JP2021032945A - Photosensitive resin composition, photosensitive dry film, production method of photosensitive dry film, production method of patterned resist film, method for manufacturing plated molded article, and polyfunctional vinyl ether compound - Google Patents

Abstract

To provide a photosensitive resin composition, from which such a resist pattern can be formed that the shape of the pattern less likely varies even in contact with a plating solution under plating conditions, while suppressing generation of cracks, a photosensitive dry film including a photosensitive resin layer made of the above photosensitive resin composition, a production method of the photosensitive dry film, a production method of a patterned resist film using the above photosensitive resin composition, a method for manufacturing a plated molded article using a substrate with a template prepared by using the above photosensitive resin composition, and a polyfunctional vinyl ether compound that can be suitably compounded in the above photosensitive resin composition.SOLUTION: A polyfunctional vinyl ether monomer (B) having a specific structure including a cyclic skeleton is incorporated into a photosensitive resin composition comprising a base polymer (A) having a carboxy group and/or a hydroxyl group.SELECTED DRAWING: None

Description

The present invention uses a photosensitive resin composition, a photosensitive dry film comprising a photosensitive resin layer composed of the photosensitive resin composition, a method for producing the photosensitive dry film, and the above-mentioned photosensitive resin composition. It can be suitably blended with a method for producing a patterned resist film, a method for producing a plated molded product using a substrate with a mold prepared by using the above-mentioned photosensitive resin composition, and the above-mentioned photosensitive resin composition. With respect to polyfunctional vinyl ether compounds.

Currently, photofabrication is the mainstream of precision microfabrication technology. Photofabrication is a method of applying a photoresist composition to the surface of a work piece to form a photoresist layer, patterning the photoresist layer by photolithography technology, and chemically etching and electrolyzing the patterned photoresist layer (photoresist pattern) as a mask. It is a general term for technologies for manufacturing various precision parts such as semiconductor packages by performing etching or electroforming mainly by electroplating.

In recent years, along with the downsizing of electronic devices, high-density mounting technology for semiconductor packages has advanced, and the packaging has become multi-pin thin film mounting, package size miniaturization, two-dimensional mounting technology by flip chip method, and three-dimensional mounting technology. Based on this, the mounting density has been improved. In such a high-density mounting technology, as connection terminals, for example, a protruding electrode (mounting terminal) such as a bump protruding on a package, or a metal post connecting a rewiring extending from a peripheral terminal on a wafer and a mounting terminal. Etc. are arranged on the substrate with high precision.

Photoresist compositions are used for photofabrication as described above, and as such photoresist compositions, chemically amplified photoresist compositions containing an acid generator are known (Patent Documents 1, 2, etc.). See). In the chemically amplified polyether composition, acid is generated from the acid generator by irradiation (exposure), the diffusion of the acid is promoted by the heat treatment, and an acid catalytic reaction is caused with the base resin or the like in the composition. The alkali solubility changes.

Such a chemically amplified positive photoresist composition is used, for example, for forming a plated object such as a bump or a metal post in a plating process. Specifically, a chemically amplified photoresist composition is used to form a photoresist layer of a desired film thickness on a support such as a metal substrate, exposed through a predetermined mask pattern, developed, and bumped. Or a photoresist pattern used as a mold in which the portion forming the metal post is selectively removed (peeled) is formed. Then, after embedding a conductor such as copper in the removed portion (non-resist portion) by plating, the bump or metal post can be formed by removing the photoresist pattern around the conductor.

Japanese Unexamined Patent Publication No. 9-176112 Japanese Unexamined Patent Publication No. 11-52562

In the photoresist composition used for forming a resist pattern that serves as a mold for forming a plated molded product such as a bump or a metal post, cracks are generated in order to stably produce a plated molded product having a desired shape. While suppressing it, 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, it is possible to form a connection terminal such as a precise bump or a metal post.

However, conventionally known phosphate compositions such as those disclosed in Patent Documents 1 and 2 are used for forming a resist pattern that serves as a template for forming plated shaped objects such as bumps and metal posts. It may not meet the above performance required for the object.

The present invention has been made in view of the above problems, and is a photosensitive resin composition capable of forming a resist pattern whose shape does not easily change even when in contact with a plating solution under plating conditions while suppressing the occurrence of cracks. A photosensitive dry film having a photosensitive resin layer composed of the photosensitive resin composition, a method for producing the photosensitive dry film, and a method for producing a patterned resist film using the above-mentioned photosensitive resin composition. To provide a method for producing a plated molded product using a substrate with a mold prepared by using the above-mentioned photosensitive resin composition, and a polyfunctional vinyl ether compound that can be suitably blended in the above-mentioned photosensitive resin composition. With the goal.

As a result of intensive studies to achieve the above object, the present inventors have identified a photosensitive resin composition containing a base polymer (A) having a carboxy group and / or a hydroxyl group, which contains a cyclic skeleton. It has been found that the above-mentioned problems can be solved by containing the polyfunctional vinyl ether monomer (B) having the structure of the above, and the present invention has been completed. Specifically, the present invention provides the following.

The first aspect of the present invention is
It contains 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 the compound represented by
In the formula (B1), R ^B is n1 divalent linking group containing a monocyclic skeleton, and / or fused cyclic skeleton in which two or more single rings condensed, the number of monocyclic skeleton in R ^B , The total number of monocycles constituting the fused cyclic skeleton is 2 or more, R ^b1 is a single bond or a divalent linking group, and 2 or more R ^b1s are different even if they are the same. It may be a photosensitive resin composition used for forming a mold for forming a plated model, in which n1 is an integer of 2 or more.

The second aspect of the present invention comprises a photosensitive resin composition having a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer comprises 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, which comprises applying the photosensitive resin composition according to the first aspect on a base film to form a photosensitive resin layer. ..

A fourth aspect of the present invention is
A laminating 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 process in which the photosensitive resin layer is regioselectively irradiated with active light rays or radiation,
A method for producing a patterned resist film, which comprises a developing step of developing a photosensitive resin layer after exposure.

A fifth aspect of the present invention is
A laminating 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 process in which the photosensitive resin layer is irradiated with active light or radiation,
A development process in which the photosensitive resin layer after exposure is developed to prepare a substrate with a mold for forming a plated model, and a development process.
The process of plating a substrate with a mold to form a plated object in the mold,
It is a manufacturing method of a plated model including.

A sixth aspect of the present invention is the following formula (B3):
R ^B1- (-CO-O-R ^b3 -O-CH = CH ₂ ) _n2 ... (B3)
Represented by
In the 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)
It is a linking group of divalent or more and tetravalent or less represented by any of the above, ^RB2 is a phenylene group which may have a substituent, and ^RB3 is a benzenetriyl group which may have a substituent. R ^b4 is a polyfunctional vinyl ether compound which is a single bond or a divalent linking group.

According to the present invention, the photosensitive resin composition comprises a photosensitive resin composition capable of forming a resist pattern whose shape does not easily change even when in contact with a plating solution under plating conditions while suppressing the occurrence of cracks. A photosensitive dry film provided with a photosensitive resin layer, a method for producing the photosensitive dry film, a method for producing a patterned resist film using the above-mentioned photosensitive resin composition, and the above-mentioned photosensitive resin composition. It is possible to provide a method for producing a plated molded product in which a plated substrate produced using the product is plated, and a polyfunctional vinyl ether compound preferably used as a component of the above-mentioned 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 for forming a mold for forming a plated model.
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)
It is a compound represented by.
In the formula (B1), R ^B is 2 or more n1 valent linking group containing a monocyclic skeleton, and / or fused cyclic skeleton in which two or more single rings condensed, R ^b1 represents a single bond, Alternatively, it is a divalent linking group, and R ^b1 of 2 or more may be the same or different, and n1 is an integer of 2 or more. It is a thing.

The mold for forming a plated model, which is formed by using the above-mentioned photosensitive resin composition, suppresses the occurrence of cracks 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 the patterned resist film used as a template for forming a plated model, many having a specific structure with the carboxy group and / or the hydroxyl group of the above-mentioned substrate polymer (A). It is considered that the above effect is obtained by causing a cross-linking reaction with the functional vinyl ether monomer (B).

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

Preferable examples of the case where the photosensitive resin composition is a negative type include a monofunctional or polyfunctional (meth) acrylate monomer in addition to the above-mentioned substrate polymer (A) and polyfunctional vinyl ether monomer (B). Examples thereof include a photosensitive resin composition containing the photopolymerizable monomer of the above and a photopolymerization initiator.

When a resist pattern is formed using such a negative photosensitive resin composition, by baking a coating film made of the photosensitive resin composition, a large number of carboxy groups and / or hydroxyl groups contained in the base polymer (A) can be obtained. The vinyloxy group of the functional vinyl ether monomer (B) reacts with each other to crosslink the molecular chain of the base polymer (A). Here, if the amount of the alkali-soluble group such as the carboxy group or the phenolic hydroxyl group contained in the base polymer (A) is set to be an excess amount than the amount of the vinyloxy group contained in the polyfunctional vinyl ether monomer (B), The crosslinked substrate polymer (A) has an alkali-soluble group. The crosslinked substrate polymer (A) exhibits alkali solubility by having an alkali-soluble group.
Then, when the coating film containing the crosslinked base material polymer (A) is exposed in a position-selective manner, the photopolymerizable monomer is polymerized by the action of the photopolymerization initiator, so that the exposed portion is insoluble in the alkaline developer. To 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 material polymer (A) is alkaline soluble.
Therefore, in addition to the above-mentioned base polymer (A) and 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 a resist pattern is formed using a negative photosensitive resin composition, a coating film made of the photosensitive resin composition is baked, and then position-selective exposure and development with an alkali developing solution are performed to make an alkali. It contains a crosslinked base polymer (A) that does not easily change its shape even when it comes into contact with the plating solution under plating conditions, while removing unexposed areas that are soluble in the developing solution and suppressing the occurrence of cracks. A resist pattern can be formed.

As a preferable example when the photosensitive resin composition is of the positive type, in addition to the above-mentioned base polymer (A) and polyfunctional vinyl ether monomer (B), an alkaline developer of the photosensitive resin composition by exposure is used. Examples thereof include a photosensitive resin composition containing a photosensitive agent (G) that enhances the solubility in a photosensitivity.

When the coating film made of the above positive photosensitive resin composition is heated, the carboxy group and / or the hydroxyl group of the base polymer (A) reacts with the vinyloxy group of the polyfunctional vinyl ether monomer (B). However, the crosslinking of the molecular chains of the base polymer (A) reduces the solubility of the photosensitive resin composition in the alkaline developing solution.
However, when the coated film after heating is exposed in a regioselective manner, the exposed portion is solubilized in the alkaline developer by the action of the photosensitizer (G).

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

The photosensitive agent (G) is a photosensitive compound that enhances the solubility of the photosensitive resin composition in an alkaline developer by a photoreaction generated in the molecule by exposure. Compounds that are solubilized in an alkaline developer by a deprotection reaction or the like due to the action of a photoacid generator or a photobase generator are not included in the photosensitizer (G). Typically, the photosensitizer (G) includes a naphthoquinone diazide group-containing compound.

