JP7339809B2 - Photosensitive resin composition, photosensitive dry film, method for producing photosensitive dry film, method for producing patterned resist film, method for producing plated modeled article, and polyfunctional vinyl ether compound - Google Patents

Description

The present invention uses a photosensitive resin composition, a photosensitive dry film having a photosensitive resin layer made of the photosensitive resin composition, a method for producing the photosensitive dry film, and the photosensitive resin composition described above. A method for producing a patterned resist film, a method for producing a plated molded article using a substrate with a template produced using the photosensitive resin composition described above, and a photosensitive resin composition described above can be suitably blended. It relates to a polyfunctional vinyl ether compound.

Currently, photofabrication is the mainstream of precision microfabrication technology. Photofabrication is a process in which a photoresist composition is applied to the surface of a workpiece to form a photoresist layer, the photoresist layer is patterned by photolithography, and the patterned photoresist layer (photoresist pattern) is used as a mask for chemical etching, electrolysis, It is a general term for techniques for manufacturing various precision parts such as semiconductor packages by performing electroforming, which is mainly based on etching or electroplating.

In recent years, with the downsizing of electronic equipment, high-density mounting technology for semiconductor packages has progressed. Based on this, the improvement of the mounting density is attempted. In such high-density mounting technology, connection terminals include protruding electrodes (mounting terminals) such as bumps protruding from the package, and metal posts that connect rewiring extending from peripheral terminals on a wafer to mounting terminals. etc. are arranged on the substrate with high precision.

A photoresist composition is used in the photofabrication as described above. As such a photoresist composition, a chemically amplified photoresist composition containing an acid generator is known (Patent Documents 1 and 2, etc.). ). In a chemically amplified photoresist composition, radiation (exposure) generates an acid from an acid generator, and heat treatment promotes the diffusion of the acid, causing an acid catalytic reaction with the base resin and the like in the composition. Alkali solubility is changed.

Such a chemically amplified positive photoresist composition is used, for example, in the formation of plated objects such as bumps and metal posts by a plating process. Specifically, using a chemically amplified photoresist composition, a photoresist layer having a desired thickness is formed on a support such as a metal substrate, exposed through a predetermined mask pattern, developed, and bumps. A photoresist pattern used as a mold is formed from which portions for forming metal posts and metal posts are selectively removed (exfoliated). Then, after embedding a conductor such as copper in the removed portion (non-resist portion) by plating, the photoresist pattern around it is removed to form bumps and metal posts.

JP-A-9-176112 JP-A-11-52562

A photoresist composition used for forming a resist pattern that serves as a mold for forming a plated product such as a bump or a metal post must be free from cracks in order to stably produce a plated product with a desired shape. It is possible to form a resist pattern that does not easily change its shape even when it comes into contact with the plating solution under plating conditions, and it has storage stability that does not cause thickening or gelation even when stored at room temperature for a certain period of time. desired. By doing so, precise connection terminals such as bumps and metal posts can be formed.

However, conventionally known photoresist compositions such as those disclosed in Patent Documents 1 and 2 are photoresist compositions used for forming resist patterns that serve as molds for forming plated objects such as bumps and metal posts. It may not meet the above performance required for the product.

The present invention has been made in view of the above problems, and provides a photosensitive resin composition capable of forming a resist pattern whose shape is difficult to change even when it comes into contact with a plating solution under plating conditions while suppressing the occurrence of cracks. and a photosensitive dry film comprising a photosensitive resin layer made of the photosensitive resin composition, a method for producing the photosensitive dry film, and a method for producing a patterned resist film using the photosensitive resin composition. and a method for producing a plated molded article using a substrate with a mold prepared using the above-described photosensitive resin composition, and a polyfunctional vinyl ether compound that can be suitably blended with the above-described photosensitive resin composition. With the goal.

The present inventors have made intensive studies to achieve the above object, and found that a photosensitive resin composition containing a base polymer (A) having a carboxy group and/or a hydroxyl group contains a cyclic skeleton. The present inventors have found that the above problems can be solved by incorporating a polyfunctional vinyl ether monomer (B) having the structure of ##STR00004## and have completed the present invention. Specifically, the present invention provides the following.

A first aspect of the present invention is
Containing a base polymer (A) and a polyfunctional vinyl ether monomer (B),
The base polymer (A) has a carboxy group and/or a hydroxyl group,
The polyfunctional vinyl ether monomer (B) has the following formula (B1):
R ^B —(—R ^b1 —O—CH═CH ₂ ) _n1 (B1)
including a compound represented by
In formula (B1), ^RB is a monovalent linking group containing a monocyclic skeleton and/or a condensed cyclic skeleton in which two or more monocycles are condensed, and the number of monocyclic skeletons in ^RB and , the total number of single rings constituting the condensed cyclic skeleton is 2 or more, R ^b1 is a single bond or a divalent linking group, and two or more R ^b1 are the same or different It is a photosensitive resin composition used for forming a mold for forming a plated model, wherein n1 is an integer of 2 or more.

A second aspect of the present invention has a substrate film and a photosensitive resin layer formed on the surface of the substrate film, and the photosensitive resin layer is made of the photosensitive resin composition according to the first aspect. It is a photosensitive dry film.

A third aspect of the present invention is a method for producing a photosensitive dry film, comprising applying the photosensitive resin composition according to the first aspect on a substrate film to form a photosensitive resin layer. .

A fourth aspect of the present invention is
A lamination step of laminating a photosensitive resin layer made of the photosensitive resin composition according to the first aspect on a substrate having a metal surface;
an exposure step of position-selectively irradiating the photosensitive resin layer with actinic rays or radiation;
and a developing step of developing the exposed photosensitive resin layer.

A fifth aspect of the present invention is
A lamination step of laminating a photosensitive resin layer made of the photosensitive resin composition according to the first aspect on a substrate having a metal surface;
An exposure step of irradiating the photosensitive resin layer with actinic rays or radiation;
A development step of developing the photosensitive resin layer after exposure to prepare a substrate with a template for forming a plated model,
a step of plating the substrate with the mold to form a plated model in the mold;
A method for manufacturing a plated modeled article.

A sixth aspect of the present invention is represented by the following formula (B3):
R ^B1 —(—CO—OR ^b3 —O—CH=CH ₂ ) _n2 (B3)
is represented by
In formula (B3), R ^b3 is a divalent hydrocarbon group, n2 is an integer of 2 or more and 4 or less, and R ^B1 is the following formulas (B3-1) to (B3-3):
-R ^B2 -R ^b4 -P ^B2 -... (B3-1)
-R ^B2 -R ^b4 -R ^B3 <... (B3-2)
>R ^B3 -R ^b4 -R ^B3 <... (B3-3)
is a linking group having a valence of 2 or more and 4 or less, represented by any one of R ^B2 is a phenylene group which may have a substituent, and R ^B3 is a benzenetriyl group which may have a substituent and R ^b4 is a single bond or a divalent linking group, a polyfunctional vinyl ether compound.

According to the present invention, a photosensitive resin composition that can form a resist pattern that is resistant to change in shape even when it comes into contact with a plating solution under plating conditions while suppressing the occurrence of cracks, and the photosensitive resin composition. A photosensitive dry film comprising a photosensitive resin layer, a method for producing the photosensitive dry film, a method for producing a patterned resist film using the photosensitive resin composition described above, and the photosensitive resin composition described above. It is possible to provide a method for producing a plated shaped article by plating a substrate with a template produced using the method, and a polyfunctional vinyl ether compound that is suitably used as a component of the above-described photosensitive resin composition.

<<Photosensitive resin composition>>
The photosensitive resin composition contains a base polymer (A) and a polyfunctional vinyl ether monomer (B). Such a photosensitive resin composition is used to form a mold for forming a plated model.
The base polymer (A) has carboxy groups and/or hydroxyl groups.
Polyfunctional vinyl ether monomer (B) has the following formula (B1):
R ^B —(—R ^b1 —O—CH═CH ₂ ) _n1 (B1)
It is a compound represented by
In formula (B1), R ^B is an n1valent linking group containing two or more monocyclic skeletons and/or a condensed cyclic skeleton in which two or more monocyclic rings are condensed, R ^b1 is a single bond, Or a divalent linking group, two or more R ^b1 may be the same or different, n1 is an integer of 2 or more, a photosensitive resin composition used for forming a mold for forming a plated model It is a thing.

A mold for forming a plated model formed using the above-described photosensitive resin composition is inhibited from cracking and does not easily change its shape even when it comes into contact with a plating solution under plating conditions.
Although the reason is not clear, in a patterned resist film used as a template for forming a plated model, the carboxyl group and/or hydroxyl group of the base polymer (A) and a polyimide having a specific structure It is believed that the above effect is obtained by the cross-linking reaction that occurs with the functional vinyl ether monomer (B).

The photosensitive resin composition may be either positive type or negative type.

Suitable examples when the photosensitive resin composition is of a negative type include, in addition to the base polymer (A) and the polyfunctional vinyl ether monomer (B), monofunctional or polyfunctional (meth)acrylate monomers, etc. and a photopolymerization initiator.

When forming a resist pattern using such a negative photosensitive resin composition, by baking a coating film made of the photosensitive resin composition, the carboxy groups and/or hydroxyl groups possessed by the base polymer (A) and The vinyloxy groups of the functional vinyl ether monomer (B) react with each other to crosslink the molecular chains of the base polymer (A). Here, if the amount of alkali-soluble groups such as carboxyl groups and phenolic hydroxyl groups possessed by the base polymer (A) is set to be in excess of the amount of vinyloxy groups possessed by the polyfunctional vinyl ether monomer (B), The crosslinked base polymer (A) has alkali-soluble groups. The crosslinked base polymer (A) exhibits alkali solubility by having alkali-soluble groups.
Then, when the coating film containing the crosslinked base polymer (A) is position-selectively exposed, the photopolymerizable monomer is polymerized by the action of the photopolymerization initiator, so that the exposed portion becomes insoluble in the alkaline developer. do.
On the other hand, the unexposed portion is soluble in an alkaline developer because the photopolymerizable monomer is not polymerized and the crosslinked base polymer (A) exhibits alkali solubility.
Therefore, in addition to the base polymer (A) and the base polymer polyfunctional vinyl ether monomer (B), a photopolymerizable monomer such as a monofunctional or polyfunctional (meth)acrylate monomer and a photopolymerization initiator are included. When forming a resist pattern using a negative photosensitive resin composition, after baking a coating film made of the photosensitive resin composition, position-selective exposure and development with an alkaline developer are performed to obtain an alkaline It contains a crosslinked base polymer (A) that is free from unexposed areas soluble in a developer, suppresses the occurrence of cracks, and does not easily change shape even when it comes into contact with a plating solution under plating conditions. A resist pattern can be formed.

A preferred example of a case where the photosensitive resin composition is of a positive type is, in addition to the base polymer (A) and the polyfunctional vinyl ether monomer (B), an alkaline developer of the photosensitive resin composition by exposure. and a photosensitive resin composition containing a photosensitive agent (G) that enhances solubility in

When the coating film made of the above positive photosensitive resin composition is heated, the carboxy groups and/or hydroxyl groups possessed by the base polymer (A) react with the vinyloxy groups possessed by the polyfunctional vinyl ether monomer (B). However, the cross-linking of the molecular chains of the base polymer (A) reduces the solubility of the photosensitive resin composition in an alkaline developer.
However, when the coated film after heating is subjected to position-selective exposure, the exposed portions are rendered soluble in an alkaline developer by the action of the photosensitive agent (G).

Therefore, in addition to the base polymer (A) and the polyfunctional vinyl ether monomer (B), a positive photosensitive composition containing a photosensitive agent (G) that enhances the solubility of the photosensitive resin composition in an alkaline developer by exposure When forming a resist pattern using a resin composition, after baking a coating film made of a photosensitive resin composition, position-selective exposure and development with an alkali developer are performed, thereby resisting the alkali developer. It is possible to form a resist pattern containing a crosslinked base polymer (A) whose shape does not easily change even when it comes into contact with a plating solution under plating conditions while removing the soluble exposed portion and suppressing the generation of cracks. .

The photosensitive agent (G) is a photosensitive compound that increases the solubility of the photosensitive resin composition in an alkaline developer by a photoreaction that occurs in the molecule upon exposure. The photosensitizer (G) does not include a compound that is solubilized in an alkaline developer by a deprotection reaction or the like caused by the action of a photoacid generator, a photobase generator, or the like. Typically, the photosensitizer (G) includes a naphthoquinonediazide group-containing compound.

Examples of quinonediazide group-containing compounds include fully esterified products and partially esterified products of phenol compounds and naphthoquinonediazide sulfonic acid compounds. Examples of the phenol compound include polyhydroxybenzophenone compounds such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone; tris(4-hydroxyphenyl)methane, bis(4- hydroxy-3-methylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-2,3,5-trimethylphenyl)-2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)- 4-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-2-hydroxyphenylmethane, bis(4- hydroxy-2,5-dimethylphenyl)-4-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3-hydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)- 2-hydroxyphenylmethane, bis(4-hydroxy-3,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-3,4-dihydroxyphenylmethane, bis(4-hydroxy-2,5-dimethylphenyl)-2,4-dihydroxyphenylmethane, bis(4-hydroxyphenyl)-3-methoxy-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy- 2-methylphenyl)-4-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)- Trisphenol type compounds such as 2-hydroxyphenylmethane, bis(5-cyclohexyl-4-hydroxy-2-methylphenyl)-3,4-dihydroxyphenylmethane; 2,4-bis(3,5-dimethyl-4- linear trinuclear phenol compounds such as hydroxybenzyl)-5-hydroxyphenol, 2,6-bis(2,5-dimethyl-4-hydroxybenzyl)-4-methylphenol; 1,1-bis[3-( 2-hydroxy-5-methylbenzyl)-4-hydroxy-5-cyclohexylphenyl]isopropane, bis[2,5-dimethyl-3-(4-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane, bis[2,5-dimethyl-3-(4-hydroxybenzyl)-4-hydroxyphenyl]methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-methylphenyl] Methane, bis[3-(3,5-dimethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy -5-methylphenyl]methane, bis[3-(3,5-diethyl-4-hydroxybenzyl)-4-hydroxy-5-ethylphenyl]methane, bis[2-hydroxy-3-(3,5-dimethyl -4-hydroxybenzyl)-5-methylphenyl]methane, bis[2-hydroxy-3-(2-hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[4-hydroxy-3-(2 -Hydroxy-5-methylbenzyl)-5-methylphenyl]methane, bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxyphenyl]methane and other linear tetranuclear compounds Phenol compounds; 2,4-bis[2-hydroxy-3-(4-hydroxybenzyl)-5-methylbenzyl]-6-cyclohexylphenol, 2,4-bis[4-hydroxy-3-(4-hydroxybenzyl) )-5-methylbenzyl]-6-cyclohexylphenol, 2,6-bis[2,5-dimethyl-3-(2-hydroxy-5-methylbenzyl)-4-hydroxybenzyl]-4-methylphenol and the like Linear polyphenol compounds such as linear pentanuclear phenol compounds; bis(2,3,4-trihydroxyphenyl)methane, bis(2,4-dihydroxyphenyl)methane, 2,3,4-trihydroxyphenyl-4 '-Hydroxyphenylmethane, 2-(2,3,4-trihydroxyphenyl)-2-(2',3',4'-trihydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2 -(2′,4′-dihydroxyphenyl)propane, 2-(4-hydroxyphenyl)-2-(4′-hydroxyphenyl)propane, 2-(3-fluoro-4-hydroxyphenyl)-2-(3 '-fluoro-4'-hydroxyphenyl)propane, 2-(2,4-dihydroxyphenyl)-2-(4'-hydroxyphenyl)propane, 2-(2,3,4-trihydroxyphenyl)-2- (4'-Hydroxyphenyl) propane, 2-(2,3,4-trihydroxyphenyl)-2-(4'-hydroxy-3',5'-dimethylphenyl) propane and other bisphenol type compounds; 1-[ 1-(4-hydroxyphenyl)isopropyl]-4-[1,1-bis(4-hydroxyphenyl)ethyl]benzene, 1-[1-(3-methyl-4-hydroxyphenyl)isopropyl]-4-[ polynuclear branched compounds such as 1,1-bis(3-methyl-4-hydroxyphenyl)ethyl]benzene; condensed phenol compounds such as 1,1-bis(4-hydroxyphenyl)cyclohexane; These can be used singly or in combination of two or more.

Examples of the naphthoquinonediazide sulfonic acid compound include naphthoquinone-1,2-diazide-5-sulfonyl chloride and naphthoquinone-1,2-diazide-4-sulfonyl chloride.

In addition, other quinonediazide group-containing compounds, such as orthobenzoquinonediazide, orthonaphthoquinonediazide, orthoanthraquinonediazide, or nuclear-substituted derivatives thereof such as orthonaphthoquinonediazide sulfonic acid esters, and further orthoquinonediazide sulfonyl chlorides and hydroxyl or amino groups. Compounds such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, esterification or ether with some hydroxyl groups left Reaction products with modified gallic acid, aniline, p-aminodiphenylamine and the like can also be used. These may be used alone or in combination of two or more.

These quinonediazide group-containing compounds are prepared, for example, by combining the above phenol compound with naphthoquinone-1,2-diazide-5-sulfonyl chloride or naphthoquinone-1,2-diazide-4-sulfonyl chloride in a suitable solvent such as dioxane. Among them, it can be produced by condensing in the presence of an alkali such as triethanolamine, alkali carbonate, or alkali hydrogencarbonate, followed by complete esterification or partial esterification.

The amount of the photosensitive agent (G) used is preferably 50% by mass or less, more preferably 40% by mass or less, based on the total mass of the base polymer (A) and the polyfunctional vinyl ether monomer (B). 30 mass % or less is particularly preferable. The lower limit of the amount of the photosensitive agent (G) used is, for example, preferably 10% by mass or more, and 15% by mass or more, based on the total mass of the base polymer (A) and the polyfunctional vinyl ether monomer (B). is more preferable, and 20% by mass or more is even more preferable.

