylsulfonyl) diazomethane a-2: Compound represented by the following formula (13)

Other acid generator α-1: Triphenylsulfonium trifluoromethanesulfonate α-2: Triphenylsulfonium 10-camphorsulfonate α-3: Diphenyliodonium trifluoromethanesulfonate

Acid-dissociable group-containing resin B-1: resin in which 34 mol% of the phenolic hydroxyl groups in poly (4-hydroxystyrene) are substituted with 1-ethoxyethyl group (Mw = 9,000)
B-2: Resin in which 25 mol% of the hydrogen atoms of the phenolic hydroxyl group in poly (4-hydroxystyrene) are substituted with 1-ethoxyethyl group and 8 mol% are substituted with t-butoxycarbonyl group (Mw = 10,000)
B-3: Resin in which 23 mol% of the hydrogen atoms of the phenolic hydroxyl group in poly (4-hydroxystyrene) were substituted with 1-ethoxyethyl group and 10 mol% were substituted with t-butyl group (Mw = 12) , 000)
B-4: a resin in which 26 mol% of the hydrogen atoms of the phenolic hydroxyl group in poly (4-hydroxystyrene) are substituted with a t-butoxycarbonyl group (Mw = 9,000)
B-5: Resin in which 32 mol% of hydrogen atoms of phenolic hydroxyl groups in poly (4-hydroxystyrene) are substituted with t-butyl groups (Mw = 15,000)
B-6: 4-hydroxystyrene / styrene / tert-butyl acrylate copolymer (copolymerization ratio = 60: 20: 20, Mw = 12,500)
B-7: 4-hydroxystyrene / acrylic acid 1-ethylcyclopentyl copolymer (copolymer molar ratio = 70: 30, Mw = 14,500)
B-8: 4-hydroxystyrene / 1-ethylcyclopentyl acrylate / 4-tert-butoxystyrene copolymer (copolymerization molar ratio = 70: 20: 10, Mw = 16,000)
B-9: 4-hydroxystyrene / acrylic acid 1-methylcyclopentyl / 4-t-butoxystyrene copolymer (copolymerization molar ratio = 70: 20: 10, Mw = 17,500)

Acid diffusion controller C-1: n-dodecyldimethylamine C-2: tri-n-hexylamine C-3: benzimidazole C-4: 2-benzylpyridine C-5: 1-benzylimidazole
Solvent S-1: Ethyl lactate S-2: Propylene glycol monomethyl ether acetate S-3: 2-heptanone

It is a schematic diagram of a line pattern.

Claims (2)

(A) a radiation-sensitive acid generator comprising a diazodisulfone compound represented by the following formula (1) as an essential component, and (B) an alkali-insoluble or hardly-alkali-soluble resin having an acid-dissociable group, the positive type radiation-sensitive resin composition characterized by containing a resin which becomes alkali easily soluble when the acid-dissociable group dissociates.

[In Formula (1), R < ¹ > -R < ⁹ > shows a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxyl group, or a C1-C4 hydroxyalkyl group mutually independently, A represents a substituted or non-substituted linear or branched divalent hydrocarbon group having 1 to 10 carbon atoms. ] The positive radiation sensitive resin composition according to claim 1, wherein A in the formula (1) according to claim 1 is a divalent group represented by the following formula (2).

[In Formula (2), R < ¹⁰ > -R < ¹³ > shows a hydrogen atom, a C1-C4 alkyl group, a C1-C4 alkoxyl group, or a C1-C4 hydroxyalkyl group mutually independently. ]

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