Examples of the quinonediazide group-containing compound include a complete esterified product and a partially esterified product of a phenol compound and a naphthoquinonediazide sulfonic acid compound. Examples of the phenol compound include polyhydroxybenzophenone compounds such as 2,3,4-trihydroxybenzophenone and 2,3,4,4'-tetrahydroxybenzophenone; tris (4-hydroshikiphenyl) methane and 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 and bis (5-cyclohexyl-4-hydroxy-2-methylphenyl) -3,4-dihydroxyphenylmethane; 2,4-bis (3,5-dimethyl-4- Linear trinuclear phenolic compounds such as hydroxybenzyl) -5-hydroxyphenol, 2,6-bis (2,5-dimethyl-4-hydroxybenzyl) -4-methylphenol; 1,1-bis [3- (3- ( 2-Hydroxy-5-methylbenzyl) -4-hydroxy-5-cyclohexylphenyl] isopropane, bis [2,5-dimethyl-3- (4-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] meta , Bis [2,5-dimethyl-3- (4-hydroxybenzyl) -4-hydroxyphenyl] methane, bis [3- (3,5-dimethyl-4-hydroxybenzyl) -4-hydroxy-5-methyl Phenyl] 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-3-3] Linear type 4 such as (2-hydroxy-5-methylbenzyl) -5-methylphenyl] methane, bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxyphenyl] methane Nuclear phenol compound; 2,4-bis [2-hydroxy-3- (4-hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,4-bis [4-hydroxy-3- (4-hydroxybenzyl) 4-hydroxy-3- (4-hydroxybenzyl) -6-cyclohexylphenol Hydroxybenzyl) -5-methylbenzyl] -6-cyclohexylphenol, 2,6-bis [2,5-dimethyl-3- (2-hydroxy-5-methylbenzyl) -4-hydroxybenzyl] -4-methylphenol Linear polyphenol compounds such as linear pentanucleic phenol compounds such as 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'-Hi Bisphenol-type compounds such as droxyphenyl) propane, 2- (2,3,4-trihydroxyphenyl) -2- (4'-hydroxy-3', 5'-dimethylphenyl) propane; 1- [1-( 4-Hydroxyphenyl) isopropyl] -4- [1,1-bis (4-hydroxyphenyl) ethyl] benzene, 1- [1- (3-methyl-4-hydroxyphenyl) isopropyl] -4- [1,1 Polynuclear branched compounds such as −bis (3-methyl-4-hydroxyphenyl) ethyl] benzene; condensed phenol compounds such as 1,1-bis (4-hydroxyphenyl) cyclohexane and the like can be mentioned. These can be used alone or in combination of two or more.

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

It also has hydroxyl or amino groups with other quinonediazide group-containing compounds such as orthobenzoquinonediazide, orthonaphthoquinonediazide, orthoanthraquinonediazide or orthonaphthoquinonediazide sulfonic acid esters and other nuclear substitution derivatives, as well as orthoquinonediazidesulfonyl chloride. Compounds such as phenol, p-methoxyphenol, dimethylphenol, hydroquinone, bisphenol A, naphthol, pyrocatechol, pyrogallol, pyrogallol monomethyl ether, pyrogallol-1,3-dimethyl ether, gallic acid, esterified or ether with some hydroxyl groups left. Reaction products with the converted 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 quinone diazide group-containing compounds include, for example, the above-mentioned phenol compound and a suitable solvent such as dioxane containing naphthoquinone-1,2-diazide-5-sulfonic acid chloride or naphthoquinone-1,2-diazide-4-sulfonic acid chloride. It can be produced by condensing in the presence of an alkali such as triethanolamine, alkali carbonate, alkali hydrogencarbonate, etc., and completely esterifying or partially esterifying.

The amount of the photosensitizer (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% by mass or less is particularly preferable. The lower limit of the amount of the photosensitizer (G) used is, for example, preferably 10% by mass or more, preferably 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 further preferable.

Other preferred examples of the positive photosensitive resin composition include a resin whose solubility in alkali is increased by the action of an acid as the base polymer (A), and a polyfunctional vinyl ether monomer (B). Examples thereof include a photosensitive resin composition containing an acid generator (C) that generates an acid by irradiation with active light or radiation.
The positive photosensitive resin composition containing the acid generator (C) is particularly preferable as the photosensitive resin composition in that it has good sensitivity and resolution.

Hereinafter, the above-mentioned base polymer (A), the polyfunctional vinyl ether monomer (B), and the acid generator (C) that generates an acid by irradiation with active light or radiation, which are particularly preferable photosensitive resin compositions, are contained. Regarding the positive photosensitive resin composition containing a resin whose solubility in alkali is increased by the action of an acid as the base polymer (A), essential or arbitrary components and a method for producing the positive photosensitive resin composition are as follows. Explain to.
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, a resin contained as the base polymer (A) in which the solubility in alkali is increased by the action of an acid in a particularly preferable positive photosensitive resin composition will be described. The resin whose solubility in alkali is increased by the action of acid is not particularly limited, and any resin whose solubility in alkali is increased by the action of acid can be used. Among them, it is preferable to contain at least one resin selected from the group consisting of novolak resin (A1), polyhydroxystyrene resin (A2), and acrylic resin (A3).
The novolak resin (A1), the polyhydroxystyrene resin (A2), and the acrylic resin (A3) all indispensably contain a carboxy group and / or a hydroxyl group.

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

In the above formula (a1), R ^1a represents an acid dissociation dissolution inhibitory group, and R ^2a and R ^3a independently represent a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms.

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

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

In the above formulas (a2) and (a3), ^R4a and ^R5a each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, and ^R6a is carbon. It represents a linear, branched or cyclic alkyl group having 1 or more and 10 or less atoms, and R ^7a represents a linear, branched or cyclic alkyl group having 1 or more and 6 or less carbon atoms. Represents 0 or 1.

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

Here, as the acid dissociative dissolution inhibitory group represented by the above formula (a2), specifically, a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, Examples thereof include 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 dissociative dissolution inhibitory group represented by the above formula (a3) include a tert-butoxycarbonyl group and a tert-butoxycarbonylmethyl group. Examples of the trialkylsilyl group include groups having 1 or more and 6 or less 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.
As described above, the base polymer (A) contains a carboxy group and / or a hydroxyl group. Therefore, the resin containing the structural unit represented by the formula (a4) as the polyhydroxystyrene resin (A2) is such that the resin is (meth) acrylic acid together with the structural unit represented by the formula (a4). It is prepared to contain a desired amount of a structural unit derived from an unsaturated carboxylic acid or a structural unit derived from hydroxystyrenes.

In the above formula (a4), R ^8a represents a hydrogen atom or an alkyl group having 1 or more and 6 or less carbon atoms, and R ^9a represents an acid dissociation dissolution inhibitory group.

The alkyl group having 1 or more and 6 or less carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 or more and 6 or less carbon atoms. Examples of the linear or branched alkyl group include a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Examples of the cyclic alkyl group include a cyclopentyl group and a cyclohexyl group.

As the ^{acid dissociative dissolution inhibitor represented by R 9a} , the same acid dissociative dissolution inhibitor as those exemplified in the above formulas (a2) and (a3) can be used.

Further, the polyhydroxystyrene resin (A2) can contain another polymerizable compound as a constituent unit for the purpose of appropriately controlling the physical and chemical properties. Examples of such a polymerizable compound include known radical polymerizable compounds and anionic 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-methacryloyloxyethyl succinic acid, 2-. Methacrylic acid derivatives having carboxy groups and ester bonds such as methacryloyloxyethyl maleic acid, 2-methacryloyloxyethylphthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (Meth) acrylic acid alkyl esters such as (meth) acrylate; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylate and 2-hydroxypropyl (meth) acrylate; phenyl (meth) acrylate, (Meta) 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; acrylonitrile, methacrylic nitrile and the like Examples thereof include nitrile group-containing polymerizable compounds; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; and amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; and the like.

[Acrylic resin (A3)]
The acrylic resin (A3) is not particularly limited as long as it is an acrylic resin whose solubility in alkali is increased by the action of an acid and has been conventionally blended in various photosensitive resin compositions.
However, the base polymer (A) contains a carboxy group and / or a hydroxyl group as described above. Therefore, the acrylic resin (A3) can be prepared by introducing an acid dissociation dissolution inhibitory group into the phenolic hydroxyl group of the novolak resin. Therefore, the acrylic resin (A3) is composed of a structural unit derived from an unsaturated carboxylic acid such as (meth) acrylic acid or an unsaturated monomer having a hydroxyl group such as hydroxyethyl (meth) acrylate. It is prepared to contain the desired amount of units.
Acrylic resin (A3) is, for example, -SO 2 _- containing cyclic group, or preferably contains a structural unit (a-3) derived from an acrylate ester containing 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, "- SO 2 _- containing cyclic group" means, -SO 2 _- within the ring skeleton thereof shows a cyclic group containing a ring containing, in particular, -SO 2 _- in the sulfur atom ( S) is a cyclic group forming a part of the cyclic skeleton of the cyclic group. _{A ring containing −SO 2} − in its ring skeleton is counted as the first ring, and if it is the ring alone, it is a monocyclic group, and if it has another ring structure, it is a polycyclic group regardless of its structure. It is called. The −SO ₂ − containing cyclic group may be monocyclic or polycyclic.

-SO ₂ - containing cyclic group, in particular, -O-SO ₂ - within the ring skeleton cyclic group containing, i.e. -O-SO ₂ - -O-S- medium is a part of the ring skeleton It is preferably a cyclic group containing a sulfurone ring to be formed.

-SO ₂ - carbon atoms containing cyclic group preferably has 3 to 30, more preferably 4 to 20, more preferably 4 to 15, particularly preferably 4 to 12. 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 substituent.

The −SO ₂ -containing cyclic group may be a −SO ₂ -containing aliphatic cyclic group or a −SO ₂ -containing aromatic cyclic group. Preferably -SO ₂ - containing aliphatic cyclic group.

As the −SO ₂ − containing aliphatic cyclic group, a hydrogen atom is obtained from an aliphatic hydrocarbon ring in which a part of carbon atoms constituting the ring skeleton is _{substituted with −SO 2} − or −O−SO _{2 −.} Examples include groups excluding at least one. More specifically, a group in which at least one hydrogen atom is removed from an aliphatic hydrocarbon ring in which _{−CH 2} − constituting the ring skeleton is _{substituted with −SO 2− , and −CH 2} − constituting the ring. Examples thereof include a group in which at least one hydrogen atom is removed 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, and more preferably 3 or more and 12 or less. The alicyclic hydrocarbon ring may be a polycyclic type or a monocyclic type. As the monocyclic alicyclic hydrocarbon group, a group obtained by removing two hydrogen atoms from a monocycloalkane having 3 or more and 6 or less carbon atoms is preferable. 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 or more and 12 or less carbon atoms, and specifically, the polycycloalkane is adamantane or norbornane. , Isobornane, tricyclodecane, tetracyclododecane and the like.

The −SO ₂ − containing cyclic group may have a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, an alkyl halide group, a hydroxyl group, an oxygen atom (= O), -COOR ", -OC (= O) R", a hydroxyalkyl group, a cyano group and the like. Can be 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 thereof 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 preferable, and a methyl group is particularly preferable.

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. Specific examples thereof include a group in which an alkyl group mentioned as the above-mentioned alkyl group as a substituent is bonded to an oxygen atom (−O−).

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 preferable.

Examples of the alkyl halide group of the substituent include a group in which a part or all of the hydrogen atom of the above-mentioned alkyl group is substituted with the above-mentioned halogen atom.

Examples of the alkyl halide group as the substituent include a group in which a part or all of the hydrogen atoms of the alkyl group mentioned as the alkyl group as the substituent are substituted with the above-mentioned halogen atom. As the alkyl halide group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

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

When R "is a linear or branched alkyl group, the number of carbon atoms of 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 of 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. Specifically, a fluorine atom. , Or monocycloalkanes that may or may not be substituted with an alkyl fluorinated group, or polycycloalkanes such as bicycloalkanes, tricycloalkanes, tetracycloalkanes, etc., except for one or more hydrogen atoms. More specifically, one or more hydrogen atoms can be obtained from monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantan, norbornan, isobornane, tricyclodecane, and tetracyclododecane. Excluded groups and the like can be mentioned.