Other preferred examples of the positive photosensitive resin composition include, in addition to the base polymer (A), a resin whose alkali solubility is increased by the action of an acid, and a polyfunctional vinyl ether monomer (B), A photosensitive resin composition containing an acid generator (C) that generates an acid upon exposure to actinic rays or radiation is exemplified.
The above positive photosensitive resin composition containing the acid generator (C) is particularly preferable as the photosensitive resin composition in terms of good sensitivity and resolution.

Below, a particularly preferred photosensitive resin composition comprising the base polymer (A), the polyfunctional vinyl ether monomer (B), and an acid generator (C) that generates an acid upon exposure to actinic rays or radiation, Regarding the positive photosensitive resin composition containing a resin whose alkali solubility is increased by the action of an acid as the base polymer (A), the essential or optional components and the method for producing the positive photosensitive resin composition are described below. to explain.
The configuration relating to the polyfunctional vinyl ether monomer (B) described below is a configuration common to all of the photosensitive resin compositions according to the present invention.

<Base polymer (A)>
Hereinafter, resins that are contained as the base polymer (A) in the particularly preferred positive photosensitive resin composition and whose solubility in alkali increases under the action of acid will be described. The resin whose alkali solubility is increased by the action of an acid is not particularly limited, and any resin whose alkali solubility is increased by the action of an acid can be used. Among these, it is preferable to contain at least one resin selected from the group consisting of novolac resin (A1), polyhydroxystyrene resin (A2), and acrylic resin (A3).
The novolak resin (A1), the polyhydroxystyrene resin (A2), and the acrylic resin (A3) all essentially contain carboxy groups and/or hydroxyl groups.

[Novolac resin (A1)]
As the novolac resin (A1), a resin containing a structural unit represented by the following formula (a1) can be used.

In formula (a1) above, R ^1a represents an acid dissociable, dissolution inhibiting group, and R ^2a and R ^3a each independently represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

A resin containing the structural unit represented by formula (a1) can be prepared by introducing an acid-dissociable, dissolution-inhibiting group to the phenolic hydroxyl group of the novolac resin. On the other hand, the base polymer (A) contains carboxy groups and/or hydroxyl groups, as described above. Therefore, when preparing the novolac resin (A1) using a novolak resin having a phenolic hydroxyl group, the amount of acid-dissociable dissolution inhibiting groups to be introduced is adjusted so that the novolak resin (A1) has a desired amount of hydroxyl groups. be done.

Examples of the acid-dissociable, dissolution-inhibiting group represented by R ^1a include groups represented by the following formulas (a2) and (a3), linear, branched, or cyclic alkyl groups having 1 to 6 carbon atoms. is preferably a group, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

In the above formulas (a2) and (a3), R ^4a and R ^5a each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to ⁶ carbon atoms; represents a linear, branched or cyclic alkyl group having 1 to 10 atoms, R ^7a represents a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms; represents 0 or 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. . Moreover, a cyclopentyl group, a cyclohexyl group, etc. are mentioned as said cyclic alkyl group.

Here, specific examples of the acid dissociable, dissolution inhibiting group represented by the above formula (a2) include a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, isobutoxyethyl group, tert-butoxyethyl group, cyclohexyloxyethyl group, methoxypropyl group, ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1-ethoxy-1-methylethyl group and the like. Specific examples of the acid-dissociable, dissolution-inhibiting group represented by formula (a3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include groups having 1 to 6 carbon atoms in each alkyl group such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (A2)]
As the polyhydroxystyrene resin (A2), a resin containing a structural unit represented by the following formula (a4) can be used.
The base polymer (A) contains carboxy groups and/or hydroxyl groups, as described above. For this reason, the resin containing the structural unit represented by the formula (a4) as the polyhydroxystyrene resin (A2) is such that the resin, together with the structural unit represented by the formula (a4), contains (meth)acrylic acid. It is prepared so as to contain a desired amount of structural units derived from unsaturated carboxylic acids and structural units derived from hydroxystyrenes.

In formula (a4) above, R ^8a represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^9a represents an acid dissociable, dissolution inhibiting group.

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched or cyclic alkyl group having 1 to 6 carbon atoms. Linear or branched alkyl groups include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. A cyclopentyl group, a cyclohexyl group, etc. are mentioned as a cyclic alkyl group.

As the acid-dissociable, dissolution-inhibiting group represented by ^R9a , the same acid-dissociable, dissolution-inhibiting groups as exemplified in the above formulas (a2) and (a3) can be used.

Furthermore, the polyhydroxystyrene resin (A2) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds. Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethylsuccinic acid, 2- Methacrylic acid derivatives having a carboxyl group and an ester bond such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) acrylic acid alkyl esters such as (meth) acrylate; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters; phenyl (meth) acrylate, (meth)acrylic acid aryl esters such as benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, vinyl group-containing aromatic compounds such as α-methylhydroxystyrene and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide;

[Acrylic resin (A3)]
The acrylic resin (A3) is not particularly limited as long as it is an acrylic resin whose solubility in alkali increases under the action of an acid and which is conventionally blended in various photosensitive resin compositions.
However, the base polymer (A) contains carboxy groups and/or hydroxyl groups as described above. Therefore, the acrylic resin (A3) can be prepared by introducing an acid-dissociable, dissolution-inhibiting group to the phenolic hydroxyl group of the novolak resin. Therefore, the acrylic resin (A3) includes structural units derived from unsaturated carboxylic acids such as (meth)acrylic acid, and structures derived from unsaturated monomers having a hydroxyl group such as hydroxyethyl (meth)acrylate. It is prepared to contain the desired amount of units.
The acrylic resin (A3) preferably contains a structural unit (a-3) derived from an acrylic acid ester containing, for example, a —SO ₂ —containing cyclic group or a lactone-containing cyclic group. In such a case, when forming a resist pattern, it is easy to form a resist pattern having a preferable cross-sectional shape.

(—SO ₂ -containing cyclic group)
Here, the “—SO ₂ —containing cyclic group” refers to a cyclic group containing a ring containing —SO ₂ — in its ring skeleton. Specifically, the sulfur atom in —SO ₂ — ( S) is a cyclic group that forms part of the ring skeleton of a cyclic group. A ring containing —SO ₂ — in its ring skeleton is counted as the first ring, and if it contains only the ring, it is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of its structure. called. The —SO ₂ —containing cyclic group may be monocyclic or polycyclic.

A —SO ₂ —containing cyclic group is particularly a cyclic group containing —O—SO ₂ — in its ring skeleton, ie, —O—S— in —O—SO ₂ — forms part of the ring skeleton. Preferred are cyclic groups containing a forming sultone ring.

The number of carbon atoms in the —SO ₂ —-containing cyclic group is preferably 3 or more and 30 or less, more preferably 4 or more and 20 or less, still more preferably 4 or more and 15 or less, and particularly preferably 4 or more and 12 or less. The number of carbon atoms is the number of carbon atoms constituting the ring skeleton, and does not include the number of carbon atoms in the substituents.

The -SO ₂ -containing cyclic group may be an -SO ₂ -containing aliphatic cyclic group or a -SO ₂ -containing aromatic cyclic group. An --SO ₂ --containing aliphatic cyclic group is preferred.

As the —SO ₂ —-containing aliphatic cyclic group, hydrogen atoms are removed from an aliphatic hydrocarbon ring in which some of the carbon atoms constituting the ring skeleton are replaced with —SO ₂ — or —O—SO ₂ —. Groups with at least one removed are included. More specifically, a group obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which —CH ₂ — constituting the ring skeleton is substituted with —SO ₂ —, or —CH ₂ — constituting the ring. Examples thereof include groups obtained by removing at least one hydrogen atom from an aliphatic hydrocarbon ring in which CH ₂ — is substituted with —O—SO ₂ —.

The number of carbon atoms in the alicyclic hydrocarbon ring is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less. The alicyclic hydrocarbon ring may be polycyclic or monocyclic. The monocyclic alicyclic hydrocarbon group is preferably a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 or more and 6 or less carbon atoms. Examples of the monocycloalkane include cyclopentane and cyclohexane. The polycyclic alicyclic hydrocarbon ring is preferably a group obtained by removing two hydrogen atoms from a polycycloalkane having 7 to 12 carbon atoms, and specific examples of the polycycloalkane include adamantane and norbornane. , isobornane, tricyclodecane, tetracyclododecane, and the like.

The —SO ₂ —-containing cyclic group may have a substituent. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, oxygen atoms (=O), -COOR'', -OC(=O)R'', hydroxyalkyl groups, cyano groups, and the like. is mentioned.

As the alkyl group as the substituent, an alkyl group having 1 to 6 carbon atoms is preferable. The alkyl group is preferably linear or branched. Specific examples include methyl group, ethyl group, n-propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, n-pentyl group, isopentyl group, neopentyl group, n-hexyl group and the like. be done. Among these, a methyl group or an ethyl group is preferred, and a methyl group is particularly preferred.

As the alkoxy group as the substituent, an alkoxy group having 1 to 6 carbon atoms is preferable. The alkoxy group is preferably linear or branched. Specifically, groups in which the alkyl group exemplified above as the alkyl group as the substituent is bonded to an oxygen atom (--O--) can be mentioned.

A halogen atom as the substituent includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the aforementioned alkyl group have been substituted with the aforementioned halogen atoms.

Examples of the halogenated alkyl group as the substituent include a group in which some or all of the hydrogen atoms of the alkyl group exemplified above as the alkyl group as the substituent are substituted with the above-described halogen atoms. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

R" in -COOR" and -OC(=O)R" described above is either a hydrogen atom or a linear, branched or cyclic alkyl group having 1 to 15 carbon atoms.

When R″ is a linear or branched alkyl group, the number of carbon atoms in the chain alkyl group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, and particularly preferably 1 or 2.

When R″ is a cyclic alkyl group, the number of carbon atoms in the cyclic alkyl group is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, and particularly preferably 5 or more and 10 or less. , or removing one or more hydrogen atoms from monocycloalkanes, which may or may not be substituted with fluorinated alkyl groups, and polycycloalkanes such as bicycloalkanes, tricycloalkanes, and tetracycloalkanes. More specifically, one or more hydrogen atoms are added from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. groups excepted.

As the hydroxyalkyl group as the substituent, a hydroxyalkyl group having 1 to 6 carbon atoms is preferable. Specifically, a group in which at least one hydrogen atom of the alkyl group exemplified above as the alkyl group as the substituent is substituted with a hydroxyl group is exemplified.

（式中、Ａ’は酸素原子若しくは硫黄原子を含んでいてもよい炭素原子数１以上５以下のアルキレン基、酸素原子又は硫黄原子であり、ｚは０以上２以下の整数であり、Ｒ^１０ａはアルキル基、アルコキシ基、ハロゲン化アルキル基、水酸基、－ＣＯＯＲ”、－ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基、又はシアノ基であり、Ｒ”は水素原子、又はアルキル基である。） More specific examples of the —SO ₂ —containing cyclic group include groups represented by the following formulas (3-1) to (3-4).

(Wherein, A′ is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom or a sulfur atom, z is an integer of 0 to 2, and R ^10a is an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group, and R" is a hydrogen atom or an alkyl group.)

In the above formulas (3-1) to (3-4), A' is an alkylene group having 1 to 5 carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-) , an oxygen atom, or a sulfur atom. The alkylene group having 1 to 5 carbon atoms in A' is preferably a linear or branched alkylene group, and examples thereof include a methylene group, an ethylene group, an n-propylene group and an isopropylene group.

When the alkylene group contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is interposed between the terminals or carbon atoms of the above-mentioned alkylene group, for example, -O- CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ - and the like. A′ is preferably an alkylene group having 1 to 5 carbon atoms or —O—, more preferably an alkylene group having 1 to 5 carbon atoms, and most preferably a methylene group.

z can be 0, 1, and 2, with 0 being most preferred. When z is 2, the plurality of R ^10a may be the same or different.

The alkyl group, alkoxy group, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group for R ^10a may each have a -SO ₂ -containing cyclic group. The alkyl group, alkoxy group, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group mentioned as substituents are the same as those described above.

Specific examples of the cyclic groups represented by formulas (3-1) to (3-4) are given below. "Ac" in the formula represents an acetyl group.

Among the above, the —SO ₂ —-containing cyclic group is preferably a group represented by the aforementioned formula (3-1), and the aforementioned chemical formulas (3-1-1) and (3-1-18). , (3-3-1), and (3-4-1) are more preferably at least one selected from the group consisting of groups represented by the above chemical formula (3-1-1) are most preferred.

(lactone-containing cyclic group)
A “lactone-containing cyclic group” refers to a cyclic group containing a ring containing —O—C(=O)— in its ring skeleton (lactone ring). A lactone ring is counted as the first ring, and a group containing only a lactone ring is called a monocyclic group, and a group containing other ring structures is called a polycyclic group regardless of the structure. A lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

As the lactone cyclic group in the structural unit (a-3), any group can be used without particular limitation. Specifically, the lactone-containing monocyclic group includes a group obtained by removing one hydrogen atom from a 4- to 6-membered ring lactone, for example, a group obtained by removing one hydrogen atom from β-propionolactone, and a group obtained by removing one hydrogen atom from γ-butyrolactone. Examples thereof include a group obtained by removing one hydrogen atom, and a group obtained by removing one hydrogen atom from δ-valerolactone. Examples of lactone-containing polycyclic groups include groups obtained by removing one hydrogen atom from bicycloalkanes, tricycloalkanes, and tetracycloalkanes having a lactone ring.

As the structural unit (a-3), the structure of the other portion is not particularly limited as long as it has a —SO ₂ —containing cyclic group or a lactone-containing cyclic group. A structural unit (a-3-S), which is a structural unit derived from an acrylic ester in which a hydrogen atom may be substituted by a substituent and contains a —SO ₂ —containing cyclic group, and a carbon atom at the α-position selected from the group consisting of a structural unit (a-3-L) containing a lactone-containing cyclic group, which is a structural unit derived from an acrylic ester in which the hydrogen atom bonded to is optionally substituted with a substituent At least one structural unit is preferred.

[Structural unit (a-3-S)]
More specific examples of the structural unit (a-3-S) include structural units represented by the following formula (a-S1).

（式中、Ｒは水素原子、炭素原子数１以上５以下のアルキル基、又は炭素原子数１以上５以下のハロゲン化アルキル基であり、Ｒ^１１ａは－ＳＯ_２－含有環式基であり、Ｒ^１２ａは単結合、又は２価の連結基である。）

(wherein R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, R ^11a is a —SO ₂ —containing cyclic group, R ^12a is a single bond or a divalent linking group.)

In formula (a-S1), R is the same as defined above.
R ^11a is the same as the —SO ₂ —containing cyclic group mentioned above.
R ^12a may be either a single bond or a divalent linking group. A divalent linking group is preferable because the effect of the present invention is excellent.

The divalent linking group for R ^12a is not particularly limited, but preferred examples include an optionally substituted divalent hydrocarbon group, a heteroatom-containing divalent linking group, and the like.

- Divalent hydrocarbon group optionally having a substituent The hydrocarbon group as the divalent linking group may be either an aliphatic hydrocarbon group or an aromatic hydrocarbon group. An aliphatic hydrocarbon group means a hydrocarbon group without aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. A saturated hydrocarbon group is usually preferred. More specifically, the aliphatic hydrocarbon group includes a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in its structure, and the like.

The number of carbon atoms in the linear or branched aliphatic hydrocarbon group is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and even more preferably 1 or more and 5 or less.

A linear alkylene group is preferable as the linear aliphatic hydrocarbon group. Specifically, methylene group [-CH ₂ -], ethylene group [-(CH ₂ ) ₂ -], trimethylene group [-(CH ₂ ) ₃ -], tetramethylene group [-(CH ₂ ) ₄ -] , a pentamethylene group [-(CH ₂ ) ₅ -] and the like.

A branched alkylene group is preferable as the branched aliphatic hydrocarbon group. Specifically, -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ CH ₃ )-, -C(CH ₃ ) Alkylmethylene groups such as (CH ₂ CH ₂ CH ₃ )-, -C(CH ₂ CH ₃ ) ₂ -; -CH(CH ₃ )CH ₂ -, -CH(CH ₃ )CH(CH ₃ )- , -C(CH ₃ ) ₂ CH ₂ -, -CH(CH ₂ CH ₃ )CH ₂ -, -C(CH ₂ CH ₃ ) ₂ -CH ₂ -, alkylethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ - and other alkyltrimethylene groups; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ - and alkylalkylene groups such as alkyltetramethylene groups such as As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The straight-chain or branched-chain aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) for substituting a hydrogen atom. Examples of the substituent include a fluorine atom, a fluorine-substituted fluorinated alkyl group having 1 to 5 carbon atoms, and an oxo group (=O).

As the aliphatic hydrocarbon group containing a ring in the above structure, a cyclic aliphatic hydrocarbon group that may contain a substituent containing a heteroatom in the ring structure (two hydrogen atoms are removed from the aliphatic hydrocarbon ring group), a group in which the cyclic aliphatic hydrocarbon group is bonded to the end of a linear or branched aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is linear or branched Examples thereof include groups interposed in the middle of aliphatic hydrocarbon groups. Examples of the straight-chain or branched-chain aliphatic hydrocarbon group include those mentioned above.

The number of carbon atoms in the cyclic aliphatic hydrocarbon group is preferably 3 or more and 20 or less, more preferably 3 or more and 12 or less.

A cyclic aliphatic hydrocarbon group may be polycyclic or monocyclic. As the monocyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane is preferable. The number of carbon atoms in the monocycloalkane is preferably 3 or more and 6 or less. Specific examples include cyclopentane and cyclohexane. As the polycyclic aliphatic hydrocarbon group, a group obtained by removing two hydrogen atoms from polycycloalkane is preferable. The number of carbon atoms in the polycycloalkane is preferably 7 or more and 12 or less. Specific examples include adamantane, norbornane, isobornane, tricyclodecane, tetracyclododecane and the like.