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 mentioned as the alkyl group as the above-mentioned substituent is substituted with a hydroxyl group can be mentioned.

（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。） -SO ₂ - containing cyclic group, and more specifically, include groups represented by the following formula (3-1) to (3-4).

(In the formula, A'is an alkylene group, an oxygen atom or a sulfur atom having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom, z is an integer of 0 or more and 2 or less, and R ^10a. Is an alkyl group, an alkoxy group, an alkyl halide 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 or more and 5 or less carbon atoms which may contain an oxygen atom (-O-) or a sulfur atom (-S-). , Oxygen atom, or sulfur atom. The alkylene group having 1 or more and 5 or less carbon atoms in A'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 a group in which -O- or -S- is interposed between the terminal or carbon atom 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. As A', an alkylene group having 1 to 5 carbon atoms or —O— is preferable, an alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group is most preferable.

z may be any of 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, alkyl halide group, -COOR ", -OC (= O) R", and hydroxyalkyl group in R ^10a _{may each have a -SO 2} -containing cyclic group. Examples of the alkyl group, alkoxy group, alkyl halide group, -COOR ", -OC (= O) R", and hydroxyalkyl group mentioned as substituents are the same as those described above.

Specific cyclic groups represented by the above formulas (3-1) to (3-4) will be illustrated below. In addition, "Ac" in the formula indicates an acetyl group.

The -SO ₂ - containing cyclic group, among the above, preferably a group represented by the formula (3-1) described above, the aforementioned chemical formula (3-1-1), (3-1-18) , (3-3-1), and (3-4-1), at least one selected from the group consisting of groups represented by any of (3-4-1) is more preferable, and it is represented by the above-mentioned chemical formula (3-1-1). The groups that are used are most preferred.

(Lactone-containing cyclic group)
The “lactone-containing cyclic group” refers to a cyclic group containing a ring (lactone ring) containing −OC (= O) − in its cyclic skeleton. The lactone ring is counted as the first ring, and when it has only a lactone ring, it is called a monocyclic group, and when it has another ring structure, it is called a polycyclic group regardless of its structure. The 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 one can be used without particular limitation. Specifically, the lactone-containing monocyclic group is 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, or γ-butyrolactone. Examples thereof include a group from which one hydrogen atom has been removed, a group from which one hydrogen atom has been removed from δ-valerolactone, and the like. Examples of the lactone-containing polycyclic group include a bicycloalkane having a lactone ring, a tricycloalkane, and a tetracycloalkane from which one hydrogen atom has been removed.

As the structural unit (a-3), -SO 2 - containing cyclic group, or a lactone-containing cyclic structure other parts as long as it has a group is not particularly limited, and bonded to the α-position carbon atom -SO 2 a structural unit is a hydrogen atom are derived substituted from even an acrylate ester with a substituent _- structural unit containing an containing cyclic group (a-3-S), and α-position carbon atom It is selected from the group consisting of a structural unit (a-3-L) derived from an acrylic acid ester in which the hydrogen atom bonded to is optionally substituted with a substituent and containing a lactone-containing cyclic group. At least one structural unit is preferred.

[Constituent unit (a-3-S)]
More specifically, as an example of the structural unit (a-3-S), a structural unit represented by the following formula (a-S1) can be mentioned.

（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 represents 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 represents a -SO 2 _- containing cyclic group, R ^12a is a single bond or a divalent linking group.)

In the formula (a-S1), R is the same as described above.
R ^11a is, -SO ₂ mentioned above - is similar to the containing cyclic group.
R ^12a may be either a single bond or a divalent linking group. Since the effect of the present invention is excellent, it is preferably a divalent linking group.

The ^{divalent linking group in R 12a} is not particularly limited, and examples thereof include a divalent hydrocarbon group which may have a substituent and a divalent linking group containing a heteroatom.

-Divalent hydrocarbon group which may have a substituent The hydrocarbon group as the divalent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. Aliphatic hydrocarbon groups mean hydrocarbon groups that do not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Saturated hydrocarbon groups are usually preferred. More specific examples of the aliphatic hydrocarbon group include a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group containing a ring in the structure, and the like.

The number of carbon atoms of 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 further preferably 1 or more and 5 or less.

As the linear aliphatic hydrocarbon group, a linear alkylene group is preferable. Specifically, a methylene group _[-CH 2 -], an ethylene group _{[- (CH 2) 2 -} ], a trimethylene group _{[- (CH 2) 3 -} ], a tetramethylene group _{[- (CH 2) 4 -} ] , Pentamethylene group [-(CH ₂ ) _5- ] and the like.

As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferable. Specifically, -CH (CH ₃ )-, -CH (CH ₂ CH ₃ )-, -C (CH ₃ ) _2- , -C (CH ₃ ) (CH ₂ CH ₃ )-, -C (CH) ₃ ) (CH ₂ CH ₂ CH ₃ )-, -C (CH ₂ CH ₃ ) ₂ -etc. Alkyl methylene groups; -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-, etc. Alkylethylene groups; -CH (CH ₃ ) CH ₂ CH ₂ −, −CH ₂ CH (CH ₃ ) CH ₂ − and other alkyl trimethylene groups; −CH (CH ₃ ) CH ₂ CH ₂ CH ₂ −, −CH ₂ CH (CH ₃ ) CH ₂ CH ₂ − Alkyltetramethylene groups such as alkylalkylene groups and the like can be mentioned. As the alkyl group in the alkylalkylene group, a linear alkyl group having 1 to 5 carbon atoms is preferable.

The linear or branched 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 fluorinated alkyl group having 1 to 5 carbon atoms substituted with a fluorine atom, and an oxo group (= O).

As the aliphatic hydrocarbon group containing a ring in the above structure, a cyclic aliphatic hydrocarbon group which may contain a substituent containing a hetero atom 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 terminal of a linear or branched aliphatic hydrocarbon group, or a cyclic aliphatic hydrocarbon group in a linear or branched chain. Examples thereof include groups intervening in the middle of the aliphatic hydrocarbon group. Examples of the above-mentioned linear or branched-chain aliphatic hydrocarbon group include the same as those described above.

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

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

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

As the alkyl group as the substituent, an alkyl group having 1 or more carbon atoms and 5 or less carbon atoms is preferable, and a methyl group, an ethyl group, a propyl group, an n-butyl group, and a tert-butyl group are more preferable.

The alkoxy group as the substituent is preferably an alkoxy group having 1 or more and 5 or less carbon atoms, and is 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 preferable, and a methoxy group and an ethoxy group are particularly preferable.

Examples of the halogen atom as the above-mentioned substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

Examples of the alkyl halide group as the above-mentioned substituent include a group in which a part or all of the hydrogen atom of the above-mentioned alkyl group is substituted with the above-mentioned halogen atom.

The cyclic aliphatic hydrocarbon group may have a part of carbon atoms constituting its ring structure substituted with -O- or -S-. The substituent containing a hetero atom, -O -, - C (= O) -O -, - S -, - S (= O) 2 -, - S (= O) 2 -O- are preferred.

The aromatic hydrocarbon group as the 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 a monocyclic type or a polycyclic type. 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, further 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.

Specifically, the aromatic ring is an aromatic hydrocarbon ring such as benzene, naphthalene, anthracene, and phenanthrene; an aromatic heterocycle in which a part of carbon atoms constituting the aromatic hydrocarbon ring is replaced with a heteroatom; And so on. Examples of the hetero atom in the aromatic heterocycle include an oxygen atom, a sulfur atom, a nitrogen atom and the like. Specific examples of the aromatic heterocycle include a pyridine ring and a thiophene ring.

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

The number of carbon atoms of the alkylene group bonded to the above 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, the hydrogen atom contained in the aromatic hydrocarbon group may be substituted with a substituent. For example, the hydrogen atom bonded to the 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, an alkyl halide group, a hydroxyl group, an oxo group (= O) and the like.

As the alkyl group as the substituent, an alkyl group having 1 or more carbon atoms and 5 or less carbon atoms is preferable, and a methyl group, an ethyl group, an n-propyl group, an n-butyl group, and a tert-butyl group are more preferable.

As the alkoxy group as the above-mentioned substituent, an alkoxy group having 1 or more and 5 or less carbon atoms is preferable, and a methoxy group, an ethoxy group, an n-propoxy group, an iso-propoxy group, an n-butoxy group, and a tert-butoxy group. Is preferable, and a methoxy group and an ethoxy group are more preferable.

Examples of the halogen atom as the above-mentioned substituent include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom and the like, and a fluorine atom is preferable.

Examples of the alkyl halide group as the above-mentioned substituent include a group in which a part or all of the hydrogen atom of the above-mentioned alkyl group is substituted with the halogen atom.

-Divalent linking group containing a hetero atom The hetero atom in the divalent linking group containing a hetero atom is an atom other than a carbon atom and a hydrogen atom, and is, for example, an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom. And so on.

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 Examples thereof include a non-hydrocarbon-based linking group such as −, and a combination of at least one of these non-hydrocarbon-based linking groups and a divalent hydrocarbon group. Examples of the divalent hydrocarbon group include those similar to the divalent hydrocarbon group which may have the above-mentioned substituent, and a linear or branched aliphatic hydrocarbon group is preferable. ..

Of the above, H in -NH-, -NH-, and -NH-C (= NH)- in -C (= O) -NH- is substituted with a substituent such as an alkyl group or an acyl group, respectively. It may have been done. The number of carbon atoms of 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.

As the ^{divalent linking group in R 12a,} a divalent linking group containing a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a heteroatom is particularly preferable.

When the ^{divalent linking group in R 12a} is a linear or branched alkylene group, the number of carbon atoms of 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 preferable, and 1 or more and 3 or less are most preferable. Specifically, in the description of the above-mentioned "divalent hydrocarbon group which may have a substituent" as the divalent linking group, it is mentioned as a linear or branched aliphatic hydrocarbon group. Examples thereof include a linear alkylene group and a branched alkylene group.

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

As the cyclic aliphatic hydrocarbon group, a group in which two or more hydrogen atoms are removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane is particularly preferable.

When the ^{divalent linking group in R 12a} is a divalent linking group containing a hetero atom, -O-, -C (= O) -O-, -C (= O) are preferable as the linking group. )-, -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 '} Groups represented by −Y ² − or −Y ¹ −OC (= O) −Y ₂₋ [Even if Y ¹ and Y ^{2 in the} formula each have independent substituents. It is a good divalent hydrocarbon group, where O is an oxygen atom and m'is an integer greater than or equal to 0 and less than or equal to 3. ] Etc. can be mentioned.

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 an acyl group. The number of carbon atoms of 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.

Wherein ^{-Y 1 -O-Y 2 -,} - [Y 1 -C (= O) -O] m '-Y 2 -, or ^{-Y 1 -O-C (= O} ) -Y 2 - In, Y ¹ and Y ² are divalent hydrocarbon groups that may independently have substituents. Examples of the divalent hydrocarbon group include the same as the “divalent hydrocarbon group which may have a substituent” mentioned in the explanation as the divalent linking group.

As Y ¹ , a linear aliphatic hydrocarbon group is preferable, a linear alkylene group is more preferable, a linear alkylene group having 1 or more carbon atoms and 5 or less carbon atoms is more preferable, and a methylene group and ethylene are preferable. Groups are particularly preferred.

As Y ² , a linear or branched aliphatic hydrocarbon group is preferable, and a methylene group, an ethylene group, and an alkyl methylene group are more preferable. The alkyl group in the alkylmethylene group is preferably a linear alkyl group having 1 to 5 carbon atoms, more preferably a linear alkyl group having 1 to 3 carbon atoms, and particularly preferably a methyl group.

Formula ^{- [Y 1 -C (= O} ) -O] m '-Y 2 - In the group represented by, m' is an integer of 0 to 3, preferably 0 to 2 integer 0 or 1 is more preferable, and 1 is particularly preferable. 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, the formula _{- (CH 2) a '-C} (= O) -O- (CH 2) b' - a group represented by are preferred. 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, still 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.

Regarding the divalent linking group in R ^{12a, as} the divalent linking group containing a hetero atom, an organic group composed of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group is preferable. Among them, a linear group containing an oxygen atom, for example, an ether bond, or a group containing an ester bond preferably as a hetero atom, formula ^-Y 1 ^-O-Y 2 described above ^{-, - [Y 1 -C (} = ^{_{O) -O] m '-Y 2}} -, or ^{-Y 1 -O-C (= O} ) -Y 2 - , more preferably a group represented by, the above formula ^{- [Y 1 -C (= O} ) -O] _{m '-Y} ² -, or ^{-Y 1 -O-C (= O} ) -Y 2 - is particularly desirable.

As the ^{divalent linking group in R 12a,} those containing an alkylene group or an ester bond (-C (= O) -O-) are preferable.

The alkylene group is preferably a linear or branched alkylene group. Preferable examples of the linear aliphatic hydrocarbon group include methylene group [−CH ₂ −], ethylene group [− (CH ₂ ) ₂ −], trimethylene group [− (CH ₂ ) ₃ −], a tetramethylene group _{[- (CH 2) 4 -} ], and a pentamethylene group _{[- (CH 2) 5 -} ] , and the like. Preferable examples of this branched alkylene group are -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 ( _{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 - alkyl ethylene such as Group; -CH (CH ₃ ) CH ₂ CH ₂ −, −CH ₂ CH (CH ₃ ) CH ₂ − and other alkyl methylene groups; −CH (CH ₃ ) CH ₂ CH ₂ CH ₂ −, −CH ₂ CH Examples thereof include alkylalkylene groups such as alkyltetramethylene groups such as (CH ₃ ) CH ₂ CH _{2- and the like.}

As the divalent linking group containing an ester bond, in particular, the formula: -R ^13a- C (= O) -O- [in the formula, R ^13a is a divalent linking group. ] Is preferred. 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。）

(In the formula, R and R ^11a are the same as described above, and R ^13a is a divalent linking group.)

The R ^13a is not particularly limited, and examples thereof include the same as the divalent linking group in the above-mentioned R ^12a.
As the ^{divalent linking group of R 13a,} a linear or branched alkylene group, an aliphatic hydrocarbon group containing a ring in the structure, or a divalent linking group containing a heteroatom is preferable, and the divalent linking group is linear. Alternatively, a branched alkylene group or a divalent linking group containing an oxygen atom as a hetero atom is preferable.

As the linear alkylene group, a methylene group or an ethylene group is preferable, and a methylene group is particularly preferable. As the branched alkylene group, an alkylmethylene group or an alkylethylene group is preferable, and -CH (CH ₃ )-, -C (CH ₃ ) _2- , or -C (CH ₃ ) ₂ CH _2- is particularly preferable. preferable.

As the divalent linking group containing an oxygen atom, an ether bond or a divalent linking group containing an ester bond is preferable, and the above-mentioned −Y ¹ −O−Y ²⁻ , − [Y ¹⁻ C (= O). ^{_{) -O] m '-Y 2 -}} , or ^{-Y 1 -O-C (= O} ) -Y 2 - is more preferable. Y ^{1 and Y 2} are divalent hydrocarbon groups that may independently have substituents, and m'is an integer of 0 or more and 3 or less. Of these, -Y ^1- OC (= O) -Y ^2- is preferable, and the _{group represented by-(CH 2} ) _c- OC (= O)-(CH ₂ ) _d- is particularly preferable. .. 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 structural unit (a-S1-12) is used. The structural unit represented is more preferable.

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

(In the formula, R, A', R ^10a , z, and R ^13a are the same as described above, respectively.)

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

As R ^13a , a linear or branched alkylene group or a divalent linking group containing an oxygen atom is preferable. The ^{linear or branched alkylene group and the divalent linking group containing an oxygen atom in R 13a} include the above-mentioned linear or branched alkylene group and a divalent linking group containing an oxygen atom, respectively. The same can be mentioned.

As the structural unit represented by the formula (a-S1-12), the 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。）

(In the formula, R and A'are the same as above, and c to e are independently integers of 1 or more and 3 or less.)

[Constituent unit (a-3-L)]
Examples of the structural unit (a-3-L) include, for example, those in which R ^11a in the above formula (a-S1) is replaced with a lactone-containing cyclic group, and more specifically, the following formula (a-3L) Examples thereof include structural units represented by a-L1) to (a-L5).

（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。）

(In the formula, R is a hydrogen atom, an alkyl group having 1 or more and 5 or less carbon atoms, or an alkyl halide group having 1 or more and 5 or less carbon atoms; R'is an independent hydrogen atom, an alkyl group, and an alkoxy group, respectively. , Alkyl halide group, hydroxyl group, -COOR ", -OC (= O) R", hydroxyalkyl group, or cyano group, where R "is a hydrogen atom or alkyl group; R ^12a is a single bond or It is a divalent linking group, where s "is an integer of 0 or more and 2 or less; A" is an alkylene group, oxygen atom, or sulfur having 1 or more and 5 or less carbon atoms which may contain an oxygen atom or a sulfur atom. It is an atom; r is 0 or 1.)

R in the formulas (a-L1) to (a-L5) is the same as described above.
The alkyl group in R ', alkoxy group, halogenated alkyl group, -COOR ", - OC (= O) R", The hydroxyalkyl group, respectively, -SO ₂ - may have the containing cyclic group Examples of the substituents include an alkyl group, an alkoxy group, an alkyl halide group, -COOR ", -OC (= O) R", and a hydroxyalkyl group similar to those described above.

R'is preferably a hydrogen atom in consideration of industrial availability and the like.
The alkyl group in "R" may be linear, branched or cyclic.
When R "is a linear or branched alkyl group, the number of carbon atoms is preferably 1 or more and 10 or less, and more preferably 1 or more and 5 or less.
When R "is a cyclic alkyl group, the number of carbon atoms is preferably 3 or more and 15 or less, more preferably 4 or more and 12 or less, and most preferably 5 or more and 10 or less. Specifically, one or more polycycloalkanes such as monocycloalcan, bicycloalcan, tricycloalcan, tetracycloalcan, which may or may not be substituted with a fluorine atom or an alkyl fluorinated group. Examples thereof include groups excluding hydrogen atoms. Specifically, one or more monocycloalkanes such as cyclopentane and cyclohexane, and polycycloalkanes such as adamantan, norbornan, isobornane, tricyclodecane, and tetracyclododecane. Examples include groups excluding hydrogen atoms.
Examples of A ″ include the same as A ′ in the above formula (3-1). A ″ is an alkylene group having 1 or more carbon atoms and 5 or less carbon atoms, an oxygen atom (−O−) or a sulfur atom. It is preferably (-S-), and more preferably an alkylene group having 1 or more and 5 or less carbon atoms, or -O-. As the alkylene group having 1 or more and 5 or less carbon atoms, a methylene group or a dimethylmethylene group is more preferable, and a methylene group is most preferable.

R ^12a is the same as ^{R 12a} in the above-mentioned formula (a-S1).
In the formula (a-L1), s "is preferably 1 or 2.
Hereinafter, specific examples of the structural units represented by the above-mentioned formulas (a-L1) to (a-L3) will be illustrated. In each of the following formulas, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

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

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), the structural unit represented by the following formulas (a-L6) to (a-L7) is also preferable.

In the formulas (a-L6) and (a-L7), R and R ^12a are the same as described above.

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

In the above formulas (a5) to (a7), R ^14a and R ^{18a to} R ^23a are independently hydrogen atoms, linear or branched alkyl groups having 1 to 6 carbon atoms, fluorine atoms, or fluorine atoms, respectively. Represents a linear or branched fluorinated alkyl group ^{having 1 or more and 6 or less carbon atoms, and R 15a to} R ^17a are independently linear or branched alkyl groups having 1 or more and 6 or less 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, and each independently has a linear chain having 1 to 6 carbon atoms. Represents a linear or branched alkyl group or a linear or branched fluorinated alkyl group having 1 or more and 6 or less carbon atoms, and R ^16a and R ^17a are bonded to each other, and both are bonded carbon atoms. together may form a hydrocarbon ring or less carbon atoms 5 or 20, Y ^a is substituted represents those 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 a methyl group, an ethyl group, a propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, a pentyl group, an isopentyl group, a neopentyl group and the like. Can be mentioned. The fluorinated alkyl group is one in which a part or all of the hydrogen atom of the alkyl group is replaced by a fluorine atom.
Specific examples of the aliphatic cyclic group include a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Specifically, a group 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. Can be mentioned. In particular, a group obtained by removing one hydrogen atom from cyclohexane or adamantane (which may further have a substituent) is preferable.

When the R ^16a and R ^17a do not bond with each other to form a hydrocarbon ring ^{, the carbon atoms of the R 15a} , R ^16a , and R ^17a are high in contrast and have good resolution, depth of focus, and the like. It is preferably a linear or branched alkyl group having a number of 2 or more and 4 or less. The R ^19a , R ^20a , R ^22a , and R ^23a are preferably hydrogen atoms or methyl groups.

The 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 atom to which both are bonded. Specific examples of such an aliphatic cyclic group include a group obtained by removing one or more hydrogen atoms from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The group is mentioned. In particular, a group obtained by removing one or more hydrogen atoms from cyclohexane or adamantane (which may further have a substituent) is preferable.

Further, ^{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 carboxy 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 preferable.

Said Y ^a is an aliphatic cyclic group or an alkyl group, and monocycloalkane, bicycloalkane, tricycloalkane, or the like groups obtained by removing one or more hydrogen atoms from polycycloalkanes such as tetramethylammonium cycloalkane .. Specifically, one or more hydrogen atoms were removed from monocycloalkanes such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, and polycycloalkanes such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane. The basis etc. can be mentioned. In particular, a group obtained by removing one or more hydrogen atoms from adamantane (which may further have a substituent) is preferable.

Furthermore, the alicyclic group of the abovementioned Y ^a is, the case of having a substituent on the ring skeleton, examples of the substituents include a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (= O) polar groups such as Examples thereof include a linear or branched alkyl group having 1 or more and 4 or less carbon atoms. As the polar group, an oxygen atom (= O) is particularly preferable.

When ^Ya is an alkyl group, it is preferably a linear or branched alkyl group having 1 or more and 20 or less carbon atoms, preferably 6 or more and 15 or less. Such an alkyl group is particularly preferably an alkoxyalkyl group, and examples of such an alkoxyalkyl group include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, and a 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 can be mentioned.

As a preferable specific example of the structural unit represented by the above formula (a5), those represented by the following formulas (a5-1) to (a5-33) can be mentioned.

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

As a preferable specific example of the structural unit represented by the above formula (a6), those represented by the following formulas (a6-1) to (a6-26) can be mentioned.

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

As a preferable specific example of the structural unit represented by the above formula (a7), those represented by the following formulas (a7-1) to (a7-15) can be mentioned.

In the above formulas (a7-1) to (a7-15), 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 from the viewpoint of easy synthesis and relatively high sensitivity. Furthermore, among the structural units represented by the formula (a6) is preferably the structural unit Y ^a is an alkyl group, the structural unit one or both of R ^19a and R ^20a is alkyl group.

Further, the acrylic resin (A3) is a resin composed of a copolymer containing the structural units represented by the above formulas (a5) to (a7) and the structural units derived from the polymerizable compound having an ether bond. Is preferable.