A cyclic aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) for substituting a hydrogen atom. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxo group (=O).

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. is more preferred, and a methoxy group and an ethoxy group are particularly preferred.

Examples of the halogen atom as the substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferred.

Examples of the halogenated alkyl group as the above substituent include groups in which some or all of the hydrogen atoms of the above alkyl group have been substituted with the above halogen atoms.

In the cyclic aliphatic hydrocarbon group, part of the carbon atoms constituting the ring structure may be substituted with -O- or -S-. Preferred heteroatom-containing substituents are -O-, -C(=O)-O-, -S-, -S(=O) ₂ - and -S(=O) ₂ -O-.

An aromatic hydrocarbon group as a divalent hydrocarbon group is a divalent hydrocarbon group having at least one aromatic ring and may have a substituent. The aromatic ring is not particularly limited as long as it is a cyclic conjugated system having 4n+2 π electrons, and may be monocyclic or polycyclic. The number of carbon atoms in the aromatic ring is preferably 5 or more and 30 or less, more preferably 5 or more and 20 or less, still more preferably 6 or more and 15 or less, and particularly preferably 6 or more and 12 or less. However, the number of carbon atoms does not include the number of carbon atoms of the substituent.

Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocyclic rings in which some of the carbon atoms constituting the aromatic hydrocarbon ring are substituted with heteroatoms; etc. The heteroatom in the aromatic heterocycle includes oxygen atom, sulfur atom, nitrogen atom and the like. Specific examples of aromatic heterocycles include pyridine rings and thiophene rings.

Specifically, the aromatic hydrocarbon group as the divalent hydrocarbon group is a group obtained by removing two hydrogen atoms from the above aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); A group obtained by removing two hydrogen atoms from an aromatic compound containing two or more aromatic rings (e.g., biphenyl, fluorene, etc.); A group obtained by removing one hydrogen atom from the above aromatic hydrocarbon ring or aromatic heterocycle ( aryl group or heteroaryl group) in which one of the hydrogen atoms is substituted with an alkylene group (e.g., benzyl group, phenethyl group, 1-naphthylmethyl group, 2-naphthylmethyl group, 1-naphthylethyl group, 2- a group obtained by removing one hydrogen atom from an aryl group in an arylalkyl group such as a naphthylethyl group); and the like.

The number of carbon atoms in the alkylene group bonded to the aryl group or heteroaryl group is preferably 1 or more and 4 or less, more preferably 1 or more and 2 or less, and particularly preferably 1.

In the above aromatic hydrocarbon group, a hydrogen atom of the aromatic hydrocarbon group may be substituted with a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be substituted with a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, and an oxo group (=O).

The alkyl group as the substituent is preferably an alkyl group having 1 to 5 carbon atoms, more preferably a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-butyl group.

The alkoxy group as the substituent is preferably an alkoxy group having 1 to 5 carbon atoms, such as a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. is preferred, and a methoxy group and an ethoxy group are more preferred.

The halogen atom as the substituent includes a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferred.

Examples of the halogenated alkyl group as the substituent include groups in which some or all of the hydrogen atoms of the above-mentioned alkyl group are substituted with the above-mentioned halogen atoms.

- Bivalent linking group containing a hetero atom The hetero atom in the bivalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, such as an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. etc.

Specific examples of the divalent linking group containing a heteroatom include -O-, -C(=O)-, -C(=O)-O-, -OC(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, -NH-, -NH-C(=O)-, -NH-C(=NH)-, =N and a combination of at least one of these non-hydrocarbon linking groups and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include the same divalent hydrocarbon groups that may have a substituent as described above, and a linear or branched aliphatic hydrocarbon group is preferable. .

Among the above, -NH-, -NH- in -C(=O)-NH-, H in -NH-C(=NH)- are substituted with substituents such as alkyl groups and acyl groups, respectively. may have been The number of carbon atoms in the substituent is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 5 or less.

The divalent linking group for R ^12a is particularly preferably a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a heteroatom-containing divalent linking group.

When the divalent linking group for R ^12a is a linear or branched alkylene group, the number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and 1 or more and 4 or less. is particularly preferred, and 1 or more and 3 or less is most preferred. Specifically, in the description of the "optionally substituted divalent hydrocarbon group" as the divalent linking group described above, the linear or branched aliphatic hydrocarbon group and the same as the straight-chain alkylene group and branched-chain alkylene group.

When the divalent linking group for R ^12a is a cyclic aliphatic hydrocarbon group, the cyclic aliphatic hydrocarbon group may have a substituent as the divalent linking group described above. The same as the cyclic aliphatic hydrocarbon group mentioned as the "aliphatic hydrocarbon group containing a ring in the structure" in the description of "divalent hydrocarbon group" can be mentioned.

The cyclic aliphatic hydrocarbon group is particularly preferably a group obtained by removing two or more hydrogen atoms from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane.

When the divalent linking group for R ^12a is a heteroatom-containing divalent linking group, preferred examples of the linking group include -O-, -C(=O)-O-, -C(=O )-, -OC(=O)-O-, -C(=O)-NH-, -NH- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, general formula -Y ¹ -O-Y ² -, -[Y ¹ -C(=O)-O] _{m '} -Y ² -, or a group represented by -Y ¹ -OC(=O)-Y ₂ - [wherein Y ¹ and Y ² each independently have a substituent It is a good divalent hydrocarbon group, O is an oxygen atom, and m' is an integer of 0 or more and 3 or less. ] and the like.

When the divalent linking group in R ^12a is -NH-, the hydrogen atom in -NH- may be substituted with a substituent such as an alkyl group or acyl. The number of carbon atoms in the substituent (alkyl group, acyl group, etc.) is preferably 1 or more and 10 or less, more preferably 1 or more and 8 or less, and particularly preferably 1 or more and 5 or less.

^{Y _ _} _{_} ^{_ _ _ 1} and Y ² are each independently a divalent hydrocarbon group optionally having a substituent. Examples of the divalent hydrocarbon group include those similar to the "optionally substituted divalent hydrocarbon group" mentioned in the description of the divalent linking group.

Y ¹ is preferably a linear aliphatic hydrocarbon group, more preferably a linear alkylene group, more preferably a linear alkylene group having 1 to 5 carbon atoms, a methylene group, and ethylene groups are particularly preferred.

^Y2 is preferably a linear or branched aliphatic hydrocarbon group, more preferably a methylene group, an ethylene group, or an alkylmethylene group. The alkyl group in the alkylmethylene group is preferably a straight-chain alkyl group having 1 to 5 carbon atoms, more preferably a straight-chain alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

In the group represented by the formula -[Y ¹ -C(=O)-O] _m' -Y ² -, m' is an integer of 0 or more and 3 or less, preferably an integer of 0 or more and 2 or less, and 0 or 1 is more preferred, and 1 is particularly preferred. That is, the group represented by the formula -[Y ¹ -C(=O)-O] _m' -Y ² - is represented by the formula -Y ¹ -C(=O)-O-Y ² - groups are particularly preferred. Among them, a group represented by the formula -(CH ₂ ) _a' -C(=O)-O-(CH ₂ ) _b' - is preferable. In the formula, a' is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, more preferably 1 or 2, and most preferably 1. b' is an integer of 1 or more and 10 or less, preferably an integer of 1 or more and 8 or less, more preferably an integer of 1 or more and 5 or less, still more preferably 1 or 2, and most preferably 1.

As for the divalent linking group for R ^12a , the heteroatom-containing divalent linking group is preferably an organic group comprising a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group. Among them, a straight-chain group having an oxygen atom as a heteroatom, such as a group containing an ether bond or an ester bond, is preferred, and the aforementioned formulas -Y ¹ -O-Y ² -, -[Y ¹ -C(= O)—O] _m′ —Y ² — or a group represented by —Y ¹ —OC(=O)—Y ² — is more preferable, and the group represented by the above formula —[Y ¹ —C(=O) A group represented by —O] _m′ —Y ² — or —Y ¹ —O—C(=O)—Y ² — is particularly preferred.

The divalent linking group for R ^12a preferably contains an alkylene group or an ester bond (--C(=O)--O--).

The alkylene group is preferably a linear or branched alkylene group. Preferable examples of the linear aliphatic hydrocarbon group include a methylene group [ _--CH.sub.2-- ], an ethylene group [--( _CH.sub.2 ) _.sub.2-- ], a trimethylene group [--( _CH.sub.2 ) _.sub.3-- ], A tetramethylene group [-(CH ₂ ) ₄ -], a pentamethylene group [-(CH ₂ ) ₅ -] and the like can be mentioned. Preferable examples of the branched chain alkylene group include -CH(CH ₃ )-, -CH(CH ₂ CH ₃ )-, -C(CH ₃ ) ₂ -, -C(CH ₃ )(CH ₂ Alkylmethylene groups such as CH ₃ )—, —C(CH ₃ )(CH ₂ CH ₂ CH ₃ )—, —C(CH ₂ CH ₃ ) ₂ —; —CH(CH ₃ )CH ₂ —, —CH( Alkyl ethylenes such as CH ₃ )CH(CH ₃ )—, —C(CH ₃ ) ₂ CH ₂ —, —CH(CH ₂ CH ₃ )CH ₂ —, —C(CH ₂ CH ₃ ) ₂ —CH ₂ — Alkyltrimethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -; -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH and alkylalkylene groups such as alkyltetramethylene groups such as (CH ₃ )CH ₂ CH ₂ —.

The divalent linking group containing an ester bond is particularly represented by the formula: -R ^13a -C(=O)-O- [wherein R ^13a is a divalent linking group. ] is preferable. That is, the structural unit (a-3-S) is preferably a structural unit represented by the following formula (a-S1-1).

（式中、Ｒ、及びＲ^１１ａはそれぞれ前記と同様であり、Ｒ^１３ａは２価の連結基である。）

(Wherein, R and R ^11a are the same as defined above, and R ^13a is a divalent linking group.)

R ^13a is not particularly limited and includes, for example, the same divalent linking groups for R ^12a described above.
The divalent linking group for R ^13a is preferably a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in its structure, or a divalent linking group containing a hetero atom. Alternatively, a branched alkylene group or a divalent linking group containing an oxygen atom as a heteroatom is preferred.

As the linear alkylene group, a methylene group or an ethylene group is preferred, and a methylene group is particularly preferred. The branched alkylene group is preferably an alkylmethylene group or an alkylethylene group, and particularly -CH(CH ₃ )-, -C(CH ₃ ) ₂ - or -C(CH ₃ ) ₂ CH ₂ -. preferable.

The divalent linking group containing an oxygen atom is preferably a divalent linking group ^{containing an} ether bond or an ester ^bond . )—O] _m′ —Y ² — or —Y ¹ —O—C(=O)—Y ² — are more preferred. Y ¹ and Y ² are each independently a divalent hydrocarbon group which may have a substituent, and m' is an integer of 0 or more and 3 or less. Among them, -Y ¹ -OC(=O)-Y ² - is preferred, and a group represented by -(CH ₂ ) _c -OC(=O)-(CH ₂ ) _d - is particularly preferred. . c is an integer of 1 or more and 5 or less, preferably 1 or 2; d is an integer of 1 or more and 5 or less, preferably 1 or 2;

As the structural unit (a-3-S), a structural unit represented by the following formula (a-S1-11) or (a-S1-12) is particularly preferable, and the formula (a-S1-12) Structural units shown are more preferred.

（式中、Ｒ、Ａ’、Ｒ^１０ａ、ｚ、及びＲ^１３ａはそれぞれ前記と同じである。）

(Wherein, R, A', R ^10a , z, and R ^13a are the same as defined above.)

In formula (a-S1-11), A' is preferably a methylene group, an oxygen atom (--O--), or a sulfur atom (--S--).

R ^13a is preferably a linear or branched alkylene group or a divalent linking group containing an oxygen atom. The straight-chain or branched-chain alkylene group and the divalent linking group containing an oxygen atom for R ^13a are the above-mentioned straight-chain or branched-chain alkylene groups and the divalent linking group containing an oxygen atom, respectively. and similar ones.

As the structural unit represented by the formula (a-S1-12), a structural unit represented by the following formula (a-S1-12a) or (a-S1-12b) is particularly preferable.

（式中、Ｒ、及びＡ’はそれぞれ前記と同じであり、ｃ～ｅはそれぞれ独立に１以上３以下の整数である。）

(Wherein, R and A' are the same as above, and c to e are each independently an integer of 1 or more and 3 or less.)

[Structural unit (a-3-L)]
Examples of the structural unit (a-3-L) include those obtained by substituting R ^11a in the above formula (a-S1) with a lactone-containing cyclic group, and more specifically, the following formula ( Structural units represented by a-L1) to (a-L5) are exemplified.

（式中、Ｒは水素原子、炭素原子数１以上５以下のアルキル基、又は炭素原子数１以上５以下のハロゲン化アルキル基であり；Ｒ’はそれぞれ独立に水素原子、アルキル基、アルコキシ基、ハロゲン化アルキル基、水酸基、－ＣＯＯＲ”、－ＯＣ（＝Ｏ）Ｒ”、ヒドロキシアルキル基、又はシアノ基であり、Ｒ”は水素原子、又はアルキル基であり；Ｒ^１２ａは単結合、又は２価の連結基であり、ｓ”は０以上２以下の整数であり；Ａ”は酸素原子若しくは硫黄原子を含んでいてもよい炭素原子数１以上５以下のアルキレン基、酸素原子、又は硫黄原子であり；ｒは０又は１である。）

(Wherein, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; R 'is each independently a hydrogen atom, an alkyl group, an alkoxy group , a halogenated alkyl group, a hydroxyl group, —COOR″, —OC(═O)R″, a hydroxyalkyl group, or a cyano group, and R″ is a hydrogen atom or an alkyl group; R ^12a is a single bond, or is a divalent linking group, s″ is an integer of 0 or more and 2 or less; A″ is an alkylene group having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom, an oxygen atom, or sulfur atom; r is 0 or 1.)

R in formulas (a-L1) to (a-L5) is the same as described above.
The alkyl group, alkoxy group, halogenated alkyl group, -COOR'', -OC(=O)R'', and hydroxyalkyl group in R' may each have a -SO ₂ -containing cyclic group. Examples of the alkyl group, alkoxy group, halogenated alkyl group, —COOR″, —OC(═O)R″, and hydroxyalkyl group mentioned above as substituents include the same groups as those described above.

R' is preferably a hydrogen atom in view of industrial availability.
The alkyl group for R″ may be linear, branched or cyclic.
When R″ is a linear or branched alkyl group, it preferably has 1 to 10 carbon atoms, more preferably 1 to 5 carbon atoms.
When R″ is a cyclic alkyl group, it preferably has 3 to 15 carbon atoms, more preferably 4 to 12 carbon atoms, and most preferably 5 to 10 carbon atoms. Specifically, from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group, one or more Examples include groups from which hydrogen atoms are removed, etc. Specifically, one or more monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. Groups other than hydrogen atoms are included.
A″ includes the same as A′ in the above formula (3-1). A″ is an alkylene group having 1 to 5 carbon atoms, an oxygen atom (—O—) or a sulfur atom. (-S-) is preferable, and an alkylene group having 1 to 5 carbon atoms or -O- is more preferable. The alkylene group having 1 to 5 carbon atoms is more preferably a methylene group or a dimethylmethylene group, most preferably a methylene group.

R ^12a is the same as R ^12a in formula (a-S1) above.
In formula (a-L1), s″ is preferably 1 or 2.
Specific examples of structural units represented by formulas (a-L1) to (a-L3) are shown below. In each formula below, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

The structural unit (a-3-L) is preferably at least one selected from the group consisting of the structural units represented by the above formulas (a-L1) to (a-L5), and the formula (a-L1 ) to (a-L3) are more preferably at least one selected from the group consisting of structural units represented by the above formula (a-L1) or (a-L3). At least one selected from the group is particularly preferred.
Among them, the above formulas (a-L1-1), (a-L1-2), (a-L2-1), (a-L2-7), (a-L2-12), (a-L2 -14), (a-L3-1), and (a-L3-5) are preferably at least one selected from the group consisting of structural units.

式（ａ－Ｌ６）及び（ａ－Ｌ７）中、Ｒ及びＲ^１２ａは前述と同様である。 Further, as the structural unit (a-3-L), structural units represented by the following formulas (a-L6) to (a-L7) are also preferable.

In formulas (a-L6) and (a-L7), R and ^R12a are the same as above.

Further, the acrylic resin (A3) is a structural unit represented by the following formulas (a5) to (a7) having an acid-dissociable group as a structural unit that enhances the alkali solubility of the acrylic resin (A3) by the action of acid. including.

In the above formulas (a5) to (a7), R ^14a and R ^18a to R ^23a are each independently a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or represents a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, and R ^15a to R ^17a each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms; represents a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, or an aliphatic cyclic group having 5 to 20 carbon atoms, each independently linear having 1 to 6 carbon atoms represents a linear or branched alkyl group, or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, wherein R ^16a and R ^17a are bonded to each other and the carbon atom to which they are bonded may form a hydrocarbon ring having 5 to 20 carbon atoms together, Y ^a represents an optionally substituted aliphatic cyclic group or an alkyl group, p is 0 to 4 It represents an integer, and q represents 0 or 1.

Examples of the linear or branched alkyl group include methyl group, ethyl group, propyl group, isopropyl group, n-butyl group, isobutyl group, tert-butyl group, pentyl group, isopentyl group, neopentyl group and the like. mentioned. A fluorinated alkyl group is one in which some or all of the hydrogen atoms of the above alkyl group are substituted with fluorine atoms.
Specific examples of aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. Specifically, groups obtained by removing one hydrogen atom from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. is mentioned. In particular, groups obtained by removing one hydrogen atom from cyclohexane and adamantane (which may further have a substituent) are preferred.