Examples of the polymerizable compound having an ether bond include a radically polymerizable compound such as a (meth) acrylic acid derivative having an ether bond and an ester bond, and specific examples thereof include 2-methoxyethyl (meth) acrylate. , 2-ethoxyethyl (meth) acrylate, methoxytriethylene glycol (meth) acrylate, 3-methoxybutyl (meth) acrylate, ethylcarbitol (meth) acrylate, phenoxypolyethylene glycol (meth) acrylate, methoxypolyethylene glycol (meth) Examples thereof include acrylate, methoxypolypropylene glycol (meth) acrylate, and tetrahydrofurfuryl (meth) acrylate. 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.

Further, the acrylic resin (A3) can contain other polymerizable compounds as a constituent unit for the purpose of appropriately controlling the physical and chemical properties. Examples of such a polymerizable compound include known radical polymerizable compounds and anionic 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-methacryloyloxyethyl succinic acid and 2-methacryloyloxy. Methacrylic acid derivatives having carboxy groups and ester bonds such as ethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, 2-methacryloyloxyethyl hexahydrophthalic acid; methyl (meth) acrylate, ethyl (meth) acrylate, butyl (meth) ) (Meta) acrylic acid alkyl esters such as acrylates and cyclohexyl (meth) acrylates; (meth) acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth) acrylates and 2-hydroxypropyl (meth) acrylates; phenyl ( (Meta) acrylic acid aryl esters such as meta) acrylates and benzyl (meth) acrylates; 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 acetate and other vinyl group-containing aliphatic compounds; butadiene, isoprene and other conjugated diolefins; Binitrile group-containing polymerizable compounds such as bnitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylicamide; and the like can be mentioned.

As described above, the acrylic resin (A3) may contain a structural unit derived from a polymerizable compound having a carboxy group, such as the monocarboxylic acids and dicarboxylic acids described above. 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 shape having a good cross-sectional shape. Is preferable. Specifically, the ratio of the structural units derived from the 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 preferably 5% by mass or less. preferable.
In the acrylic resin (A3), the acrylic resin containing a relatively large amount of the structural unit derived from the polymerizable compound having a carboxy group contains or does not contain a small amount of the structural unit derived from the polymerizable compound having a carboxy group. 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, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group and the like are particularly preferable in terms of being easily available industrially. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

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

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

Acrylic resin (A3) is, -SO ₂ - containing cyclic group, or containing a structural unit containing a lactone-containing cyclic group (a-3), acrylic resin (A3) structural unit in (a-3) The content is preferably 5% by mass or more, more preferably 10% by mass or more, particularly preferably 10% by mass or more and 50% by mass or less, and most preferably 10% by mass or more and 30% by 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 of the structural units represented by the above formulas (a5) to (a7), more preferably 10% by mass or more, and 10% by mass or more. It is particularly preferable to contain 50% by mass or less.

The acrylic resin (A3) preferably contains a structural unit derived from the above-mentioned 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, and more preferably 5% by mass or more and 30% by mass or less.

The acrylic resin (A3) preferably contains a structural unit derived from the (meth) acrylic acid esters having the above-mentioned acid non-dissociative aliphatic polycyclic group. The content of the structural unit derived from the (meth) acrylic acid ester having an acid-non-dissociable aliphatic polycyclic group in the acrylic resin (A3) is preferably 0% by mass or more and 50% by mass or less. More preferably, it is by mass% or more and 30% by mass or less.

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). The 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 further preferably 30,000 or more and 300,000 or less. By setting such a mass average molecular weight, it is possible to maintain sufficient strength of the photosensitive resin layer without lowering the peelability from the substrate, and further, it is possible to prevent profile swelling and cracks during plating. it can.

The dispersity of the base polymer (A) is preferably 1.05 or more. Here, the degree of dispersion is a value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting such a dispersion degree, it is possible to avoid problems such as stress resistance to the desired plating and the tendency of the metal layer obtained by the plating treatment 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). The polyfunctional vinyl ether monomer (B) has the following formula (B1):
R ^B- (-R ^b1 -O-CH = CH ₂ ) _n1 ... (B1)
Includes compounds represented by.
In the formula (B1), R ^B is an n1 valent linking group containing a monocyclic skeleton, and / or fused cyclic skeleton in which two or more single rings condensed. Total The number of monocyclic skeleton, the number of single-ring constituting the condensed cyclic skeleton in R ^B is 2 or more. R ^b1 is a single bond or a divalent linking group. Two or more R ^b1s may be the same or different. n1 is an integer of 2 or more.

The positive photosensitive resin composition contains the above-mentioned polyfunctional vinyl ether monomer together with the above-mentioned base polymer (A), so that the shape can be formed even if it comes into contact with the plating solution under plating conditions while suppressing the occurrence of cracks. Can form a resist pattern that does not easily change.
When the positive photosensitive resin composition contains the polyfunctional vinyl ether monomer (B) together with the above-mentioned base polymer (A), the coating film composed of the positive photosensitive resin composition is heated when forming the resist pattern. This is because the carboxy group and / or hydroxyl group of the base polymer (A) reacts with the polyfunctional vinyl ether monomer (B) to crosslink the molecular chain of the base polymer (A). ..

In the formula (B1), n1 or bonds with the R ^B is, the group which is bonded with a monocyclic skeleton or fused ring skeleton contained in R ^B is preferred.
Monocyclic skeleton contained in R ^B may be a aliphatic hydrocarbon ring skeleton, also in aliphatic heterocyclic skeleton in the aromatic hydrocarbon backbone may be an aromatic heterocyclic skeleton, an aromatic hydrocarbon skeleton is preferable. Examples of the monocyclic skeleton as R ^B, the following cycloalkane skeleton 10 6 or more carbon atoms, or a benzene skeleton are preferable, benzene skeleton is more preferable.
Condensed cyclic skeleton contained in R ^B may be a aliphatic hydrocarbon ring skeleton, also in aliphatic heterocyclic skeleton in the aromatic hydrocarbon skeleton, or an aromatic heterocyclic skeleton. Further, the condensed ring type skeleton may be a skeleton based on a condensed ring in which an aliphatic ring and an aromatic ring are condensed. The condensed cyclic skeleton contained in R ^B, adamantane skeleton, norbornane skeleton, isobornane skeleton, tricyclodecane skeleton, tetracyclododecane skeleton, naphthalene skeleton, a benzoxazole skeleton, benzothiazole skeleton, benzimidazole, fluorene skeleton, and A carbazole skeleton is preferred.
The number of single-ring constituting the condensed cyclic skeleton contained in R ^B is preferably 2 to 4, 2 or 3 is more preferable.

Monocyclic or fused give monocyclic skeleton or fused cyclic skeleton in R ^B may have one or more substituents. The substituents include an alkyl group having 1 to 6 carbon atoms, an alkoxy group having 1 to 6 carbon atoms, an aliphatic acyl group having 2 to 6 carbon atoms, and an aliphatic group having 2 to 6 carbon atoms. Examples thereof include an acyloxy group, a halogen atom, a cyano group, and a nitro group.

The number of monocyclic skeleton in R ^B, the sum of the number of single-ring constituting the condensed cyclic skeleton is 2 or more, preferably 2 to 4, 2 or 3 is more preferable.

R ^B is, 2 or more monocyclic skeleton, or including fused cyclic skeleton, the plurality of cyclic skeleton, a single bond, or is linked by divalent or higher polyvalent linking group. The plurality of cyclic skeletons are preferably bonded by a single bond or a divalent linking group.

The divalent linking group that links the plurality of cyclic skeletons includes an alkylene group having 1 to 6 carbon atoms, an unsaturated aliphatic hydrocarbon group having 2 to 6 carbon atoms, and an ester bond (-CO-O). -), Amid bond (-CO-NH-), ether bond (-O-), carbonyl group (-CO-), sulfide bond (-S-), disulfide bond (-S-S-), sulfonyl group (-) -SO _2- ), sulfinyl group (-SO-), imino group (-NH-), azo group (-N = N-) and the like can be mentioned.
Examples of the alkylene group having 1 or more and 6 or less carbon atoms include a methylene group, an ethane-1,1-diyl group, an ethylene group (ethane-1,2-diyl group), a propane-2,2-diyl group and the like. Can be mentioned.
Examples of unsaturated aliphatic hydrocarbon groups having 2 or more and 6 or less carbon atoms include vinylene group (ethylene-1,2-diyl group) and 2-butylene-1,2-diyl group (-CH _2- CH =). CH-CH _2- ), 1,3-butadiene-1,4-diyl group (-CH = CH-CH = CH-) and the like can be mentioned.

n1 is an integer of 2 or more. The 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 the formula (B1) can be easily synthesized or obtained.

Specific preferable examples of R ^B, include linking groups tetravalent following following divalent or higher.

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

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-), and a carbonyl group (-CO). -), Sulf group (-S-), disulfide bond (-S-S-), sulfonyl group (-SO _2- ), sulfinyl group (-SO-), imino group (-NH-), and azo group (-). One kind or a combination of two or more kinds selected from the group consisting of −N = N−) is preferable.
As a more preferable divalent linking group, a group represented by ^{−R b2} −R ^{b3− in the formula (B2) described later can be mentioned.}

Since it is particularly easy to form a resist pattern whose shape does not easily change even when it comes into contact with the plating solution under plating conditions while suppressing the occurrence of cracks, the compound represented by the formula (B1) is described below. Equation (B2):
^{R B - (- R b2 -R} b3 -O-CH = CH 2) n1 ··· (B2)
It 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 direction of the ester bond as R ^{b2 is not particularly limited.} That is, the compound represented by the formula (B2) corresponds to any of the compounds represented by the following formulas (B2-1) to (B2-3).
^{R B - (- O-R} 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 of the divalent hydrocarbon group as ^{R b3 is not particularly limited.} The ^{number of carbon atoms of 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 further 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 as R ^b3 , an aliphatic hydrocarbon group is preferable because it is flexible and easily suppresses cracks in the resist pattern. The aliphatic hydrocarbon group may be a linear 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 chain 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 preferable.

Specific examples of the divalent hydrocarbon group as R ^b3 include a p-phenylene group, an m-phenylene group, an o-phenylene group, a methylene group, an ethane-1,1-diyl group, and an ethylene group (ethane-1,1-diyl group). 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 , Pentan-1,5-diyl group, hexane-1,6-diyl group, heptane-1,7-diyl group, octane-1,8-diyl group, nonan-1,9-diyl group, decane-1, Examples thereof include a 10-diyl group, a cyclohexane-1,4-diyl group, a cyclohexane-1,3-diyl group, and a cyclohexane-1,2-diyl group.
Among these, an ethylene group (ethane-1,2-diyl group), a propane-1,3-diyl group, and a propane-1,2-diyl group are preferable.

The compound represented by the formula (B2) is represented by the following formula (B3):
R ^B1- (-CO-O-R ^b3 -O-CH = CH ₂ ) _n2 ... (B3)
It is preferably a compound represented by.
In formula (B3), R ^b3 is similar to ^{R b3} in formula (B2). n2 is an integer of 2 or more and 4 or less. R ^B1 is expressed 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)
It is a linking group of divalent or more and tetravalent or less represented by any of. ^RB2 is a phenylene group which may have a substituent. ^RB3 is a benzenetriyl group which may have a substituent. R ^b4 is a single bond or divalent linking group.

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

A phenylene group as R ^B2, or as as the benzenetriyl group has also substituents have as R ^B3, the number 1 to 6 an alkyl group having a carbon atom, 1 to 6 alkoxy group carbon atoms , An aliphatic acyl group having 2 or more and 6 or less carbon atoms, an aliphatic acyloxy group having 2 or more and 6 or less carbon atoms, a halogen atom, a cyano group, a nitro group and the like.

R ^b4 is a single bond or divalent linking group. The ^{divalent linking group as 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-), a sulfide bond (-S-), disulfide bond (-S-S-), a sulfonyl group (-SO ₂ - ), Sulfinyl group (-SO-), imino group (-NH-), azo group (-N = N-) and the like.

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

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

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

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

As a preferable specific example of the compound represented by the formula (B1) described above, a compound in which the groups represented by the following formulas (B1-i) to (B1-vi) are bonded to the following divalent groups. Can be mentioned. Two different groups selected from the groups represented by the following formulas (B1-i) to (B1-vi) may be bonded to the following divalent groups, but two groups of the same type may be bonded. It is preferable to combine.
-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 or more. It is even more preferably mass% or more, and particularly preferably 100% by mass.

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)
Synthesis method, taking into account the structure of ^{R B} and ^{R b1,} are appropriately selected.
Hereinafter, the synthesis method will be described using the compound represented by the above formula (B2) as a typical example.

As described above, the compound represented by the formula (B2) corresponds to the compound represented by any of the following formulas (B2-1) to (B2-3).
^{R B - (- O-R} 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 compound represented by the formula ^(B2-1), R B - the polyol represented by _{(OH) ^n1,} a halogen-containing vinyl ether compound represented by Hal-R b3 -O-CH = CH 2 It can be synthesized by carrying out a reaction according to a so-called Halogen's ether synthesis method. Here, Hall is a halogen atom. As the halogen atom, a chlorine atom and a bromine atom are preferable.

The compound represented by the formula ^(B2-2), R B - and a polycarboxylic acid compound represented by _{(COOH) ^n1,} an alcohol represented by HO-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, R B - and acid halides of the polyvalent carboxylic acid represented by _{(COHal) ^n1,} an alcohol represented by HO-R b3 -O-CH = CH 2, by a method of reacting the formula (B2 The compound represented by -2) can be synthesized. Here, Hall is a halogen atom. As the halogen atom, a chlorine atom and a bromine atom are preferable.

For compounds of the formula ^{(B2-3), R B - (} OH) a polyol represented by ^_n1, 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, R B - and the polyol represented by _{(OH) ^n1,} an acid halide of a vinyloxy group-containing carboxylic acid represented by ^{Hal-CO-R b3 -O-} CH = CH 2, by a method of reacting, The compound represented by the formula (B2-3) can be synthesized. Here, Hall is a halogen atom. As the halogen atom, a chlorine atom and a bromine atom are preferable.

The solvent used in each of the above reactions is not particularly limited as long as it is a solvent that is inert to each reaction. Solvents that can be used in each of the above reactions include aliphatic hydrocarbons such as hexane, heptane, and octane; aromatic hydrocarbons such as toluene, xylene, and mesityrene; halogenated hydrocarbons such as methylene chloride; acetone, methyl ethyl ketone, and diethyl. Ketones such as ketones, cyclohexanones, acetophenones and benzophenones; esters such as ethyl acetate and n-butyl acetate can be mentioned.
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 conditions in the range usually adopted 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 the formula (B1) include ethylene glycol divinyl ether, diethylene glycol divinyl ether, triethylene glycol divinyl ether, and polyethylene glycol divinyl ether. , Propropylene 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 , 6-Hexanediol divinyl ether, 1,8-octanediol divinyl ether, 1,10-decanediol divinyl ether, neopentyl glycol divinyl ether, trimethylpropandivinyl ether, pentaerythritol divinyl ether and other chain aliphatic divinyl ethers. Cyclic aliphatic divinyl ethers such as 1,4-cyclohexanediol divinyl ether and 1,4-cyclohexanedimethanol divinyl ether; 1,4-dibinyloxybenzene, 1,3-dibinyloxybenzene, 1,2- Aromatic divinyl ethers such as divinyloxybenzene, 1,4-benzenedimethanol divinyl ether, 1,3-benzenedimethanol divinyl ether, and 1,2-benzenedimethanol divinyl ether; trimethylpropantrivinyl ether, pentaerythritol Examples thereof include trivalent or higher-valent polyvalent vinyl ethers such as tetravinyl ether, sorbitol tetravinyl ether, sorbitol pentavinyl ether, dipentaerythritol pentavinyl ether, and dipentaerythritol hexavinyl ether.

The content of the polyfunctional vinyl ether monomer (B) in the positive photosensitive resin composition is not particularly limited as long as it does not impair the object of the present invention. In a positive photosensitive resin composition, it is particularly easy to suppress the occurrence of cracks during the formation of a resist pattern, and 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. 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, and more preferably 1 part by mass or more and 30 parts by mass or less with respect to 100 parts by mass of the base polymer (A). ..

<Acid generator (C) that generates acid by irradiation with active light or radiation>
The acid generator (C) is a compound that generates an acid by irradiation with active light or radiation, and is not particularly limited as long as it is a compound that directly or indirectly generates an acid by light. As the acid generator (C), the acid generators of the first to fifth aspects described below are preferable. Hereinafter, preferred embodiments of the acid generator (C) preferably used in the positive photosensitive resin composition will be described as the first to fifth embodiments.

As the first aspect of the acid generator (C), a compound represented by the following formula (c1) can be mentioned.

In the above formula (c1), X ^1c represents a sulfur atom or an iodine atom having a valence of g, and 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} , 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, and the like. Represents an alkenyl group having 2 to 30 carbon atoms or an alkynyl group having 2 to 30 carbon atoms, and R ^1c represents alkyl, hydroxy, alkoxy, alkylcarbonyl, arylcarbonyl, alkoxycarbonyl, aryloxycarbonyl, arylthio. At least one selected from the group consisting of carbonyl, asyloxy, arylthio, alkylthio, aryl, heterocyclic, aryloxy, alkylsulfinyl, arylsulfinyl, alkylsulfonyl, arylsulfonyl, alkyleneoxy, amino, cyano, nitro groups, and halogens. It may be replaced with a seed. The number of R ^1c is g + h (g-1) + 1, and R ^1a may be the same or different from each other. Also, directly with each other two or more ^{R 1c,} 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 may be bonded to form a ring structure containing ^{X 1c.} R ^2a is an alkyl group having 1 or less carbon atoms and 5 or more carbon atoms or an aryl group having 6 or less carbon atoms and 10 or more carbon atoms.

X ^2c has 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. Represented, X ^4c consists of a group consisting of alkyl having 1 to 8 carbon atoms, alkoxy having 1 to 8 carbon atoms, aryl, hydroxy, cyano, and nitro groups having 6 to 10 carbon atoms, and halogen. It may be replaced with at least one selected. X ^5c is _{-O -, - S -, -} SO -, - SO 2 -, - NH -, - NR 2c -, - CO -, - COO -, - CONH-, carbon atom number of 1 to 3 alkylene Represents a group or a phenylene group. h represents the number of repeating units of the structure in parentheses. The h + 1 X ^4c and the h X ^5c may be the same or different, respectively. R ^2a is the same as the above definition.

X ^{3c- is a counterion of onium, and examples thereof} include a fluorinated alkylfluorophosphate anion represented by the following formula (c17) and a borate anion represented by the following formula (c18).

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

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

Examples of the onium ion in the compound represented by the above formula (c1) include triphenylsulfonium, tri-p-tolylsulfonium, 4- (phenylthio) phenyldiphenylsulfonium, and 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-dihydroanthracene-2-yldi-p-tolylsulfonium, 7-isopropyl-9-oxo-10 -Thia-9,10-dihydroanthracene-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 ( Examples thereof include p-tolyl) iodonium and 4-isobutylphenyl (p-tolyl) iodonium.

Among the onium ions in the compound represented by the above formula (c1), preferable onium ions include sulfonium ions represented by the following formula (c19).

In the above formula (c19), R ^8c is independently composed of a hydrogen atom, an alkyl, a hydroxy, an alkoxy, an alkylcarbonyl, an alkylcarbonyloxy, an alkyloxycarbonyl, a halogen atom, and an aryl, an arylcarbonyl, which may have a substituent. Represents a group selected from the group. X ^2c represents the same meaning as ^{X 2c} in the formula (c1).

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) Examples thereof include −acetophenylthio) phenyl] diphenylsulfonium and 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, and the preferable number of carbon atoms is 1 or more and 8 or less, and the more preferable number of carbon atoms is 1 or more. It is 4 or less. Specific examples of the alkyl group include linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl and octyl; branched alkyl groups such as isopropyl, isobutyl, sec-butyl and tert-butyl; and further cyclopropyl, cyclobutyl and cyclopentyl. , Cycloalkyl group such as cyclohexyl, and the like, and the ratio of the hydrogen atom of the alkyl group substituted with the fluorine atom is usually 80% or more, preferably 90% or more, and more preferably 100%. When the substitution rate of the fluorine atom is less than 80%, the acid strength of the onium fluorinated alkylfluorophosphate represented by the above formula (c1) decreases.

Particularly preferable R ^3c is a linear or branched perfluoroalkyl group having 1 or more and 4 or less carbon atoms and a fluorine atom substitution rate of 100%. Specific examples thereof include CF ₃ and CF ₃ CF. _{2, (CF 3) 2 CF} , CF 3 CF 2 CF 2, CF 3 CF 2 CF 2 CF 2, (CF 3) 2 CFCF 2, CF 3 CF 2 (CF 3) CF, is _{(CF 3)} 3 C Can be 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 ] ^- , [((CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ , [((CF ₃ ) ₂ CFCF ₂ ) ₃ PF ₃ ] ⁻ , [(CF ₃ CF ₂ CF ₂ CF ₂ ) ₂ PF ₄ ] ⁻ , or [(CF ₃ CF ₂ CF ₂ ) ₃ PF ₃ ] ^- , among these, [(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 CF) CF ₃ ) ₂ CFCF ₂ ) ₂ PF ₄ ] ⁻ is particularly preferable.

Specific preferred examples of the borate anion represented by the formula (c18), 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. Of these, tetrakis (pentafluorophenyl) borate ([B (C ₆ F ₅ ) ₄ ] ⁻ ) is particularly preferable.

The second aspect of the acid generator (C) is 2,4-bis (trichloromethyl) -6-piperonyl-1,3,5-triazine, 2,4-bis (trichloromethyl) -6- [2. -(2-Frill) 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 the like according to the following formula (c3). Examples thereof include halogen-containing triazine compounds represented by.

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

In addition, as a third aspect of the acid generator (C), α- (p-toluenesulfonyloxyimino) -phenylacetonitrile, α- (benzenesulfonyloxyimino) -2,4-dichlorophenylacetonitrile, α- (benzene) Contains sulfonyloxyimino) -2,6-dichlorophenylacetonitrile, α- (2-chlorobenzenesulfonyloxyimino) -4-methoxyphenylacetonitrile, α- (ethylsulfonyloxyimino) -1-cyclopentenyl acetonitrile, and oxime sulfonate group Examples thereof include compounds represented by the following formula (c4).

In the above formula (c4), 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. Represents, 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 a compound exhibiting physical and chemical properties peculiar to an aromatic compound, for example, an aryl group such as a phenyl group or a naphthyl group, a frill group, or a thienyl group. Heteroaryl groups such as groups can be mentioned. These may have one or more suitable substituents such as a halogen atom, an alkyl group, an alkoxy group, a nitro group and the like on the ring. Further, R ^13c is particularly preferably an alkyl group having 1 or more and 6 or less carbon atoms, and examples thereof include a methyl group, an ethyl group, a propyl group and a butyl group. In particular, ^{a compound in which R 12c} is an aromatic group and R ^13c is an alkyl group having 1 or more and 4 or less carbon atoms is preferable.