When the above R ^16a and R ^17a do not bind to each other to form a hydrocarbon ring, as the above R ^15a , R ^16a and R ^17a , a carbon atom A linear or branched alkyl group having a number of 2 or more and 4 or less is preferable. R ^19a , R ^20a , R ^22a and R ^23a are preferably hydrogen atoms or methyl groups.

R ^16a and R ^17a may form an aliphatic cyclic group having 5 or more and 20 or less carbon atoms together with the carbon atoms to which they are bonded. Specific examples of such aliphatic cyclic groups include groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes and tetracycloalkanes. Specifically, one or more hydrogen atoms are removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. groups. In particular, groups obtained by removing one or more hydrogen atoms from cyclohexane and adamantane (which may further have a substituent) are preferred.

Furthermore, when the aliphatic cyclic group formed by R ^16a and R ^17a has a substituent on its ring skeleton, examples of the substituent include a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (=O ), and linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferred.

Y ^a above is an aliphatic cyclic group or an alkyl group, and includes groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as monocycloalkanes, bicycloalkanes, tricycloalkanes, and tetracycloalkanes. . Specifically, one or more hydrogen atoms are removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane and tetracyclododecane. and the like. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferred.

Furthermore, when the aliphatic cyclic group of Y ^a has a substituent on its ring skeleton, examples of the substituent include a polar group such as a hydroxyl group, a carboxyl group, a cyano group, and an oxygen atom (=O). and linear or branched alkyl groups having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferred.

When Y ^a is an alkyl group, it is preferably a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms. Such alkyl groups are particularly preferably alkoxyalkyl groups, and examples of such alkoxyalkyl groups include 1-methoxyethyl group, 1-ethoxyethyl group, 1-n-propoxyethyl group, 1-isopropoxy ethyl group, 1-n-butoxyethyl group, 1-isobutoxyethyl group, 1-tert-butoxyethyl group, 1-methoxypropyl group, 1-ethoxypropyl group, 1-methoxy-1-methyl-ethyl group, 1 -ethoxy-1-methylethyl group and the like.

Preferable specific examples of the structural unit represented by the above formula (a5) include those represented by the following formulas (a5-1) to (a5-33).

In formulas (a5-1) to (a5-33) above, R ^24a represents a hydrogen atom or a methyl group.

Preferable specific examples of the structural unit represented by the formula (a6) include those represented by the following formulas (a6-1) to (a6-26).

In formulas (a6-1) to (a6-26) above, R ²⁴ a represents a hydrogen atom or a methyl group.

Preferable specific examples of the structural unit represented by the above formula (a7) include those represented by the following formulas (a7-1) to (a7-15).

In formulas (a7-1) to (a7-15) above, R ^24a represents a hydrogen atom or a methyl group.

Among the structural units represented by the formulas (a5) to (a7) described above, the structural unit represented by the formula (a6) is preferable because it is easy to synthesize and the sensitivity is relatively high. Further, among the structural units represented by formula (a6), structural units in which Y ^a is an alkyl group are preferable, and structural units in which one or both of R ^19a and R ^20a are alkyl groups are preferable.

Furthermore, the acrylic resin (A3) is a resin composed of a copolymer containing structural units derived from a polymerizable compound having an ether bond together with the structural units represented by the above formulas (a5) to (a7). is preferred.

Examples of the polymerizable compound having an ether bond include radically polymerizable compounds such as (meth)acrylic acid derivatives having an ether bond and an ester bond, and specific examples include 2-methoxyethyl (meth)acrylate. , 2-ethoxyethyl (meth)acrylate, methoxytriethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl carbitol (meth)acrylate, phenoxypolyethylene glycol (meth)acrylate, methoxypolyethylene glycol (meth)acrylate Acrylate, methoxypolypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate and the like. Moreover, the polymerizable compound having an ether bond is preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, or methoxytriethylene glycol (meth)acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Furthermore, the acrylic resin (A3) can contain other polymerizable compounds as structural units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radically polymerizable compounds and anionically polymerizable compounds.

Examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid and crotonic acid; dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid; 2-methacryloyloxyethylsuccinic acid and 2-methacryloyloxy Methacrylic acid derivatives having a carboxy group and an ester bond such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) acrylate, cyclohexyl (meth) acrylate and other (meth) acrylic acid alkyl esters; 2-hydroxyethyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate and other (meth) acrylic acid hydroxyalkyl esters; phenyl ( (meth)acrylic acid aryl esters such as meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl fumarate; styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene , hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene and other vinyl group-containing aromatic compounds; vinyl group-containing aliphatic compounds such as vinyl acetate; butadiene, isoprene and other conjugated diolefins; acrylonitrile, methacrylic nitrile group-containing polymerizable compounds such as ronitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide;

As described above, the acrylic resin (A3) may contain a structural unit derived from a polymerizable compound having a carboxy group such as the above monocarboxylic acids or dicarboxylic acids. However, the acrylic resin (A3) does not substantially contain a structural unit derived from a polymerizable compound having a carboxy group, because it is easy to form a resist pattern including a non-resist portion having a rectangular cross-sectional shape. is preferred. Specifically, the ratio of structural units derived from a polymerizable compound having a carboxy group in the acrylic resin (A3) is preferably 20% by mass or less, more preferably 15% by mass or less, and particularly 5% by mass or less. preferable.
In the acrylic resin (A3), the acrylic resin containing a relatively large amount of structural units derived from a polymerizable compound having a carboxy group contains only a small amount of structural units derived from a polymerizable compound having a carboxy group, or does not contain It is preferably used in combination with an acrylic resin.

Examples of the polymerizable compound include (meth)acrylic acid esters having an acid non-dissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds, and the like. As the acid non-dissociable aliphatic polycyclic group, a tricyclodecanyl group, adamantyl group, tetracyclododecanyl group, isobornyl group, norbornyl group and the like are particularly preferred in terms of industrial availability. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

Specific examples of (meth)acrylic acid esters having an acid non-dissociable aliphatic polycyclic group include those having structures of the following formulas (a8-1) to (a8-5). can.

In formulas (a8-1) to (a8-5) above, R ^25a represents a hydrogen atom or a methyl group.

When the acrylic resin (A3) contains a structural unit (a-3) containing a —SO ₂ —containing cyclic group or a lactone-containing cyclic group, the structural unit (a-3) in the acrylic resin (A3) The content is preferably 5 mass % or more, more preferably 10 mass % or more, particularly preferably 10 mass % or more and 50 mass % or less, and most preferably 10 mass % or more and 30 mass % or less. When the positive photosensitive resin composition contains the structural unit (a-3) in an amount within the above range, it is easy to achieve both good developability and good pattern shape.

Further, the acrylic resin (A3) preferably contains 5% by mass or more, more preferably 10% by mass or more, and 10% by mass or more of the structural units represented by the above formulas (a5) to (a7). It is particularly preferable to contain 50% by mass or less.

The acrylic resin (A3) preferably contains a structural unit derived from the polymerizable compound having an ether bond. The content of the structural unit derived from the polymerizable compound having an ether bond in the acrylic resin (A3) is preferably 0% by mass or more and 50% by mass or less, more preferably 5% by mass or more and 30% by mass or less.

The acrylic resin (A3) preferably contains structural units derived from the (meth)acrylic acid esters having the acid non-dissociable aliphatic polycyclic group. In the acrylic resin (A3), the content of structural units derived from (meth)acrylic acid esters having an acid non-dissociable aliphatic polycyclic group is preferably 0% by mass or more and 50% by mass or less. % by mass or more and 30% by mass or less is more preferable.

As long as the positive photosensitive resin composition contains a predetermined amount of the acrylic resin (A3), an acrylic resin other than the acrylic resin (A3) described above can also be used as the base polymer (A). Such an acrylic resin other than the acrylic resin (A3) is not particularly limited as long as it contains the structural units represented by the above formulas (a5) to (a7).

The polystyrene equivalent mass average molecular weight of the base polymer (A) described above is preferably 10,000 or more and 600,000 or less, more preferably 20,000 or more and 400,000 or less, and still more preferably 30,000 or more and 300,000 or less. Such a mass average molecular weight allows the photosensitive resin layer to retain sufficient strength without deteriorating the releasability from the substrate, and furthermore prevents profile bulging and cracks from occurring during plating. can.

Moreover, the dispersion degree of the base polymer (A) is preferably 1.05 or more. Here, the degree of dispersion is a value obtained by dividing the weight average molecular weight by the number average molecular weight. Such a degree of dispersion makes it possible to avoid the problem of the desired stress resistance to plating and the tendency of the metal layer obtained by plating to swell.

The content of the base polymer (A) is preferably 5% by mass or more and 60% by mass or less with respect to the total mass of the positive photosensitive resin composition.

<Polyfunctional Vinyl Ether Monomer (B)>
A preferred positive photosensitive resin composition contains a polyfunctional vinyl ether monomer (B). Polyfunctional vinyl ether monomer (B) has the following formula (B1):
R ^B —(—R ^b1 —O—CH═CH ₂ ) _n1 (B1)
Including the compound represented by.
In formula (B1), ^RB is a monovalent linking group containing a monocyclic skeleton and/or a condensed cyclic skeleton in which two or more monocyclic rings are condensed. The sum of the number of monocyclic skeletons in R ^B and the number of monocyclic rings constituting the condensed ring skeleton is 2 or more. R ^b1 is a single bond or a divalent linking group. Two or more R ^b1 may be the same or different. n1 is an integer of 2 or more.

By including the polyfunctional vinyl ether monomer together with the base polymer (A) described above, the positive photosensitive resin composition suppresses the occurrence of cracks and retains its shape even when in contact with the plating solution under plating conditions. It is possible to form a resist pattern in which is difficult to change.
When the positive photosensitive resin composition contains the base polymer (A) and the polyfunctional vinyl ether monomer (B), the coating film made of the positive photosensitive resin composition is heated when forming the resist pattern. This is because the carboxy groups and/or hydroxyl groups of the base polymer (A) react with the polyfunctional vinyl ether monomer (B) to crosslink the molecular chains of the base polymer (A). .

In formula (B1), n1 bonds possessed by ^RB are preferably bonded to a monocyclic skeleton or condensed cyclic skeleton contained in ^RB .
The monocyclic skeleton contained in ^RB may be an aliphatic hydrocarbon ring skeleton, an aliphatic heterocyclic ring skeleton, an aromatic hydrocarbon skeleton, or an aromatic heterocyclic ring skeleton, and is preferably an aromatic hydrocarbon skeleton. The monocyclic skeleton for R ^{2 B} is preferably a cycloalkane skeleton having 6 to 10 carbon atoms or a benzene skeleton, more preferably a benzene skeleton.
The condensed ring skeleton contained in ^RB may be an aliphatic hydrocarbon ring skeleton, an aliphatic heterocyclic ring skeleton, an aromatic hydrocarbon ring skeleton, or an aromatic heterocyclic ring skeleton. Also, the condensed ring skeleton may be a skeleton based on a condensed ring in which an aliphatic ring and an aromatic ring are condensed. The condensed cyclic skeletons contained in ^RB include an adamantane skeleton, a norbornane skeleton, an isobornane skeleton, a tricyclodecane skeleton, a tetracyclododecane skeleton, a naphthalene skeleton, a benzoxazole skeleton, a benzothiazole skeleton, a benzimidazole skeleton, a fluorene skeleton, and A carbazole skeleton is preferred.
The number of monocyclic rings constituting the condensed cyclic skeleton contained in ^RB is preferably 2 or more and 4 or less, more preferably 2 or 3.

A monocyclic ring or condensed ring giving a monocyclic skeleton or condensed ring skeleton in R ^B may have one or more substituents. Examples of substituents include alkyl groups having 1 to 6 carbon atoms, alkoxy groups having 1 to 6 carbon atoms, aliphatic acyl groups having 2 to 6 carbon atoms, and aliphatic groups having 2 to 6 carbon atoms. acyloxy groups, halogen atoms, cyano groups, nitro groups, and the like.

The sum of the number of monocyclic skeletons in R ^B and the number of monocyclic rings constituting the condensed ring skeleton is 2 or more, preferably 2 or more and 4 or less, more preferably 2 or 3.

When R ^B contains two or more monocyclic skeletons or condensed cyclic skeletons, the multiple cyclic skeletons are linked via a single bond or a polyvalent linking group having a valence of two or more. A plurality of cyclic skeletons are preferably linked by a single bond or a divalent linking group.

The divalent linking group that links multiple cyclic skeletons includes an alkylene group having 1 to 6 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 6 carbon atoms, an ester bond (-CO-O -), amide bond (-CO-NH-), ether bond (-O-), carbonyl group (-CO-), sulfide bond (-S-), disulfide bond (-SS-), sulfonyl group ( -SO ₂ -), sulfinyl group (-SO-), imino group (-NH-), azo group (-N=N-) and the like.
Examples of alkylene groups having 1 to 6 carbon atoms include methylene group, ethane-1,1-diyl group, ethylene group (ethane-1,2-diyl group), propane-2,2-diyl group and the like. is mentioned.
Examples of unsaturated aliphatic hydrocarbon groups having 2 to 6 carbon atoms include vinylene group (ethylene-1,2-diyl group), 2-butene-1,2-diyl group (-CH ₂ -CH= CH—CH ₂ —), and 1,3-butadiene-1,4-diyl group (—CH═CH—CH═CH—).

n1 is an integer of 2 or more. n1 is preferably 2 or more and 4 or less, more preferably 2 or 3, and even more preferably 2, because the compound represented by formula (B1) can be easily synthesized or obtained.

Preferred specific examples of ^RB include the following divalent to tetravalent linking groups.

Among the above specific examples, the following linking groups are more preferred.

R ^b1 is a single bond or a divalent linking group. The divalent linking group is not particularly limited. For example, the divalent linking group includes a divalent hydrocarbon group, an ester bond (-CO-O-), an amide bond (-CO-NH-), an ether bond (-O-), a carbonyl group (-CO -), sulfide bond (-S-), disulfide bond (-SS-), sulfonyl group (-SO ₂ -), sulfinyl group (-SO-), imino group (-NH-), and azo group ( -N=N-), or a combination of two or more selected from the group consisting of.
A more preferable divalent linking group includes a group represented by -R ^b2 -R ^b3 - in formula (B2) described later.

Since it is particularly easy to form a resist pattern whose shape does not easily change even when it comes into contact with a plating solution under plating conditions while suppressing the generation of cracks, the compound represented by formula (B1) is Formula (B2):
R ^B —(—R ^b2 —R ^b3 —O—CH=CH ₂ ) _n1 (B2)
is preferably a compound represented by
In formula (B2), R ^B and n1 are the same as R ^B and n1 in formula (B1). R ^b2 is an ether bond or an ester bond. R ^b3 is a divalent hydrocarbon group.

The orientation of the ester bond as R ^b2 is not particularly limited. That is, the compound represented by formula (B2) corresponds to any one of the compounds represented by formulas (B2-1) to (B2-3) below.
R ^B —(—OR ^b3 —O—CH=CH ₂ ) _n1 (B2-1)
R ^B —(—CO—O—R ^b3 —O—CH=CH ₂ ) _n1 (B2-2)
R ^B —(—O—CO—R ^b3 —O—CH=CH ₂ ) _n1 (B2-3)

The number of carbon atoms in the divalent hydrocarbon group for R ^b3 is not particularly limited. The number of carbon atoms in the divalent hydrocarbon group as R ^b3 is preferably 1 or more and 10 or less, more preferably 1 or more and 6 or less, and still more preferably 2 or 3.

The divalent hydrocarbon group as R ^b3 may be an aliphatic group, an aromatic group, or a combination of an aliphatic group and an aromatic group. As the divalent hydrocarbon group for R ^b3 , an aliphatic hydrocarbon group is preferred because it is flexible and tends to suppress cracking of the resist pattern. The aliphatic hydrocarbon group may be a straight-chain aliphatic hydrocarbon group, a branched-chain aliphatic hydrocarbon group, a cyclic aliphatic hydrocarbon group, or a combination thereof. . As the aliphatic hydrocarbon group, a linear aliphatic hydrocarbon group or a branched aliphatic hydrocarbon group is preferable, and a linear aliphatic hydrocarbon group is more preferable. The aliphatic hydrocarbon group may have an unsaturated bond. As the aliphatic hydrocarbon group, a saturated aliphatic hydrocarbon group is preferred.

Specific examples of the divalent hydrocarbon group for R ^b3 include p-phenylene group, m-phenylene group, o-phenylene group, methylene group, ethane-1,1-diyl group, ethylene group (ethane-1, 2-diyl group), propane-1,3-diyl group, propane-1,2-diyl group, propane-1,1-diyl group, propane-1,3-diyl group, butane-1,4-diyl group , pentane-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonane-1,9-diyl group, decane-1, 10-diyl group, cyclohexane-1,4-diyl group, cyclohexane-1,3-diyl group, and cyclohexane-1,2-diyl group.
Among these, ethylene group (ethane-1,2-diyl group), propane-1,3-diyl group and propane-1,2-diyl group are preferred.

The compound represented by formula (B2) has the following formula (B3):
R ^B1 —(—CO—OR ^b3 —O—CH=CH ₂ ) _n2 (B3)
is preferably a compound represented by
In formula (B3), R ^b3 is the same as R ^b3 in formula (B2). n2 is an integer of 2 or more and 4 or less. R ^B1 is represented by the following formulas (B3-1) to (B3-3):
-R ^B2 -R ^b4 -R ^B2 -... (B3-1)
-R ^B2 -R ^b4 -R ^B3 <... (B3-2)
>R ^B3 -R ^b4 -R ^B3 <... (B3-3)
is a linking group having a valence of 2 or more and 4 or less, represented by any one of R ^B2 is a phenylene group optionally having a substituent. R ^B3 is a benzenetriyl group optionally having a substituent. R ^b4 is a single bond or a divalent linking group.