As the acid generator represented by the above formula (c4), when n = 1, R ^12c is any of a phenyl group, a methyl phenyl group, and a methoxy phenyl group, and R ^{13 c} is a compound having a methyl group, specifically. Specifically, α- (methylsulfonyloxyimino) -1-phenyl acetonitrile, α- (methylsulfonyloxyimino) -1- (p-methylphenyl) acetonitrile, α- (methylsulfonyloxyimino) -1- (p-) Examples thereof include methoxyphenyl) acetonitrile, [2- (propylsulfonyloxyimino) -2,3-dihydroxythiophene-3-iriden] (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.

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

As the cation portion of the onium salt having a naphthalene ring in such a cation portion, 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 with 1 to 6 carbon atoms. Represents an alkyl group, 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 independently linear or branched with 1 to 6 carbon atoms. It is an alkylene group of, and these ends may be bonded to form a cyclic.

In the above formula (c6), R ^17c and R ^18c are independently hydroxyl groups, linear or branched alkoxy groups having 1 to 6 carbon atoms, or linear or branched having 1 to 6 carbon atoms, respectively. It represents a branched alkyl group, and R ^19c represents a linear or branched alkylene group having 1 to 6 carbon atoms which may have a single bond or a substituent. 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 there are a plurality of R 17c} , they may be the same or different from each other. Further, ^{when a plurality of 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 compound stability, and the rest is directly formed with 1 or more and 6 or less carbon atoms. It is a chain or branched alkylene group, and these ends may be bonded to form a cyclic group. In this case, the above 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.

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

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 having 1 to 6 carbon atoms. The group and the like can be mentioned.

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

The cation portion may be an iodonium salt or a sulfonium salt, but a sulfonium salt is preferable from the viewpoint of acid generation efficiency and the like.

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

The anion portion of such an acid generator is a fluoroalkyl sulfonic acid ion or an aryl sulfonic acid ion in which a part or all of hydrogen atoms are fluorinated.

The alkyl group in the fluoroalkyl sulfonic acid ion may be linear, branched or cyclic with 1 or more and 20 or less carbon atoms, and has 1 or more and 10 or less carbon atoms from the bulkiness of the generated acid and its diffusion distance. Is preferable. In particular, branched or cyclic alkyl groups are preferable because they have a short diffusion distance. Moreover, since it can be synthesized at low cost, a methyl group, an ethyl group, a propyl group, a butyl group, an octyl group and the like can be mentioned as preferable ones.

Examples of the aryl group in the aryl sulfonic acid ion include an aryl group having 6 to 20 carbon atoms, 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 to 10 carbon atoms is preferable because it can be synthesized at low cost. Specific examples of the preferred aryl group include a phenyl group, a toluenesulfonyl group, an ethylphenyl group, a naphthyl group, a methylnaphthyl group and the like.

In the above fluoroalkyl sulfonic acid ion or aryl sulfonic acid ion, the fluorination rate when a part or all of hydrogen atoms is fluorinated is preferably 10% or more and 100% or less, more preferably 50% or more and 100%. The following is particularly preferable, in which all hydrogen atoms are replaced with fluorine atoms because the strength of the acid becomes stronger. Specific examples thereof include trifluoromethanesulfonate, perfluorobutane sulfonate, perfluorooctane sulfonate, and perfluorobenzene sulfonate.

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

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

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

Further, as the anion portion, a nitrogen-containing anion portion represented by the following formulas (c13) and (c14) can also be used.

The formula (c13), (c14) in, X ^c represents a linear or branched alkylene group having at least one hydrogen atom is substituted with a fluorine atom, the number of carbon atoms of the alkylene group 2 to 6 It is preferably 3 or more and 5 or less, and most preferably the number of carbon atoms is 3. Further, 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 of the alkyl group is 1 or more and 10 or less. It is preferably 1 or more and 7 or less, and more preferably 1 or more and 3 or less.

The smaller the number of carbon atoms of the alkylene group of ^{X c or the number of carbon atoms of the alkyl group of Y c} and Z ^c , the better the solubility in an organic solvent, which is preferable.

Further, in the alkylene group of ^{X c or the alkyl group of Y c} and Z ^c , the larger 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 atomically substituted perfluoroalkylene group or perfluoroalkyl group.

Preferable compounds as an onium salt having a naphthalene ring in such a cation portion 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-) Dimethylphenylsulfonyl) Bissulfonyldiazomethanes such as diazomethane; p-toluenesulfonic acid 2-nitrobenzyl, p-toluenesulfonic acid 2,6-dinitrobenzyl, nitrobenzyltosylate, dinitrobenzyltosylate, nitrobenzylsulfonate, nitro Nitrobenzyl derivatives such as benzylcarbonate and dinitrobenzylcarbonate; pyrogalloltrimesylate, pyrogalloltritosylate, benzyltosylate, benzylsulfonate, N-methylsulfonyloxysuccinimide, N-trichloromethylsulfonyloxysuccinimide, N-phenylsulfonyl 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, N- (trifluoromethylsulfonyloxy) -4-butylthio-1,8-naphthalimide; diphenyliodonium hexafluorophosphate , (4-methoxyphenyl) phenyliodonium trifluoromethanesulphonate, bis (p-tert-butylphenyl) iodonium trifluoromethanesulphonate, triphenylsulfonium hexafluorophosphate, (4-methoxyphenyl) diphenylsulfonium trifluoromethanesulphonate, Onium salts such as (p-tert-butylphenyl) diphenylsulfonium trifluoromethanesulfonate; benzointosylates such as benzointosylate and α-methylbenzointosylate; other diphenyliodonium salts, triphenylsulfonium salts, phenyldiazonium salts , Benzylcarbonate and the like.

The acid generator (C) may be used alone or in combination of two or more. 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 content mass of the positive photosensitive resin composition. Is more preferable. By setting the amount of the acid generator (C) to be used in the above range, it is easy to prepare a photosensitive resin composition having good sensitivity, a uniform solution, and excellent storage stability.

<Crosslinking agent (D)>
The positive photosensitive resin composition preferably contains a cross-linking agent (D) that catalytically promotes a 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 above-mentioned cross-linking reaction. Preferred cross-linking agent (D) includes a compound having a phenolic hydroxyl group.
In some cases, 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), have a phenolic hydroxyl group. .. 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) described later also has the effect of catalytically promoting the cross-linking reaction between the base polymer (A) and the polyfunctional vinyl ether monomer (B).
Hereinafter, the compound having a phenolic hydroxyl group will be described.

The compound having a phenolic hydroxyl group is a compound having one or more phenolic hydroxyl groups. Hereinafter, phenols as a compound having a phenolic hydroxyl group will be described.

The 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 contained in one molecule of phenols is not particularly limited. The number of phenolic hydroxyl groups contained in one molecule of phenols is, for example, 1 or more and 6 or less, preferably 1 or more and 4 or less.

Preferable specific examples of phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethylphenol, m-ethylphenol, p-ethylphenol, o-butylphenol, m-butylphenol, 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 Glycoic acid esters such as 5-trimethylphenol, p-phenylphenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, fluoroglycinol, 4,4'-dihydroxybiphenyl, bisphenol A, carous acid, methyl carnivorate and ethyl carnivorate. , Α-naphthol, β-naphthol and the like.

The amount of the compound having a phenolic hydroxyl group used 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 is adjusted to the mass of the base polymer (A) because the effect of promoting the cross-linking reaction between the base polymer (A) and the polyfunctional vinyl ether monomer (B) is good. On the other hand, it is preferably 10% by mass or more and 20% by mass or less, preferably 100% by mass or more and 15% by mass or less, and particularly preferably 200% by mass or more and 10% by mass or less.

<Sulfur-containing compound (E)>
The positive photosensitive resin composition preferably contains the sulfur-containing compound (E). The sulfur-containing compound (E) is a compound containing a sulfur atom that can coordinate with a metal. Regarding a compound capable of producing two or more tautomers, when at least one tautomer contains a sulfur atom coordinated with a metal constituting the metal layer, the compound corresponds to a sulfur-containing compound. ..
When a resist pattern used as a plating mold is formed on a surface made of a metal such as Cu, defects in cross-sectional shape such as footing are likely to occur. However, when the positive photosensitive resin composition contains the sulfur-containing compound (E), it is easy to suppress the occurrence of cross-sectional shape defects such as footing even when a resist pattern is formed on the metal surface of the substrate. ..

The sulfur atoms that can coordinate with the metal are, 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 easy to coordinate with a 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。） A preferable example of the sulfur-containing compound having a mercapto group is a compound represented by the following formula (e1).

(In the formula, 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 is a u-valent fat which may contain an atom other than carbon. Indicates a group group, and u indicates an integer of 2 or more and 4 or less.)

When R ^e1 and R ^e2 are alkyl groups, the alkyl group may be linear or branched, and is preferably linear. When R ^e1 and R ^e2 are alkyl groups, the number of carbon atoms of the alkyl group is not particularly limited as long as the object of the present invention is not impaired. The number of carbon atoms of the alkyl group is preferably 1 or more and 4 or less, particularly preferably 1 or 2, and most preferably 1. As ^{a 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 ^Re3 is an alkylene group, the alkylene group may be linear or branched, and is preferably linear. When ^Re3 is an alkylene group, the number of carbon atoms of the alkylene group is not particularly limited as long as it does not impair the object of the present invention. The number of carbon atoms of 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.

^Re4 is an aliphatic group having a divalent value or more and a tetravalent value or less, which may contain an atom other than carbon. ^Examples of the atom other than carbon that Re4 may contain include a nitrogen atom, an oxygen atom, a sulfur atom, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom. Structure of the aliphatic group is an R ^e4 may be linear, may be branched, may be cyclic, may be a structure combining 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), the compound represented by the following formula (e2) is more preferable.

(In equation (e2), ^Re4 and u agree with equation (e1).)

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

（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 mentioned as preferable examples of sulfur-containing compounds having a mercapto group.

(In the formulas (e3-L1) to (e3-L7), R', s", A ", and r are the same as the formulas (a-L1) to (a-L7) described above for the acrylic resin (B3). The same is true.)

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 mentioned as preferable 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 acrylic resin (A3) and the formulas (3-1) to (3-4) described above.)

Preferable specific examples of the mercapto compounds represented by the above formulas (e3-1) to (e3-4) 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, as a preferable example of the compound having a mercapto group, the compound represented by the following formula (e4) can be mentioned.

(In the 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, and 1 to 4 carbon atoms. It is a group selected from the group consisting of the following hydroxyalkyl groups, mercaptoalkyl groups having 1 or more and 4 or less carbon atoms, alkyl halide groups having 1 or more and 4 or less carbon atoms, and halogen atoms, and k1 is an integer of 0 or more and 3 or less. When k0 is an integer of 0 or more and 3 or less and k1 is 2 or 3, ^Re5 may be the same or different.)

Specific example of R ^e5 is an alkyl group which may have a hydroxyl group or less carbon atoms having 1 to 4 include a methyl group, an ethyl group, n- propyl group, an isopropyl group, n- butyl group, isobutyl Groups, sec-butyl groups, and tert-butyl groups can be mentioned. Among these alkyl groups, a methyl group, a hydroxymethyl group, and an ethyl group are preferable.

^{Specific examples of the case where Re5} is an alkoxy group having 1 or more carbon atoms and 4 or less carbon atoms include a methoxy group, an ethoxy group, an n-propyloxy group, an isopropyloxy group, an n-butyloxy group, an isobutyloxy group and a sec-butyloxy group. Groups and tert-butyloxy groups can be mentioned. Among these alkoxy groups, a methoxy group and an ethoxy group are preferable, and a methoxy group is more preferable.