The phenylene group for R ^B2 is preferably a p-phenylene group and an m-phenylene group, more preferably a p-phenylene group. The benzenetriyl group for R ^B3 is preferably a benzene-1,3,5-triyl group and a benzene-1,3,4-triyl group, more preferably a benzene-1,3,5-triyl group.

Examples of substituents that the phenylene group as R ^B2 or the benzenetriyl group as R ^B3 may have include an alkyl group having 1 to 6 carbon atoms and an alkoxy group having 1 to 6 carbon atoms. , an aliphatic acyl group having 2 to 6 carbon atoms, an aliphatic acyloxy group having 2 to 6 carbon atoms, a halogen atom, a cyano group, a nitro group, and the like.

R ^b4 is a single bond or a divalent linking group. The divalent linking group for R ^b4 includes an alkylene group having 1 to 6 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 6 carbon atoms, an ester bond (—CO—O—), and an amide. bond (-CO-NH-), ether bond (-O-), carbonyl group (-CO-), sulfide bond (-S-), disulfide bond (-SS-), sulfonyl group (-SO ₂ - ), a sulfinyl group (--SO--), an imino group (--NH--), and an azo group (--N=N--).

As the divalent linking group represented by formula (B3-1), the following groups are preferable.

As the trivalent linking group represented by formula (B3-2), the following groups are preferable.

As the tetravalent linking group represented by formula (B3-3), the following groups are more preferable.

Among the linking groups represented by formulas (B3-1) to (B3-3), the divalent linking group represented by formula (B3-1) is preferred. Preferred specific examples of the divalent linking group represented by formula (B3-1) include the following groups.

Preferred specific examples of the compound represented by the formula (B1) described above include compounds in which groups represented by the following formulas (B1-i) to (B1-vi) are bonded to the following divalent groups. is mentioned. Two different groups selected from the groups represented by the following formulas (B1-i) to (B1-vi) may be bound to the following divalent group, but the same two groups A combination is preferred.
-CO-O-CH ₂ CH ₂ -O-CH=CH ₂ (B1-i)
—O—CO—CH ₂ CH ₂ —O—CH=CH ₂ (B1-ii)
-O-CH ₂ CH ₂ -O-CH=CH ₂ (B1-iii)
-CO-O-CH ₂ CH ₂ CH ₂ -O-CH=CH ₂ (B1-iv)
—O—CO—CH ₂ CH ₂ CH ₂ —O—CH=CH ₂ (B1-v)
-O-CH ₂ CH ₂ CH ₂ -O-CH=CH ₂ (B1-vi)

The ratio of the mass of the compound represented by the formula (B1) to the mass of the polyfunctional vinyl ether monomer (B) is preferably 50% by mass or more, more preferably 70% by mass or more, further preferably 80% by mass or more, and 90% by mass. % by mass or more is even more preferred, and 100% by mass is particularly preferred.

The method for synthesizing the compound represented by the following formula (B1) described above is not particularly limited.
R ^B —(—R ^b1 —O—CH═CH ₂ ) _n1 (B1)
A synthesis method is appropriately selected in consideration of the structures of ^RB and ^Rb1 .
The synthesis method will be described below using the compound represented by the above formula (B2) as a representative example.

As described above, the compound represented by formula (B2) corresponds to the compound represented by any one of the following formulas (B2-1) to (B2-3).
R ^B —(—OR ^b3 —O—CH=CH ₂ ) _n1 (B2-1)
R ^B —(—CO—O—R ^b3 —O—CH=CH ₂ ) _n1 (B2-2)
R ^B —(—O—CO—R ^b3 —O—CH=CH ₂ ) _n1 (B2-3)

For the compound represented by formula (B2-1), a halogen-containing vinyl ether compound represented by Hal-R ^b3 --O--CH=CH ₂ is added to the polyol represented by R ^B --(OH) _n1 . can be synthesized by carrying out a reaction according to the so-called Williamson's ether synthesis method. Here, Hal is a halogen atom. As the halogen atom, a chlorine atom and a bromine atom are preferred.

For the compound represented by formula (B2-2), a polyvalent carboxylic acid compound represented by R ^B —(COOH) _n1 and an alcohol represented by HO—R ^b3 —O—CH═CH ₂ are , can be synthesized by a method of condensing in the presence of a condensing agent. As the condensing agent, carbodiimide compounds such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and dicyclohexylcarbodiimide, carbonyldiimidazole, and the like can be used.
Further, a method of reacting an acid halide of a polyvalent carboxylic acid represented by R ^B —(COHal) _n1 with an alcohol represented by HO—R ^b3 —O—CH═CH ₂ also yields the formula (B2 -2) can be synthesized. Here, Hal is a halogen atom. As the halogen atom, a chlorine atom and a bromine atom are preferred.

For the compound represented by formula (B2-3), a polyol represented by R ^B —(OH) _n1 and a vinyloxy group-containing carboxylic acid represented by HO—CO—R ^b3 —O—CH═CH ₂ can be synthesized by a method of condensing in the presence of a condensing agent. As the condensing agent, carbodiimide compounds such as 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide and dicyclohexylcarbodiimide, carbonyldiimidazole, and the like can be used.
Also, by a method of reacting a polyol represented by R ^B —(OH) _n1 with an acid halide of a vinyloxy group-containing carboxylic acid represented by Hal—CO—R ^b3 —O—CH=CH ₂ , A compound represented by formula (B2-3) can be synthesized. Here, Hal is a halogen atom. As the halogen atom, a chlorine atom and a bromine atom are preferred.

The solvent used in each of the above reactions is not particularly limited as long as it is inert to each reaction. Solvents that can be used in the above reactions include aliphatic hydrocarbons such as hexane, heptane and octane; aromatic hydrocarbons such as toluene, xylene and mesitylene; halogenated hydrocarbons such as methylene chloride; ketones such as ketones, cyclohexanone, acetophenone and benzophenone; and esters such as ethyl acetate and n-butyl acetate.
The temperature and time in each of the above reactions are not particularly limited. The reaction temperature and the reaction temperature are appropriately selected from the range of conditions normally employed in each of the above reactions.

Specific examples of the compound that the polyfunctional vinyl ether monomer (B) may contain together with the compound represented by formula (B1) include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and polyethylene glycol divinyl ether. , propylene glycol divinyl ether, dipropylene glycol divinyl ether, tripropylene glycol divinyl ether, polypropylene glycol divinyl ether, 1,3-propanediol divinyl ether, 1,4-butanediol divinyl ether, 1,5-pentanediol divinyl ether, 1 Chain aliphatic divinyl ether such as ,6-hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,10-decanediol divinyl ether, neopentyl glycol divinyl ether, trimethylolpropane divinyl ether, pentaerythritol divinyl ether cycloaliphatic divinyl ethers such as 1,4-cyclohexanediol divinyl ether and 1,4-cyclohexanedimethanol divinyl ether; 1,4-divinyloxybenzene, 1,3-divinyloxybenzene, 1,2- Aromatic divinyl ethers such as divinyloxybenzene, 1,4-benzenedimethanol divinyl ether, 1,3-benzenedimethanol divinyl ether, and 1,2-benzenedimethanol divinyl ether; trimethylolpropane trivinyl ether, pentaerythritol Trivalent or higher polyvalent vinyl ethers such as tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexavinyl ether can be mentioned.

The content of the polyfunctional vinyl ether monomer (B) in the positive photosensitive resin composition is not particularly limited as long as the object of the present invention is not impaired. It is particularly easy to suppress the occurrence of cracks when forming a resist pattern, and it is particularly easy to form a resist pattern that does not change its shape even when it comes into contact with a plating solution under plating conditions. , The content of the polyfunctional vinyl ether monomer (B) is preferably 0.5 parts by mass or more and 50 parts by mass or less, more preferably 1 part by mass or more and 30 parts by mass or less, relative to 100 parts by mass of the base polymer (A). .

<Acid Generator (C) Generating Acid by Exposure to Actinic Rays or Radiation>
The acid generator (C) is a compound that generates an acid upon exposure to actinic rays or radiation, and is not particularly limited as long as it is a compound that directly or indirectly generates an acid upon exposure to light. As the acid generator (C), the acid generators of the first to fifth embodiments described below are preferred. Preferred embodiments of the acid generator (C) suitably used in the positive photosensitive resin composition are described below as first to fifth embodiments.

A first aspect of the acid generator (C) includes compounds represented by the following formula (c1).

In formula (c1) above, X ^1c represents a sulfur atom or an iodine atom with a valence of g, where g is 1 or 2. h represents the number of repeating units of the structure in parentheses. R ^1c is an organic group bonded to X ^1c , and is an aryl group having 6 to 30 carbon atoms, a heterocyclic group having 4 to 30 carbon atoms, an alkyl group having 1 to 30 carbon atoms, represents an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, and R ^1c is alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthio at least one selected from the group consisting of carbonyl, acyloxy, arylthio, alkylthio, aryl, heterocycle, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, and nitro groups, and halogen seeds may be substituted. The number of R ^1c is g+h(g−1)+1, and each R ^1a may be the same or different. Two or more R ^1c may be directly connected to each other, or -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2a -, -CO-, -COO-, -CONH- , an alkylene group having 1 to 3 carbon atoms, or a phenylene group to form a ring structure containing X ^1c . R ^2a is an alkyl group having 1 to 5 carbon atoms or aryl group having 6 to 10 carbon atoms.

^X2c is a structure represented by the following formula (c2).

In the above formula (c2), X ^4c is an alkylene group having 1 to 8 carbon atoms, an arylene group having 6 to 20 carbon atoms, or a divalent group of a heterocyclic compound having 8 to 20 carbon atoms. X ^4c is selected from the group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl having 6 to 10 carbon atoms, hydroxy, cyano, nitro groups, and halogen It may be substituted with at least one selected. X ^5c is -O-, -S-, -SO-, -SO ₂ -, -NH-, -NR ^2c -, -CO-, -COO-, -CONH-, alkylene having 1 to 3 carbon atoms group, or a phenylene group. h represents the number of repeating units of the structure in parentheses. The h+1 X ^4c's and the h X ^5c 's may be the same or different. ^R2a is the same as defined above.

X ^3c- is a counter ion of onium, and includes a fluorinated alkylfluorophosphate anion represented by the following formula (c17) or a borate anion represented by the following formula (c18).

In formula (c17) above, ^R3c represents an alkyl group in which 80% or more of the hydrogen atoms are substituted with fluorine atoms. j indicates the number and is an integer of 1 or more and 5 or less. j R ^3c may be the same or different.

In the above formula (c18), R ^4c to R ^7c each independently represent a fluorine atom or a phenyl group, and part or all of the hydrogen atoms in the phenyl group are selected from the group consisting of a fluorine atom and a trifluoromethyl group. may be substituted with at least one of

The onium ion in the compound represented by the above formula (c1) includes triphenylsulfonium, tri-p-tolylsulfonium, 4-(phenylthio)phenyldiphenylsulfonium, bis[4-(diphenylsulfonio)phenyl]sulfide, bis[4-{bis[4-(2-hydroxyethoxy)phenyl]sulfonio}phenyl]sulfide, bis{4-[bis(4-fluorophenyl)sulfonio]phenyl}sulfide, 4-(4-benzoyl-2- Chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 7-isopropyl-9-oxo-10-thia-9,10-dihydroanthracen-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -thia-9,10-dihydroanthracen-2-yldiphenylsulfonium, 2-[(diphenyl)sulfonio]thioxanthone, 4-[4-(4-tert-butylbenzoyl)phenylthio]phenyldi-p-tolylsulfonium, 4- (4-benzoylphenylthio)phenyldiphenylsulfonium, diphenylphenacylsulfonium, 2-naphthylmethyl(1-ethoxycarbonyl)ethylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4- (4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4-acetophenylthio)phenyl]diphenylsulfonium, octadecylmethylphenacylsulfonium, diphenyliodonium, di-p-tolyliodonium, bis(4-dodecylphenyl) ) Iodonium, bis(4-methoxyphenyl)iodonium, (4-octyloxyphenyl)phenyliodonium, bis(4-decyloxy)phenyliodonium, 4-(2-hydroxytetradecyloxy)phenylphenyliodonium, 4-isopropylphenyl ( p-tolyl)iodonium, 4-isobutylphenyl(p-tolyl)iodonium, and the like.

Of the onium ions in the compound represented by formula (c1) above, preferred onium ions include sulfonium ions represented by formula (c19) below.

In the above formula (c19), each R ^8c is independently from a hydrogen atom, alkyl, hydroxy, alkoxy, alkylcarbonyl, alkylcarbonyloxy, alkyloxycarbonyl, halogen atom, optionally substituted aryl, arylcarbonyl, represents a group selected from the group consisting of X ^2c has the same meaning as X ^2c in formula (c1) above.

Specific examples of the sulfonium ion represented by the above formula (c19) include 4-(phenylthio)phenyldiphenylsulfonium, 4-(4-benzoyl-2-chlorophenylthio)phenylbis(4-fluorophenyl)sulfonium, 4- (4-benzoylphenylthio)phenyldiphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]4-biphenylsulfonium, phenyl[4-(4-biphenylthio)phenyl]3-biphenylsulfonium, [4-(4 -acetophenylthio)phenyl]diphenylsulfonium, diphenyl[4-(p-terphenylthio)phenyl]diphenylsulfonium.

In the fluorinated alkylfluorophosphate anion represented by the above formula (c17), R ^3c represents an alkyl group substituted with a fluorine atom, preferably has 1 or more and 8 or less carbon atoms, more preferably 1 or more carbon atoms. 4 or less. Specific examples of alkyl groups include straight chain alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; further cyclopropyl, cyclobutyl and cyclopentyl. , cycloalkyl groups such as cyclohexyl, etc., and the ratio of hydrogen atoms in the alkyl groups substituted with fluorine atoms is usually 80% or more, preferably 90% or more, more preferably 100%. If the substitution rate of fluorine atoms is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by the formula (c1) is lowered.

Particularly preferred R ^3c is a linear or branched perfluoroalkyl group having 1 to 4 carbon atoms and having a fluorine atom substitution rate of 100%, and specific examples thereof include CF ₃ and CF ₃ CF. _{2 ,} ( _{CF3 ) 2CF} , _{CF3CF2CF2 , CF3CF2CF2CF2 ,} ( _{CF3 ) 2CFCF2 , CF3CF2} ( _CF3 )CF, ( _{CF3 ) 3C} mentioned. The number j of R ^3c is an integer of 1 or more and 5 or less, preferably 2 or more and 4 or less, and particularly preferably 2 or 3.

Specific examples of preferred fluorinated alkylfluorophosphate anions include [(CF ₃ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ ) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ⁻ , [ ⁽ ( _CF3 ) _{2CFCF2 ) 2PF4} ] ^- _{, [} ( _{( CF3 ) 2CFCF2} ) _3PF3 ] _{- , [} (CF3CF2CF2CF2) _{2PF4 ]} ^- , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among which [(CF ₃ CF ₂ ) ₃ PF ₃ ] ^- , [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , [((CF ₃ ) ₂ CF) ₃ PF ₃ ] ⁻ , [((CF ₃ ) ₂ CF) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , or [(( CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ^- is particularly preferred.

Preferred specific examples of the borate anion represented by the above formula (c18) include tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ), tetrakis[(trifluoromethyl)phenyl]borate ( [B(C ₆ H ₄ CF ₃ ) ₄ ] ⁻ ), difluorobis(pentafluorophenyl)borate ([(C ₆ F ₅ ) ₂ BF ₂ ] ⁻ ), trifluoro(pentafluorophenyl)borate ([(C ₆ F ₅ )BF ₃ ] ⁻ ), tetrakis(difluorophenyl)borate ([B(C ₆ H ₃ F ₂ ) ₄ ] ⁻ ), and the like. Among these, tetrakis(pentafluorophenyl)borate ([B(C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferred.

As a second embodiment of the acid generator (C), 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methyl-2-furyl)ethenyl]-s-triazine, 2,4-bis( trichloromethyl)-6-[2-(5-ethyl-2-furyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-propyl-2-furyl)ethenyl ]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dimethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2 -(3,5-diethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,5-dipropoxyphenyl)ethenyl]-s-triazine, 2, 4-bis(trichloromethyl)-6-[2-(3-methoxy-5-ethoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3-methoxy- 5-propoxyphenyl)ethenyl]-s-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-methylenedioxyphenyl)ethenyl]-s-triazine, 2,4-bis( trichloromethyl)-6-(3,4-methylenedioxyphenyl)-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)phenyl-s-triazine, 2,4 -bis-trichloromethyl-6-(2-bromo-4-methoxy)phenyl-s-triazine, 2,4-bis-trichloromethyl-6-(2-bromo-4-methoxy)styrylphenyl-s-triazine, 2,4-bis-trichloromethyl-6-(3-bromo-4-methoxy)styrylphenyl-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-1,3, 5-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(2-furyl)ethenyl]-4,6-bis( trichloromethyl)-1,3,5-triazine, 2-[2-(5-methyl-2-furyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[ 2-(3,5-dimethoxyphenyl)ethenyl]-4,6-bis(trichloromethyl)-1,3,5-triazine, 2-[2-(3,4-dimethoxyphenyl)ethenyl]-4,6 -bis(trichloromethyl)-1,3,5-triazine, 2-(3,4-methylenedioxyphenyl)-4,6-bis(trichloromethyl)-1,3,5-triazine, tris(1, 3-dibromopropyl)-1,3,5-triazine, tris(2,3-dibromopropyl)-1,3,5-triazine and other halogen-containing triazine compounds, and tris(2,3-dibromopropyl) isocyanurate and halogen-containing triazine compounds represented by the following formula (c3).

In formula (c3) above, R ^9c , R ^10c , and R ^11c each independently represent a halogenated alkyl group.

Further, as a third aspect of the acid generator (C), α-(p-toluenesulfonyloxyimino)-phenylacetonitrile, α-(benzenesulfonyloxyimino)-2,4-dichlorophenylacetonitrile, α-(benzene sulfonyloxyimino)-2,6-dichlorophenylacetonitrile, α-(2-chlorobenzenesulfonyloxyimino)-4-methoxyphenylacetonitrile, α-(ethylsulfonyloxyimino)-1-cyclopentenylacetonitrile, and oxime sulfonate groups and a compound represented by the following formula (c4).

In formula (c4) above, R ^12c represents a monovalent, divalent, or trivalent organic group, and R ^13c is a substituted or unsubstituted saturated hydrocarbon group, unsaturated hydrocarbon group, or aromatic group. and n represents the number of repeating units of the structure in parentheses.

In the above formula (c4), the aromatic group refers to a group of compounds exhibiting physical and chemical properties specific to aromatic compounds, for example, aryl groups such as phenyl group and naphthyl group, furyl group, thienyl and heteroaryl groups such as These may have one or more suitable substituents such as halogen atoms, alkyl groups, alkoxy groups, nitro groups, etc. on the ring. Further, R ^13c is particularly preferably an alkyl group having 1 to 6 carbon atoms, such as a methyl group, an ethyl group, a propyl group and a butyl group. Particularly preferred are compounds in which R ^12c is an aromatic group and R ^13c is an alkyl group having 1 to 4 carbon atoms.

As the acid generator represented by the above formula (c4), when n=1, R ^12c is any one of a phenyl group, a methylphenyl group, or a methoxyphenyl group, and R ^13c is a methyl group. Specifically, α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl)acetonitrile, α-(methylsulfonyloxyimino)-1-(p- methoxyphenyl)acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophen-3-ylidene](o-tolyl)acetonitrile and the like. When n=2, the acid generator represented by the above formula (c4) specifically includes an acid generator represented by the following formula.

A fourth aspect of the acid generator (C) is an onium salt having a naphthalene ring in the cation moiety. The phrase "having a naphthalene ring" means having a structure derived from naphthalene, and means that at least two ring structures and their aromaticity are maintained. The naphthalene ring has a substituent such as a linear or branched alkyl group having 1 to 6 carbon atoms, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. good too. The structure derived from the naphthalene ring may be a monovalent group (one free atom valence) or a divalent group (two free atom valences) or more, but it is preferable that it is a monovalent group. Desirable (however, at this time, free valences shall be counted excluding the portions bonded to the above substituents). The number of naphthalene rings is preferably 1 or more and 3 or less.

As the cation moiety of such an onium salt having a naphthalene ring in the cation moiety, a structure represented by the following formula (c5) is preferable.

In the above formula (c5), at least one of R ^14c , R ^15c , and R ^16c represents a group represented by the following formula (c6), and the rest are linear or branched having 1 to 6 carbon atoms , a phenyl group which may have a substituent, a hydroxyl group, or a linear or branched alkoxy group having 1 to 6 carbon atoms. Alternatively, one of R ^14c , R ^15c , and R ^16c is a group represented by the following formula (c6), and the remaining two are each independently linear or branched having 1 to 6 carbon atoms and these terminals may be combined to form a ring.

In the above formula (c6), R ^17c and R ^18c each independently represent a hydroxyl group, a linear or branched alkoxy group having 1 to 6 carbon atoms, or a linear or branched alkoxy group having 1 to 6 carbon atoms. represents a branched alkyl group, and R ^19c represents a single bond or an optionally substituted linear or branched alkylene group having 1 to 6 carbon atoms. l and m each independently represent an integer of 0 or more and 2 or less, and l+m is 3 or less. However, when multiple R ^17c are present, they may be the same or different. Moreover, when multiple R ^18c are present, they may be the same or different from each other.

Of the above R ^14c , R ^15c , and R ^16c , the number of groups represented by the above formula (c6) is preferably one from the viewpoint of the stability of the compound, and the rest are straight groups having 1 to 6 carbon atoms. It is a chain or branched alkylene group, and these terminals may be combined to form a ring. In this case, the two alkylene groups form a 3- to 9-membered ring including a sulfur atom. The number of atoms (including sulfur atoms) constituting the ring is preferably 5 or more and 6 or less.

Further, examples of the substituent that the alkylene group may have include an oxygen atom (in this case, forming a carbonyl group together with the carbon atoms constituting the alkylene group), a hydroxyl group, and the like.

Further, the substituents that the phenyl group may have include a linear or branched alkoxy group having 1 to 6 carbon atoms, and a linear or branched alkyl group having 1 to 6 carbon atoms. and the like.

Examples of cations suitable for these cation moieties include cations represented by the following formulas (c7) and (c8), and the structure represented by the following formula (c8) is particularly preferable.

Such a cation moiety may be an iodonium salt or a sulfonium salt, but a sulfonium salt is preferable from the viewpoint of acid generation efficiency.

Therefore, an anion capable of forming a sulfonium salt is desirable as an anion suitable for the anion portion of the onium salt having a naphthalene ring in the cation portion.

The anion part of such an acid generator is a fluoroalkylsulfonate ion or an arylsulfonate ion in which some or all of the hydrogen atoms are fluorinated.

The alkyl group in the fluoroalkylsulfonate ion may have 1 to 20 carbon atoms and may be linear, branched, or cyclic, and the number of carbon atoms should be 1 to 10, considering the bulkiness of the generated acid and its diffusion distance. is preferred. In particular, a branched or cyclic alkyl group is preferred because of its short diffusion distance. Moreover, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group, and the like can be mentioned as preferable ones because they can be synthesized at low cost.

The aryl group in the arylsulfonate ion is an aryl group having 6 to 20 carbon atoms, and includes an alkyl group, a phenyl group which may or may not be substituted with a halogen atom, and a naphthyl group. In particular, an aryl group having 6 or more and 10 or less carbon atoms is preferable because it can be synthesized at low cost. Specific examples of preferred aryl groups include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group and the like.

In the above fluoroalkylsulfonate ion or arylsulfonate ion, when some or all of the hydrogen atoms are fluorinated, the fluorination rate is preferably 10% or more and 100% or less, more preferably 50% or more and 100%. It is below, and it is particularly preferable to replace all the hydrogen atoms with fluorine atoms because the strength of the acid increases. Specific examples of such compounds include trifluoromethanesulfonate, perfluorobutanesulfonate, perfluorooctane sulfonate, and perfluorobenzenesulfonate.

Among these, preferred anion moieties include those represented by the following formula (c9).

In formula (c9) above, R ^20c is a group represented by formulas (c10), (c11), and (c12) below.

In the above formula (c10), x represents an integer of 1 or more and 4 or less. In the above formula (c11), R ^21c is a hydrogen atom, a hydroxyl group, a linear or branched alkyl group having 1 to 6 carbon atoms, or a linear or branched chain having 1 to 6 carbon atoms. represents an alkoxy group, and y represents an integer of 1 or more and 3 or less. Among these, trifluoromethanesulfonate and perfluorobutanesulfonate are preferred from the viewpoint of safety.

As the anion moiety, an anion moiety containing nitrogen represented by the following formulas (c13) and (c14) can also be used.

In the above formulas (c13) and (c14), X ^c represents a linear or branched alkylene group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms in the alkylene group is 2 or more and 6 or less, preferably 3 or more and 5 or less, most preferably 3 carbon atoms. Y ^c and Z ^c each independently represent a linear or branched alkyl group in which at least one hydrogen atom is substituted with a fluorine atom, and the number of carbon atoms in the alkyl group is 1 or more and 10 or less. , preferably 1 or more and 7 or less, more preferably 1 or more and 3 or less.

The smaller the number of carbon atoms in the alkylene group of ^Xc or the number of carbon atoms in the alkyl groups of Yc ^{and Zc} , the better the solubility in organic solvents, which is preferable.

Moreover, in the alkylene group of X ^c or the alkyl group of Y ^c and Z ^c , the greater the number of hydrogen atoms substituted with fluorine atoms, the stronger the acid strength, which is preferable. The ratio of fluorine atoms in the alkylene group or alkyl group, that is, the fluorination rate is preferably 70% or more and 100% or less, more preferably 90% or more and 100% or less, and most preferably all hydrogen atoms are fluorine It is an atom-substituted perfluoroalkylene group or perfluoroalkyl group.

Preferred compounds as such onium salts having a naphthalene ring in the cation moiety include compounds represented by the following formulas (c15) and (c16).

Further, as a fifth aspect of the acid generator (C), bis(p-toluenesulfonyl)diazomethane, bis(1,1-dimethylethylsulfonyl)diazomethane, bis(cyclohexylsulfonyl)diazomethane, bis(2,4- bissulfonyldiazomethanes such as dimethylphenylsulfonyl)diazomethane; 2-nitrobenzyl p-toluenesulfonate, 2,6-dinitrobenzyl p-toluenesulfonate, nitrobenzyl tosylate, dinitrobenzyl tosylate, nitrobenzylsulfonate, nitro Nitrobenzyl derivatives such as benzyl carbonate and dinitrobenzyl carbonate; Sulfonic acid esters such as oxymaleimide and N-methylsulfonyloxyphthalimide; N-(trifluoromethylsulfonyloxy)phthalimide, N-(trifluoromethylsulfonyloxy)-1,8-naphthalimide, N-(trifluoromethyl trifluoromethanesulfonic acid esters such as sulfonyloxy)-4-butyl-1,8-naphthalimide and N-(trifluoromethylsulfonyloxy)-4-butylthio-1,8-naphthalimide; diphenyliodonium hexafluorophosphate , (4-methoxyphenyl)phenyliodonium trifluoromethanesulfonate, bis(p-tert-butylphenyl)iodonium trifluoromethanesulfonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl)diphenylsulfonium trifluoromethanesulfonate, Onium salts such as (p-tert-butylphenyl)diphenylsulfonium trifluoromethanesulfonate; benzoin tosylate such as benzoin tosylate and α-methylbenzoin tosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts , benzyl carbonate and the like.

The acid generator (C) may be used alone or in combination of two or more. In addition, the content of the acid generator (C) is preferably 0.1% by mass or more and 10% by mass or less, and 0.3% by mass or more and 5% by mass, based on the total solid mass of the positive photosensitive resin composition. is more preferred. By setting the amount of the acid generator (C) to be used within the above range, it is easy to prepare a photosensitive resin composition that has good sensitivity, is a uniform solution, and has excellent storage stability.

<Crosslinking agent (D)>
The positive photosensitive resin composition preferably contains a cross-linking agent (D) that catalytically accelerates the cross-linking reaction between the base polymer (A) and the polyfunctional vinyl ether monomer (B). The cross-linking agent (D) is not particularly limited as long as it is a compound capable of promoting the cross-linking reaction described above. A preferred cross-linking agent (D) is a compound having a phenolic hydroxyl group.
Components other than the cross-linking agent (D), such as the base polymer (A), the polyfunctional vinyl ether monomer (B), the acid generator (C), and the photosensitizer (G), may have phenolic hydroxyl groups. . In this case, even if the positive photosensitive resin composition does not contain the cross-linking agent (D), the cross-linking reaction between the base polymer (A) and the polyfunctional vinyl ether monomer (B) is promoted.
In addition, the sulfur-containing compound (E), which will be described later, also catalytically promotes the cross-linking reaction between the base polymer (A) and the polyfunctional vinyl ether monomer (B).
Compounds having a phenolic hydroxyl group are described below.

A compound having a phenolic hydroxyl group is a compound having one or more phenolic hydroxyl groups. Phenols as compounds having a phenolic hydroxyl group are described below.

Phenols are not particularly limited as long as they are compounds having a phenolic hydroxyl group. Phenols may have an aliphatic group as long as they have a phenolic hydroxyl group. The number of phenolic hydroxyl groups that the phenols have in one molecule is not particularly limited. The number of phenolic hydroxyl groups in one molecule of the phenol is, for example, 1 or more and 6 or less, preferably 1 or more and 4 or less.

Preferred specific examples of phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol and p-butylphenol. , 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethylphenol, 3,4, Gallic acid esters such as 5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglucinol, 4,4'-dihydroxybiphenyl, bisphenol A, gallic acid, methyl gallate and ethyl gallate , α-naphthol, and β-naphthol.

The amount of the compound having a phenolic hydroxyl group is not particularly limited as long as the object of the present invention is not impaired. The amount of the compound having a phenolic hydroxyl group to be used depends on the mass of the base polymer (A), since it has a good effect of promoting the cross-linking reaction between the base polymer (A) and the polyfunctional vinyl ether monomer (B). On the other hand, it is 10 mass ppm or more and 20 mass % or less, preferably 100 mass ppm or more and 15 mass % or less, and particularly preferably 200 mass ppm or more and 10 mass % or less.

<Sulfur-containing compound (E)>
The positive photosensitive resin composition preferably contains a sulfur-containing compound (E). A sulfur-containing compound (E) is a compound containing a sulfur atom capable of coordinating to a metal. In addition, regarding compounds that can produce two or more tautomers, if at least one tautomer contains a sulfur atom that coordinates to the metal that constitutes the metal layer, the compound corresponds to a sulfur-containing compound. .
When forming a resist pattern used as a mold for plating on a surface made of a metal such as Cu, problems in the cross-sectional shape such as footing are likely to occur. However, when the positive photosensitive resin composition contains the sulfur-containing compound (E), even when a resist pattern is formed on the metal surface of the substrate, it is easy to suppress the occurrence of cross-sectional defects such as footing. .

Sulfur atoms that can coordinate to metals include, for example, a mercapto group (-SH), a thiocarboxy group (-CO-SH), a dithiocarboxy group (-CS-SH), and a thiocarbonyl group (-CS-). etc. are included in sulfur-containing compounds.
It is preferable that the sulfur-containing compound has a mercapto group because it is easily coordinated to the metal and has an excellent effect of suppressing footing.

（式中、Ｒ^ｅ１及びＲ^ｅ２は、それぞれ独立に水素原子又はアルキル基を示し、Ｒ^ｅ３は単結合又はアルキレン基を示し、Ｒ^ｅ４は炭素以外の原子を含んでいてもよいｕ価の脂肪族基を示し、ｕは２以上４以下の整数を示す。） Preferred examples of sulfur-containing compounds having a mercapto group include compounds represented by the following formula (e1).

(Wherein, R ^e1 and R ^e2 each independently represent a hydrogen atom or an alkyl group, R ^e3 represents a single bond or an alkylene group, and R ^e4 represents a u-valent aliphatic which may contain an atom other than carbon. group group, and u is an integer of 2 or more and 4 or less.)

When R ^e1 and R ^e2 are alkyl groups, the alkyl groups may be linear or branched, preferably linear. When R ^e1 and R ^e2 are alkyl groups, the number of carbon atoms in the alkyl group is not particularly limited as long as the object of the present invention is not impaired. The number of carbon atoms in the alkyl group is preferably 1 or more and 4 or less, particularly preferably 1 or 2, and most preferably 1. As for the combination of R ^e1 and R ^e2 , one is preferably a hydrogen atom and the other is an alkyl group, and one is particularly preferably a hydrogen atom and the other is a methyl group.

When R ^e3 is an alkylene group, the alkylene group may be linear or branched, preferably linear. When R ^e3 is an alkylene group, the number of carbon atoms in the alkylene group is not particularly limited as long as the object of the present invention is not impaired. The number of carbon atoms in the alkylene group is preferably 1 or more and 10 or less, more preferably 1 or more and 5 or less, particularly preferably 1 or 2, and most preferably 1.

R ^e4 is a divalent to tetravalent aliphatic group which may contain an atom other than carbon. Atoms other than carbon that R ^e4 may contain include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, and the like. The structure of the aliphatic group represented by R ^e4 may be linear, branched, cyclic, or a combination of these structures.

（式（ｅ２）中、Ｒ^ｅ４及びｕは、式（ｅ１）と同意である。） Among the compounds represented by the formula (e1), compounds represented by the following formula (e2) are more preferable.

(In formula (e2), R ^e4 and u are the same as in formula (e1).)

Among the compounds represented by formula (e2) above, the following compounds are preferred.

（式（ｅ３－Ｌ１）～（ｅ３－Ｌ７）中、Ｒ’、ｓ”、Ａ”、及びｒは、アクリル樹脂（Ｂ３）について前述した、式（ａ－Ｌ１）～（ａ－Ｌ７）と同様である。） Compounds represented by the following formulas (e3-L1) to (e3-L7) are also preferred examples of sulfur-containing compounds having a mercapto group.

(In the formulas (e3-L1) to (e3-L7), R′, s″, A″, and r are the formulas (a-L1) to (a-L7) described above for the acrylic resin (B3). It is the same.)

Preferable specific examples of the mercapto compounds represented by the above formulas (e3-L1) to (e3-L7) include the following compounds.

（式（ｅ３－１）～（ｅ３－４）中の略号の定義については、アクリル樹脂（Ａ３）に関して前述した、式（３－１）～（３－４）について前述した通りである。） Compounds represented by the following formulas (e3-1) to (e3-4) are also preferred examples of sulfur-containing compounds having a mercapto group.

(The definitions of the abbreviations in the formulas (e3-1) to (e3-4) are as described above for the formulas (3-1) to (3-4) for the acrylic resin (A3).)

Preferred specific examples of the mercapto compounds represented by formulas (e3-1) to (e3-4) above include the following compounds.

（式（ｅ４）において、Ｒ^ｅ５は、水酸基、炭素原子数１以上４以下のアルキル基、炭素原子数１以上４以下のアルコキシ基、炭素数１以上４以下のアルキルチオ基、炭素数１以上４以下のヒドロキシアルキル基、炭素数１以上４以下のメルカプトアルキル基、炭素数１以上４以下のハロゲン化アルキル基及びハロゲン原子からなる群より選択される基であり、ｋ１は０以上３以下の整数であり、ｋ０は０以上３以下の整数であり、ｋ１が２又は３である場合、Ｒ^ｅ５は同一であっても異なっていてもよい。） Moreover, suitable examples of compounds having a mercapto group include compounds represented by the following formula (e4).

(In formula (e4), R ^e5 is a hydroxyl group, an alkyl group having 1 to 4 carbon atoms, an alkoxy group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, an alkylthio group having 1 to 4 carbon atoms, A group selected from the group consisting of the following hydroxyalkyl groups, mercaptoalkyl groups having 1 to 4 carbon atoms, halogenated alkyl groups having 1 to 4 carbon atoms and halogen atoms, and k1 is an integer of 0 to 3 and k0 is an integer of 0 or more and 3 or less, and when k1 is 2 or 3, ^Re5 may be the same or different.)

Specific examples of when R ^e5 is an alkyl group optionally having a hydroxyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group and an isobutyl group. groups, sec-butyl groups, and tert-butyl groups. Among these alkyl groups, methyl group, hydroxymethyl group and ethyl group are preferred.

Specific examples of R ^e5 being an alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, n-propyloxy, isopropyloxy, n-butyloxy, isobutyloxy, sec-butyloxy and tert-butyloxy groups. Among these alkoxy groups, a methoxy group and an ethoxy group are preferred, and a methoxy group is more preferred.

Specific examples of R ^e5 being an alkylthio group having 1 to 4 carbon atoms include methylthio, ethylthio, n-propylthio, isopropylthio, n-butylthio, isobutylthio and sec-butylthio. , and tert-butylthio groups. Among these alkylthio groups, a methylthio group and an ethylthio group are preferred, and a methylthio group is more preferred.

Specific examples of R ^e5 being a hydroxyalkyl group having 1 to 4 carbon atoms include a hydroxymethyl group, a 2-hydroxyethyl group, a 1-hydroxyethyl group, a 3-hydroxy-n-propyl group, and 4 -hydroxy-n-butyl group and the like. Among these hydroxyalkyl groups, hydroxymethyl group, 2-hydroxyethyl group and 1-hydroxyethyl group are preferred, and hydroxymethyl group is more preferred.

Specific examples of R ^e5 being a mercaptoalkyl group having 1 to 4 carbon atoms include a mercaptomethyl group, a 2-mercaptoethyl group, a 1-mercaptoethyl group, a 3-mercapto-n-propyl group, and 4 -Mercapto-n-butyl group and the like. Among these mercaptoalkyl groups, mercaptomethyl group, 2-mercaptoethyl group and 1-mercaptoethyl group are preferred, and mercaptomethyl group is more preferred.

When R ^e5 is a halogenated alkyl group having 1 to 4 carbon atoms, examples of the halogen atom contained in the halogenated alkyl group include fluorine, chlorine, bromine and iodine. Specific examples of the case where R ^e5 is a halogenated alkyl group having 1 to 4 carbon atoms include a chloromethyl group, a bromomethyl group, an iodomethyl group, a fluoromethyl group, a dichloromethyl group, a dibromomethyl group, a difluoromethyl group, trichloromethyl group, tribromomethyl group, trifluoromethyl group, 2-chloroethyl group, 2-bromoethyl group, 2-fluoroethyl group, 1,2-dichloroethyl group, 2,2-difluoroethyl group, 1-chloro- 2-fluoroethyl group, 3-chloro-n-propyl group, 3-bromo-n-propyl group, 3-fluoro-n-propyl group, 4-chloro-n-butyl group and the like. Among these halogenated alkyl groups, chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trichloromethyl group, tribromomethyl group and trifluoromethyl group is preferred, and chloromethyl group, dichloromethyl group, trichloromethyl group and trifluoromethyl group are more preferred.

Specific examples of R ^e5 being a halogen atom include fluorine, chlorine, bromine, and iodine.

In formula (e4), k1 is an integer of 0 or more and 3 or less, and 1 is more preferable. When k1 is 2 or 3, multiple ^Re5 may be the same or different.

In the compound represented by formula (e4), the substitution position of ^Re5 on the benzene ring is not particularly limited. The substitution position of R ^e5 on the benzene ring is preferably meta or para with respect to the bonding position of —(CH ₂ ) _k0 —SH.

The compound represented by formula (e4) is preferably a compound having at least one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as R ^e5 , and R ^e5 is an alkyl More preferred are compounds having one group selected from the group consisting of groups, hydroxyalkyl groups, and mercaptoalkyl groups. When the compound represented by formula (e4) has one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as R ^e5 , an alkyl group, a hydroxyalkyl group, or a mercaptoalkyl group The substitution position on the benzene ring of the group is preferably meta or para to the bonding position of —(CH ₂ ) _k0 —SH, more preferably para.

In formula (e4), k0 is an integer of 0 or more and 3 or less. k0 is preferably 0 or 1, more preferably 0, because of ease of compound preparation and availability.

Specific examples of the compound represented by formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4-(methylthio)benzenethiol, 4-methoxybenzenethiol, 3-methoxybenzenethiol, 4-ethoxybenzenethiol, 4-isopropyloxybenzenethiol, 4-tert-butoxybenzenethiol, 3,4-dimethoxybenzenethiol, 3,4,5-trimethoxybenzenethiol, 4-ethylbenzenethiol, 4-isopropylbenzenethiol , 4-n-butylbenzenethiol, 4-tert-butylbenzenethiol, 3-ethylbenzenethiol, 3-isopropylbenzenethiol, 3-n-butylbenzenethiol, 3-tert-butylbenzenethiol, 3,5-dimethylbenzene Thiol, 3,4-dimethylbenzenethiol, 3-tert-butyl-4-methylbenzenethiol, 3-tert-4-methylbenzenethiol, 3-tert-butyl-5-methylbenzenethiol, 4-tert-butyl- 3-methylbenzenethiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol, 4-(mercaptomethyl)phenol, 3-(mercaptomethyl)phenol, 1,4-di(mercaptomethyl)phenol, 1,3-di (mercaptomethyl)phenol, 4-fluorobenzenethiol, 3-fluorobenzenethiol, 4-chlorobenzenethiol, 3-chlorobenzenethiol, 4-bromobenzenethiol, 4-iodobenzenethiol, 3-bromobenzenethiol, 3,4- dichlorobenzenethiol, 3,5-dichlorobenzenethiol, 3,4-difluorobenzenethiol, 3,5-difluorobenzenethiol, 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3, 5-di-tert-butyl-4-methoxybenzenethiol, 4-bromo-3-methylbenzenethiol, 4-(trifluoromethyl)benzenethiol, 3-(trifluoromethyl)benzenethiol, 3,5-bis( trifluoromethyl)benzenethiol, 4-methylthiobenzenethiol, 4-ethylthiobenzenethiol, 4-n-butylthiobenzenethiol, 4-tert-butylthiobenzenethiol, and the like.

Moreover, suitable examples of compounds having a mercapto group include compounds represented by the following formula (e5).

（式（ｅ５）中、Ａ^ｅは１以上の置換基を有してもよく、ヘテロ原子を含んでいてもよい、（ｍ０＋ｍ１）価の脂肪族環式基であり、Ｒ^ｅ１０は、水素原子、炭化水素基、又は酸解離性基であり、ｍ１は１以上４以下の整数であり、ｍ０が１又は２であり、Ｒ^ｅ１０の少なくとも１つは、水素原子、又は酸解離性基である。）

(In formula (e5), A ^e is a (m0+m1)-valent aliphatic cyclic group which may have one or more substituents and may contain a heteroatom, and R ^e10 is a hydrogen atom , a hydrocarbon group, or an acid-dissociable group, m1 is an integer of 1 or more and 4 or less, m0 is 1 or 2, and at least one of R ^e10 is a hydrogen atom or an acid-dissociable group. .)

（式（ｅ５－１）中、Ｒ^ｅ１１は、水素原子、炭化水素基、又は酸解離性基であり、Ｒ^ｅ１２、及びＲ^ｅ１６は、それぞれ独立に水素原子、又はアルキル基であるか、又はＲ^ｅ１２とＲ^ｅ１６とが、互いに結合して－Ｏ－、－Ｓ－、－ＣＨ_２－、及び－Ｃ（ＣＨ_３）_２－からなる群より選択される２価基を形成してもよく、Ｒ^ｅ１３、Ｒ^ｅ１４、Ｒ^ｅ１５、Ｒ^ｅ１７は、それぞれ独立に水素原子、又はメルカプト基であり、Ｒ^ｅ１９は、水素原子、炭化水素基、又は酸解離性基であり、Ｒ^ｅ１１、及び^Ｒｅ１９の少なくとも一方は、水素原子、又は酸解離性基であり、Ｒ^ｅ１３、Ｒ^ｅ１４、Ｒ^ｅ１５、及びＲ^ｅ１７の少なくとも１つはメルカプト基である。）
で表されるメルカプト化合物が好ましい。 As the mercapto compound represented by the above formula (e5), the following formula (e5-1):

(In formula (e5-1), R ^e11 is a hydrogen atom, a hydrocarbon group, or an acid-dissociable group, and R ^e12 and R ^e16 are each independently a hydrogen atom or an alkyl group, or R ^e12 and R ^e16 may combine with each other to form a divalent group selected from the group consisting of —O—, —S—, —CH ₂ —, and —C(CH ₃ ) ₂ — , R ^e13 , R ^e14 , R ^e15 and R ^e17 are each independently a hydrogen atom or a mercapto group, R ^e19 is a hydrogen atom, a hydrocarbon group or an acid dissociable group, R ^e11 and ^Re19 is a hydrogen atom or an acid-labile group, and at least one of R ^e13 , R ^e14 , R ^e15 and R ^e17 is a mercapto group.)
A mercapto compound represented by is preferred.

Preferable specific examples of the compound represented by formula (e5-1) include the following compounds.

Examples of sulfur-containing compounds having a mercapto group include compounds containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group, and tautomers of compounds containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group. be done.
Preferred specific examples of nitrogen-containing aromatic heterocycles include imidazole, pyrazole, 1,2,3-triazole, 1,2,4-triazole, oxazole, thiazole, pyridine, pyrimidine, pyridazine, pyrazine, 1,2, 3-triazine, 1,2,4-triazine, 1,3,5-triazine, indole, indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinoline, cinnoline, phthalazine, quinazoline, quinoxaline, and 1,8-naphthyridine.

Specific examples of nitrogen-containing heterocyclic compounds suitable as sulfur-containing compounds and suitable tautomers of nitrogen-containing heterocyclic compounds include the following compounds.

When the positive photosensitive resin composition contains the sulfur-containing compound (E), the amount used is preferably 0.01 parts by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the base polymer (A). 02 parts by mass or more and 3 parts by mass or less is more preferable, and 0.05 parts by mass or more and 2 parts by mass or less is particularly preferable.

<Acid diffusion control agent (F)>
The positive photosensitive resin composition may further contain an acid diffusion control agent (F) in order to improve the shape of the resist pattern used as a template and the storage stability of the positive photosensitive resin film. preferable. As the acid diffusion controller (F), a nitrogen-containing compound (F1) is preferable, and if necessary, an organic carboxylic acid, or an oxoacid of phosphorus or a derivative thereof (F2) can be contained.

[Nitrogen-containing compound (F1)]
Nitrogen-containing compounds (F1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine, tribenzylamine, diethanolamine, triethanolamine, and n-hexylamine. , n-heptylamine, n-octylamine, n-nonylamine, ethylenediamine, N,N,N',N'-tetramethylethylenediamine, tetramethylenediamine, hexamethylenediamine, 4,4'-diaminodiphenylmethane, 4,4 '-diaminodiphenyl ether, 4,4'-diaminobenzophenone, 4,4'-diaminodiphenylamine, formamide, N-methylformamide, N,N-dimethylformamide, acetamide, N-methylacetamide, N,N-dimethylacetamide, propion Amide, benzamide, pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benz imidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 2,4,6-tri(2-pyridyl)-S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4- dimethylpiperazine, 1,4-diazabicyclo[2.2.2]octane, pyridine, 2,6-di-tert-butylpyridine, 2,6-diphenylpyridine, 2,4,6-triphenylpyridine, etc. and substituted pyridines. Also, tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate, 1,2,3,4-butanetetracarboxylic acid and 1,2, 2,6,6,-pentamethyl-4-piperidinol and β,β,β',β'-tetramethyl-3,9-(2,4,8,10-tetraoxaspiro[5,5]undecane)- Hindered amine compounds such as condensates with diethanol and polymers of dimethyl succinate and 4-hydroxy-2,2,6,6-tetramethyl-1-piperidineethanol can also be used as the nitrogen-containing compound (E1). These may be used alone or in combination of two or more.

The nitrogen-containing compound (F1) is usually in the range of 0 parts by mass or more and 5 parts by mass or less with respect to a total of 100 parts by mass of the mass of the base polymer (A) and the mass of the polyfunctional vinyl ether compound (B). It is preferably used, and particularly preferably in the range of 0 to 3 parts by mass.

[Organic carboxylic acid, or phosphorus oxoacid or derivative thereof (F2)]
Among the organic carboxylic acids and phosphorus oxo acids or derivatives thereof (F2), malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, and the like are preferable as the organic carboxylic acids. , especially salicylic acid.

Phosphorus oxoacids or derivatives thereof include phosphoric acid, phosphoric acid such as di-n-butyl phosphate, diphenyl phosphate, and derivatives such as esters thereof; Phosphonic acids such as di-n-butyl ester, phenylphosphonic acid, diphenyl phosphonate, dibenzyl phosphonate and derivatives such as esters thereof; phosphinic acids such as phosphinic acid, phenylphosphinic acid and esters thereof; derivatives; and the like. Among these, phosphonic acid is particularly preferred. These may be used alone or in combination of two or more.

The organic carboxylic acid or phosphorus oxo acid or derivative thereof (F2) is usually 0 mass with respect to 100 parts by mass of the mass of the base polymer (A) and the mass of the polyfunctional vinyl ether compound (B). It is preferably used in the range of 0 to 5 parts by mass, and particularly preferably in the range of 0 to 3 parts by mass.

In addition, in order to form a salt and stabilize it, it is preferable to use the organic carboxylic acid, phosphorus oxoacid or derivative thereof (F2) in an amount equivalent to that of the nitrogen-containing compound (F1).

<Photosensitizer (G)>
The positive photosensitive resin composition may contain the aforementioned photosensitive agent (G).

<Organic solvent (S)>
The positive photosensitive resin composition preferably contains an organic solvent (S) for the purpose of adjusting coatability. The type of the organic solvent (S) is not particularly limited as long as it does not interfere with the object of the present invention, and can be appropriately selected from organic solvents conventionally used in positive photosensitive resin compositions and used. .

Specific examples of the organic solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate. , dipropylene glycol, dipropylene glycol monoacetate monomethyl ether, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether and other polyhydric alcohols and their derivatives; dioxane and other cyclic ethers; ethyl formate, lactic acid Methyl, ethyl lactate, methyl acetate, ethyl acetate, butyl acetate, methyl pyruvate, methyl acetoacetate, ethyl acetoacetate, ethyl pyruvate, ethyl ethoxyacetate, methyl methoxypropionate, ethyl ethoxypropionate, methyl 2-hydroxypropionate , ethyl 2-hydroxypropionate, ethyl 2-hydroxy-2-methylpropionate, methyl 2-hydroxy-3-methylbutanoate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, and other esters; toluene , aromatic hydrocarbons such as xylene; and the like. These may be used alone or in combination of two or more.

The content of the organic solvent (S) is not particularly limited as long as the object of the present invention is not impaired. When the positive photosensitive resin composition is used for a thick film application in which the film thickness of the photosensitive resin layer obtained by a spin coating method or the like is 10 μm or more, the solid content concentration of the positive photosensitive resin composition is It is preferable to use the organic solvent (S) within a range of preferably 20 parts by mass or more and 80% by mass or less, more preferably 30% by mass or more and 70% by mass or less.

<Other ingredients>
The positive photosensitive resin composition may further contain a polyvinyl resin in order to improve plasticity. Specific examples of polyvinyl resins include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, and copolymers thereof. . The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition point.

In addition, the positive photosensitive resin composition may further contain an adhesion aid in order to improve the adhesion between the mold formed using the positive photosensitive resin composition and the metal substrate.

The positive photosensitive resin composition may further contain a surfactant in order to improve coating properties, defoaming properties, leveling properties, and the like. As the surfactant, for example, fluorine-based surfactants and silicone-based surfactants are preferably used.
Specific examples of fluorosurfactants include BM-1000, BM-1100 (all manufactured by BM Chemie), Megafac F142D, Megafac F172, Megafac F173, and Megafac F183 (all from Dainippon Ink and Chemicals). company), Florado FC-135, Florado FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surflon S-112, Surfon S-113, Surfon S-131, Surfon S- 141, Surflon S-145 (both manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (both manufactured by Toray Silicone Co., Ltd.) and other commercially available fluorine-based surfactants include, but are not limited to.

Examples of silicone-based surfactants include unmodified silicone-based surfactants, polyether-modified silicone-based surfactants, polyester-modified silicone-based surfactants, alkyl-modified silicone-based surfactants, aralkyl-modified silicone-based surfactants, and A reactive silicone surfactant or the like can be preferably used.
A commercially available silicone surfactant can be used as the silicone surfactant. Specific examples of commercially available silicone surfactants include Paintad M (manufactured by Dow Corning Toray Co., Ltd.), Topica K1000, Topica K2000, Topica K5000 (all manufactured by Takachiho Sangyo Co., Ltd.), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), BYK-310 (polyester-modified silicone surfactant, manufactured by BYK-Chemie), and the like.

The positive photosensitive resin composition may further contain an acid, an acid anhydride, or a high-boiling solvent in order to finely adjust the solubility in the developer.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; lactic acid, 2-hydroxybutyric acid, Hydroxymonocarboxylic acids such as 3-hydroxybutyric acid; oxalic acid, succinic acid, glutaric acid, adipic acid, maleic acid, itaconic acid, hexahydrophthalic acid, phthalic acid, isophthalic acid, terephthalic acid, 1,2-cyclohexanedicarboxylic acid , 1,2,4-cyclohexanetricarboxylic acid, butanetetracarboxylic acid, trimellitic acid, pyromellitic acid, cyclopentanetetracarboxylic acid, butanetetracarboxylic acid, 1,2,5,8-naphthalenetetracarboxylic acid and the like. carboxylic anhydride; itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenylsuccinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1, 2, 3, 4-butanetetracarboxylic anhydride, cyclopentanetetracarboxylic dianhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic anhydride, ethylene glycol bis anhydride trimellitate, glycerol tris anhydride trimellitate, etc. acid anhydride; and the like.

Further, specific examples of high-boiling solvents include N-methylformamide, N,N-dimethylformamide, N-methylformanilide, N-methylacetamide, N,N-dimethylacetamide, N-methylpyrrolidone, dimethylsulfoxide, benzyl Ethyl ether, dihexyl ether, acetonylacetone, isophorone, caproic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate , propylene carbonate, phenyl cellosolve acetate, and the like.

The positive photosensitive resin composition may further contain a sensitizer in order to improve sensitivity.

<Method for preparing photosensitive resin composition>
The photosensitive resin composition is prepared by mixing and stirring the above components in a usual manner. Apparatuses that can be used for mixing and stirring the above components include a dissolver, a homogenizer, a three-roll mill, and the like. After uniformly mixing the above components, the resulting mixture may be filtered using a mesh, membrane filter, or the like.

≪Photosensitive dry film≫
A photosensitive dry film has a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer is made of the aforementioned photosensitive resin composition.

As the substrate film, a film having optical transparency is preferable. Specifically, a polyethylene terephthalate (PET) film, a polypropylene (PP) film, a polyethylene (PE) film, etc. are mentioned. A polyethylene terephthalate (PET) film is preferred because it has an excellent balance of light transmittance and breaking strength.

A photosensitive dry film is produced by applying the aforementioned photosensitive resin composition onto a substrate film to form a photosensitive resin layer.
When the photosensitive resin layer is formed on the base film, an applicator, bar coater, wire bar coater, roll coater, curtain flow coater, etc. are used to form the layer so that the film thickness after drying on the base film is preferably 0.5. The photosensitive resin composition is applied to a thickness of 5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, particularly preferably 3 μm or more and 100 μm or less, and dried.

The photosensitive dry film may further have a protective film on the photosensitive resin layer. Examples of the protective film include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, and the like.

<<Method for manufacturing patterned resist film and substrate with template>>
A method for forming a patterned resist film on a metal surface of a substrate having a metal surface using the photosensitive resin composition described above is not particularly limited. Such a patterned resist film is suitably used as a mold for forming a plated model.
A suitable method is
A lamination step of laminating a photosensitive resin layer made of a photosensitive resin composition on the metal surface of a substrate having a metal surface;
an exposure step of exposing the photosensitive resin layer by position-selectively irradiating it with actinic rays or radiation;
A developing step of developing the photosensitive resin layer after exposure;
A patterned resist film containing
A method for manufacturing a template-equipped substrate having a template for forming a plated model includes, in a development step, preparing a template for forming the plated model by development, and manufacturing a patterned resist film. Similar to the method.

The substrate on which the photosensitive resin layer is laminated is not particularly limited, and conventionally known substrates can be used. be able to. A substrate having a metal surface is used as the substrate, and the metal species constituting the metal surface is preferably copper, gold or aluminum, more preferably copper.

The photosensitive resin layer is laminated on the substrate, for example, as follows. Specifically, a liquid photosensitive resin composition is applied onto a substrate, and the solvent is removed by heating to form a photosensitive resin layer having a desired thickness. The thickness of the photosensitive resin layer is not particularly limited as long as a resist pattern to be a template can be formed with a desired thickness. The thickness of the photosensitive resin layer is not particularly limited, but is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, particularly preferably 1 μm or more and 150 μm or less, and most preferably 3 μm or more and 100 μm or less.

Methods such as spin coating, slit coating, roll coating, screen printing, and applicator methods can be employed as methods for applying the photosensitive resin composition onto the substrate. It is preferable to pre-bake the photosensitive resin layer. Pre-baking conditions vary depending on the type of each component in the photosensitive resin composition, the mixing ratio, the coating film thickness, etc., but are usually 70° C. or higher and 200° C. or lower, preferably 80° C. or higher and 150° C. or lower, for 2 minutes or more. About 120 minutes or less.

The photosensitive resin layer formed as described above is selectively irradiated (exposure) with actinic rays or radiation such as ultraviolet rays or visible rays having a wavelength of 300 nm or more and 500 nm or less through a mask of a predetermined pattern. be done.

Low-pressure mercury lamps, high-pressure mercury lamps, ultra-high-pressure mercury lamps, metal halide lamps, argon gas lasers, and the like can be used as radiation sources. Radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays, electron beams, proton beams, neutron beams, ion beams, and the like. Although the dose of radiation varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive resin layer, and the like, it is 100 mJ/cm ² or more and 10000 mJ/cm ² or less when using an ultra-high pressure mercury lamp, for example. Radiation also includes light rays that activate the acid generator (A) to generate acid.

After the exposure, the photosensitive resin layer is heated by a known method to promote the diffusion of the acid, thereby changing the alkali solubility of the photosensitive resin layer in the exposed portions of the photosensitive resin film. .

Then, the exposed photosensitive resin layer is developed according to a conventionally known method, and the insoluble portion is dissolved and removed to form a mold for forming a predetermined resist pattern or a plated model. At this time, an alkaline aqueous solution is used as the developer.

Examples of the developer include sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, aqueous ammonia, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyldiethylamine, dimethylethanolamine, triethanolamine, tetramethylammonium hydroxide, tetraethylammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3, Aqueous solutions of alkalis such as 0]-5-nonane can be used. Further, an aqueous solution prepared by adding an appropriate amount of a water-soluble organic solvent such as methanol or ethanol or a surfactant to the aqueous solution of the above alkalis can be used as a developer.

The development time varies depending on the composition of the photosensitive resin composition, the film thickness of the photosensitive resin layer, etc., but is usually between 1 minute and 30 minutes. The developing method may be any of a liquid-filling method, a dipping method, a puddle method, a spray developing method, and the like.

After development, washing with running water is performed for 30 seconds or more and 90 seconds or less, and drying is performed using an air gun, an oven, or the like. Thus, a resist pattern patterned into a desired shape is formed on the metal surface of the substrate having the metal surface. Moreover, in this way, a substrate with a template provided with a resist pattern serving as a template on the metal surface of a substrate having a metal surface can be manufactured.

≪Manufacturing method of plated model≫
A plated shaped article is manufactured by plating the substrate with the template manufactured by the above method. Specifically, by embedding a conductor such as a metal by plating in the non-resist part (the part removed by the developer) in the mold of the substrate with the mold formed by the above method, for example, bumps and metal posts It is possible to form a plated shaped article such as a connection terminal such as. The plating method is not particularly limited, and conventionally known various methods can be employed. Solder plating, copper plating, gold plating, and nickel plating solutions are particularly suitable as the plating solution. The remaining template is finally removed using a stripping solution or the like according to conventional methods.

EXAMPLES The present invention will be described in more detail below with reference to Examples, but the present invention is not limited to these Examples.

[Preparation Example 1]
(Synthesis of resin (A))
91.8 g of methoxybutyl acetate was added to a three-necked flask equipped with a condenser tube and a nitrogen inlet tube and heated to 80°C.
Separately, 70.0 g of ethyl cyclohexyl acrylate (ECHA), 10.0 g of methacrylic acid (MA), 14.0 g of n-butyl acrylate (n-BA), 46.0 g of dicyclopentanyl methacrylate (DCPMA), 60.0 g of tetrahydrofurfuryl acrylate (THFA) and 24.9 g of initiator V-601HP (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) were dissolved in 252 g of methoxybutyl acetate to prepare a dropping solution.
The prepared dropping solution was added dropwise to the three-necked flask over 3 hours. After the dropwise addition was completed, the mixture was stirred for 3 hours while maintaining the temperature at 80°C. Reprecipitation with methanol gave 101.3 g of resin P1. By dissolving this in methoxybutyl acetate, a solution of resin P1 having a solid component concentration of 70% was obtained.
The mass average molecular weight of the obtained resin P1 was Mw 10,600.

[Preparation Examples 2 to 8]
Resins P2 to P8 shown in Table 1 below were synthesized in the same manner as in Preparation Example 1, except that the composition of the monomer was changed to that shown in Table 1 below.

ｎ－ＢＭＡ：ブチルメタクリレート
ＧＢＬＡ：γ－ブチロラクトンメタクリレート

n-BMA: butyl methacrylate GBLA: γ-butyrolactone methacrylate

[Preparation Example 9]
10 g of biphenyl-4,4′-dicarboxylic acid, 24.35 g of 1-ethyl-3-(3-dimethylaminopropyl)carbodiimide hydrochloride, 0.1 g of N,N-dimethyl-4-aminopyridine, and ethylene glycol monovinyl ether 10 g was stirred in 40 g of methylene chloride at room temperature for 24 hours under a nitrogen atmosphere. Then, after washing the reaction liquid with 50 g of pure water five times, the solvent was distilled off from the washed reaction liquid to obtain a crude product. The resulting crude product was recrystallized with methylene chloride to obtain 4.38 g of VE2 below, which is a polyfunctional vinyl ether monomer (B).
The results of ¹ H-NMR measurement of VE2 were as follows. ¹ H-NMR: cation δ (ppm) = 8.08 (4H, d), 7.92 (4H, d), 6.57 (2H, dd), 4.53 (4H, t), 4.28 (2H, d), 4.04 (6H, m)

[Preparation Example 10]
In the same manner as in Preparation Example 9, except that 10 g of biphenyl-4,4'-dicarboxylic acid was changed to 10 g of biphenyl-4,4'-dicarboxylic acid and equimolar stilbene-4,4'-dicarboxylic acid. The following VE3, which is a polyfunctional vinyl ether monomer (B), was obtained.
The measurement results of ¹ H-NMR of VE3 were as follows. ¹ H-NMR: cation δ (ppm) = 7.98 (4H, d), 7.75 (4H, d), 7.50 (2H, s), 6.57 (2H, dd), 4.50 (4H, t), 4.24 (2H, d), 4.04 (6H, m)

[Examples 1 to 14 and Comparative Examples 1 to 16]
In Examples and Comparative Examples, VE1 to VE4 below were used as the polyfunctional vinyl ether monomer (B) (component (B)). As VE1, the following compound synthesized by the method described in Journal of Materials Chemistry, Volume 19, Issue 24, Pages 4085-4087 was used.

In Examples and Comparative Examples, the following PAG1 to PAG4 were used as the acid generator (C) (component (C)) that generates an acid upon exposure to actinic rays or radiation.

In Examples and Comparative Examples, hydroquinone monomethyl ether, which is a compound having a phenolic hydroxyl group, was used as the cross-linking agent (D) (component (D)).

In Examples and Comparative Examples, the following compounds were used as the sulfur-containing compound (E).

In the examples and comparative examples, the following E1 to E4 were used as the acid diffusion control agent (F) (component (F)).
E1: tri-n-pentylamine E2: tetrakis(1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butane tetracarboxylate E3: 2,6-diphenylpyridine E4: 2,4,6-triphenylpyridine

100 parts by mass of the base polymer (A) of the type shown in Table 2, the polyfunctional vinyl ether monomer (B) of the type and amount shown in Table 2, and the acid generator (C) of the type and amount shown in Table 2 ), hydroquinone monomethyl ether as a crosslinking agent (D) in the amount shown in Table 2, a sulfur-containing compound (E) in the amount shown in Table 2, and an acid diffusion controller in the type and amount shown in Table 2. (F) and 0.05 parts by mass of a surfactant (BYK310, manufactured by BYK-Chemie) are uniformly mixed and dissolved in 3-methoxybutyl acetate so that the solid content concentration is 60% by mass. Photosensitive resin compositions of Examples and Comparative Examples were obtained.

Using the obtained photosensitive resin compositions of Examples and Comparative Examples, crack resistance and plating resistance were evaluated according to the following methods. These evaluation results are shown in Table 2.

<Crack resistance evaluation>
The photosensitive resin composition of each example and comparative example was applied onto a copper substrate having a diameter of 8 inches to form a photosensitive resin layer having a thickness of 55 μm. The photosensitive resin layer was then pre-baked at 140° C. for 5 minutes. After pre-baking, using a square pattern mask with a diameter of 30 μm and an exposure apparatus Prisma GHI (manufactured by Ultratech), at an exposure amount that forms a pattern of a predetermined size (the CD of the top of the resist pattern is 35 μm), It was pattern-exposed with ghi rays. The substrate was then placed on a hot plate and subjected to post-exposure baking (PEB) at 100° C. for 3 minutes. Thereafter, a 2.38% by weight aqueous solution of tetramethylammonium hydroxide (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is added dropwise to the exposed photosensitive resin layer, followed by standing at 23° C. for 60 seconds. was repeated four times in total. Thereafter, the surface of the resist pattern was washed with running water and then blown with nitrogen to obtain a resist pattern. This resist pattern was observed with a scanning electron microscope to observe the presence or absence of cracks.
A case where cracks were observed was evaluated as x, and a case where cracks were not observed was evaluated as ◯.

<Plating resistance evaluation>
The resist pattern formed in the crack resistance evaluation is immersed in a copper sulfate plating solution at 28 ° C. for 1 hour, and then the CD of the top of the resist pattern is measured. A case where the variation with respect to the CD of the top of the pattern was ±5% or more was determined as x, and a case where the above-mentioned variation was less than ±5% was determined as ◯.

From Table 2, a photosensitive resin of an example containing a base polymer (A) having a carboxy group and/or a hydroxyl group and a polyfunctional vinyl ether monomer (B) having a predetermined structure represented by formula (B1) It can be seen that the composition can suppress the occurrence of cracks and form a resist pattern whose shape does not easily change even when it comes into contact with a plating solution under plating conditions.
On the other hand, from the comparative examples, even if the photosensitive resin composition contains the base polymer (A) having a carboxyl group and/or a hydroxyl group, it does not contain the polyfunctional vinyl ether monomer (B) or has the formula (B1 ) contains a polyfunctional vinyl ether monomer (B) having a structure that does not correspond to the structure represented by ), a photosensitive resin composition that is excellent in both crack resistance and plating resistance cannot be obtained.

Claims (10)

Containing a base polymer (A) and a polyfunctional vinyl ether monomer (B),
The base polymer (A) has a carboxy group and/or a hydroxyl group,
The polyfunctional vinyl ether monomer (B) has the following formula (B1):
R ^B —(—R ^b1 —O—CH═CH ₂ ) _n1 (B1)
including a compound represented by
In the formula (B1), R ^B is a monovalent linking group containing a monocyclic skeleton and/or a condensed cyclic skeleton in which two or more monocyclic rings are condensed, and the number of monocyclic skeletons in R ^B and the number of single rings constituting the condensed cyclic skeleton is 2 or more, R ^b1 is a single bond or a divalent linking group, and two or more R ^b1 are the same or different n1 is an integer of 2 or more,
The compound represented by the formula (B1) is represented by the following formula (B2):
R ^B —(—R ^b2 —R ^b3 —O—CH=CH ₂ ) _n1 (B2)
is a compound represented by
In formula (B2), R ^B and n1 are the same as in formula (B1), R ^b2 is an ester bond, and R ^b3 is a divalent hydrocarbon group. Photosensitive resin composition used in. containing an acid generator (C) that generates an acid upon exposure to actinic rays or radiation,
2. The photosensitive resin composition according to claim 1, wherein the base polymer (A) is a resin (C1) whose alkali solubility increases under the action of an acid. The photosensitive resin composition according to claim 2, wherein the base polymer (A) contains a (meth)acrylic polymer (A3). The photosensitive resin composition according to claim 2 or 3, comprising an acid diffusion controller (F). 2. The photosensitive resin composition according to claim 1, comprising a photosensitive agent (G) having a quinonediazide group. The compound represented by the formula (B2) is represented by the following formula (B3):
R ^B1 —(—CO—OR ^b3 —O—CH=CH ₂ ) _n2 (B3)
is a compound represented by
In the above formula (B3), R ^b3 is the same as in the above formula (B2), n2 is an integer of 2 or more and 4 or less, and R ^B1 is the following formulas (B3-1) to (B3-3):
-R ^B2 -R ^b4 -R ^B2 -... (B3-1)
-R ^B2 -R ^b4 -R ^B3 <... (B3-2)
>R ^B3 -R ^b4 -R ^B3 <... (B3-3)
is a linking group having a valence of 2 or more and 4 or less, represented by any one of R ^B2 is a phenylene group which may have a substituent, and R ^B3 is a benzenetriyl group which may have a substituent and R ^b4 is a single bond or a divalent linking group, the photosensitive resin composition according to any one of claims 1 to 5. It has a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer is made of the photosensitive resin composition according to any one of claims 1 to 6. photosensitive dry film. A method for producing a photosensitive dry film, comprising applying the photosensitive resin composition according to any one of claims 1 to 6 on a substrate film to form a photosensitive resin layer. A lamination step of laminating a photosensitive resin layer composed of the photosensitive resin composition according to any one of claims 1 to 6 on a substrate having a metal surface;
an exposure step of position-selectively irradiating the photosensitive resin layer with actinic rays or radiation;
and a developing step of developing the photosensitive resin layer after exposure. A lamination step of laminating a photosensitive resin layer composed of the photosensitive resin composition according to any one of claims 1 to 6 on a substrate having a metal surface;
An exposure step of irradiating the photosensitive resin layer with actinic rays or radiation;
A developing step of developing the photosensitive resin layer after exposure to prepare a substrate with a template for forming a plated modeled article;
a step of plating the substrate with the mold to form a plated model in the mold;
A method for manufacturing a plated modeled object.