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

^{Specific examples of the case where Re5} is a hydroxyalkyl group having 1 or more carbon atoms and 4 or less 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 can be mentioned. Among these hydroxyalkyl groups, a hydroxymethyl group, a 2-hydroxyethyl group, and a 1-hydroxyethyl group are preferable, and a hydroxymethyl group is more preferable.

^{Specific examples of the case where Re5} is a mercaptoalkyl group having 1 or more carbon atoms and 4 or less 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 can be mentioned. Among these mercaptoalkyl groups, a mercaptomethyl group, a 2-mercaptoethyl group, and a 1-mercaptoethyl group are preferable, and a mercaptomethyl group is more preferable.

When ^Re5 is an alkyl halide group having 1 or more and 4 or less carbon atoms, examples of the halogen atom contained in the alkyl halide group include fluorine, chlorine, bromine, and iodine. Specific example of R ^e5 is a halogenated alkyl group having 1 to 4 carbon atoms are chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, dichloromethyl group, 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- Examples thereof include 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 alkyl halide groups, chloromethyl group, bromomethyl group, iodomethyl group, fluoromethyl group, dichloromethyl group, dibromomethyl group, difluoromethyl group, trichloromethyl group, tribromomethyl group, and trifluoromethyl group Is preferable, and a chloromethyl group, a dichloromethyl group, a trichloromethyl group, and a trifluoromethyl group are more preferable.

^{Specific examples of the case where Re5} is a halogen atom include fluorine, chlorine, bromine, and iodine.

In the 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, the plurality of ^Re5s may be the same or different.

In the compound represented by the formula (e4), ^{the substitution position of Re5} on the benzene ring is not particularly limited. The substitution position of ^Re5 on the benzene ring is preferably the meta position or the para position with respect to the bond position _{of − (CH 2} ) _{k0 −SH.}

Examples of the compound represented by formula (e4), as R ^e5, alkyl group, hydroxyalkyl group, and a group selected from the group consisting of mercaptoalkyl group, a compound having at least one is preferable, as R ^e5, alkyl A compound having one group selected from the group consisting of a group, a hydroxyalkyl group, and a mercaptoalkyl group is more preferable. When the compound represented by the formula (e4) has one group selected from the group consisting of an alkyl group, a hydroxyalkyl group, and a mercaptoalkyl group as ^{Re5, an alkyl group, a hydroxyalkyl group, or a mercaptoalkyl group is used.} The substitution position of the group on the benzene ring is preferably the meta-position or the para-position with respect to the bond position of _{− (CH 2} ) _{k0-SH, and more preferably the para-position.}

In the equation (e4), k0 is an integer of 0 or more and 3 or less. Since the compound can be easily prepared and obtained, k0 is preferably 0 or 1, and more preferably 0.

Specific examples of the compound represented by the formula (e4) include p-mercaptophenol, p-thiocresol, m-thiocresol, 4- (methylthio) benzenethiol, 4-methoxybenzenethiol, 3-methoxybenzenethiol, and the like. 4-ethoxybenzene thiol, 4-isopropyloxybenzene thiol, 4-tert-butoxybenzene thiol, 3,4-dimethoxybenzene thiol, 3,4,5-trimethoxybenzene thiol, 4-ethylbenzene thiol, 4-isopropylbenzene thiol , 4-n-butylbenzene thiol, 4-tert-butylbenzene thiol, 3-ethylbenzene thiol, 3-isopropylbenzene thiol, 3-n-butylbenzene thiol, 3-tert-butylbenzene thiol, 3,5-dimethylbenzene Thiol, 3,4-dimethylbenzene thiol, 3-tert-butyl-4-methylbenzene thiol, 3-tert-4-methylbenzene thiol, 3-tert-butyl-5-methylbenzene thiol, 4-tert-butyl- 3-Methylbenzene thiol, 4-mercaptobenzyl alcohol, 3-mercaptobenzyl alcohol, 4- (mercaptomethyl) phenol, 3- (mercaptomethyl) phenol, 1,4-di (mercaptomethyl) phenol, 1,3-di (Mercaptomethyl) phenol, 4-fluorobenzene thiol, 3-fluorobenzene thiol, 4-chlorobenzene thiol, 3-chlorobenzene thiol, 4-bromobenzene thiol, 4-iodobenzene thiol, 3-bromobenzene thiol, 3,4- Dichlorobenzene thiol, 3,5-dichlorobenzene thiol, 3,4-difluorobenzene thiol, 3,5-difluorobenzene thiol, 4-mercaptocatechol, 2,6-di-tert-butyl-4-mercaptophenol, 3, 5-Di-tert-butyl-4-methoxybenzenethiool, 4-bromo-3-methylbenzenethiool, 4- (trifluoromethyl) benzenethiool, 3- (trifluoromethyl) benzenethiool, 3,5-bis ( Examples thereof include trifluoromethyl) benzene thiol, 4-methyl thiobenzene thiol, 4-ethyl thiobenzene thiol, 4-n-butyl thiobenzene thiol, 4-tert-butyl thiobenzene thiol and the like.

Moreover, as a preferable example of the compound having a mercapto group, the compound represented by the following formula (e5) can be mentioned.

（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 the 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. , Hydrocarbon group, or 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 Re10} 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。 Examples of the mercapto compound represented by the above formula (e5) include the following formula (e5-1):

(In the formula (e5-1), ^Re11 is a hydrogen atom, a hydrocarbon group, or an acid dissociable group, and ^Re12 and ^Re16 are independently hydrogen atoms or alkyl groups, respectively. 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, 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 at least one of the hydrogen atom, or an acid-dissociable ^{group, R e13, R e14, R} e15, and at least one of ^{R e17} is a mercapto group.)
The mercapto compound represented by is preferable.

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

Examples of the sulfur-containing compound having a mercapto group include tautomers of a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group and a compound containing a nitrogen-containing aromatic heterocycle substituted with a mercapto group. Be done.
Suitable specific examples of the nitrogen-containing aromatic heterocycle 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, indol, indazole, benzimidazole, benzoxazole, benzothiazole, 1H-benzotriazole, quinoline, isoquinolin, cinnoline, phthalazine, quinazoline, quinoxalin, And 1,8-naphthylidine.

Suitable specific examples of the nitrogen-containing heterocyclic compound suitable as the sulfur-containing compound and the tautomer of the nitrogen-containing heterocyclic compound include the following compounds.

When the positive photosensitive resin composition contains the sulfur-containing compound (E), the amount used is preferably 0.01 part by mass or more and 5 parts by mass or less with respect to 100 parts by mass of the base polymer (A), and is 0. It is more preferably 0.02 parts by mass or more and 3 parts by mass or less, and particularly preferably 0.05 parts by mass or more and 2 parts by mass or less.

<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 retention stability of the positive photosensitive resin film. preferable. As the acid diffusion control agent (F), a nitrogen-containing compound (F1) is preferable, and if necessary, an organic carboxylic acid, or an oxo acid of phosphorus or a derivative thereof (F2) can be contained.

[Nitrogen-containing compound (F1)]
Examples of the nitrogen-containing compound (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 Amido, 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-oxyquinolin, acrydin, purine, pyrrolidine, piperidine, 2,4,6-tri (2-pyridyl) -S-triazine, morpholin, 4-methylmorpholin, piperazin, 1,4- Dimethylpiperazin, 1,4-diazabicyclo [2.2.2] octane, and pyridine, 2,6-di-tert-butylpyridine, and 2,6-diphenylpyridine, 2,4,6-triphenylpyridine, etc. Substituted pyridines and the like can be mentioned. In addition, 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- (2,4,5,10-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-piperidinethanol 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 it is particularly preferable to use it in the range of 0 parts by mass or more and 3 parts by mass or less.

[Organic carboxylic acid, or phosphorus oxo acid or derivative thereof (F2)]
Of the organic carboxylic acid, or the oxo acid of phosphorus or a derivative thereof (F2), the organic carboxylic acid is specifically malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid and the like. , Particularly salicylic acid is preferred.

Phosphonic oxo acids or derivatives thereof include phosphoric acids such as phosphoric acid, di-n-butyl ester of phosphoric acid, diphenyl ester of phosphoric acid and derivatives such as their esters; phosphonic acid, dimethyl phosphonic acid ester, phosphonic acid- Phosphonates such as di-n-butyl ester, phenylphosphonic acid, phosphonic acid diphenyl ester, phosphonic acid dibenzyl ester and derivatives such as their esters; such as phosphinic acid such as phosphinic acid, phenylphosphinic acid and their esters. Derivatives; etc. Of these, phosphonic acid is particularly preferable. These may be used alone or in combination of two or more.

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

Further, in order to form and stabilize the salt, it is preferable to use the same amount of the organic carboxylic acid, or the oxo acid of phosphorus or its derivative (F2) as that of the nitrogen-containing compound (F1).

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

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

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, and propylene glycol monoacetate. , Dipropylene glycol, monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, monophenyl ether and other polyvalent alcohols and derivatives thereof; cyclic ethers such as dioxane; ethyl acetate, 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 it does not impair the object of the present invention. When the positive photosensitive resin composition is used in a thick film application in which the 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 increased. It is preferable to use the organic solvent (S) in the 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 the plasticity. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinylbenzoic acid, polyvinylmethyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinylpyrrolidone, and copolymers thereof. .. The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition point.

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

The positive photosensitive resin composition may further contain a surfactant in order to improve coatability, defoaming property, leveling property and the like. As the surfactant, for example, a fluorine-based surfactant or a silicone-based surfactant is preferably used.
Specific examples of fluorine-based surfactants include BM-1000 and BM-1100 (all manufactured by BM Chemie), Megafuck F142D, Megafuck F172, Megafuck F173, and Megafuck F183 (all manufactured by Dainippon Ink and Chemicals Co., Ltd.). , Florard FC-135, Florard FC-170C, Florard FC-430, Florard FC-431 (all manufactured by Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S- Commercially available fluorine-based surfactants such as 141, Surflon S-145 (all manufactured by Asahi Glass Co., Ltd.), SH-28PA, SH-190, SH-193, SZ-6032, SF-8428 (all manufactured by Toray Silicone Co., Ltd.) However, the present invention is not limited to these.

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

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

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutylic 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, etc. Valuable carboxylic acids; itaconic acid anhydride, succinic acid anhydride, citraconic acid anhydride, dodecenyl succinic acid anhydride, tricarbanyl anhydride, maleic anhydride, hexahydrophthalic anhydride, methyltetrahydrophthalic anhydride, hymic anhydride, 1, 2, 3, 4-Butanetetracarboxylic acid anhydride, cyclopentanetetracarboxylic acid dianhydride, phthalic acid anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenonetetracarboxylic acid anhydride, ethylene glycol bis anhydride trimellitate, glycerintris anhydride trimeritate, etc. Acid anhydride; etc. can be mentioned.

Specific examples of the high boiling point solvent include N-methylformamide, N, N-dimethylformamide, N-methylformamide, N-methylacetamide, N, N-dimethylacetamide, N-methylpyrrolidone, dimethyl sulfoxide, and benzyl. Ethyl ether, dihexyl ether, acetonyl acetone, isophorone, caproic acid, capricic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate , Propylene carbonate, phenylcellosolveacetate and the like.

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

<Method of preparing photosensitive resin composition>
The photosensitive resin composition is prepared by mixing and stirring each of the above components by a usual method. Examples of an apparatus that can be used when mixing and stirring each of the above components include a dissolver, a homogenizer, and a three-roll mill. After uniformly mixing each of the above components, the obtained mixture may be further filtered using a mesh, a membrane filter or the like.

≪Photosensitive dry film≫
The 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 above-mentioned photosensitive resin composition.

As the base film, a film having light transmission is preferable. Specific examples thereof include polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film and the like. A polyethylene terephthalate (PET) film is preferable because it has an excellent balance between light transmission and breaking strength.

A photosensitive dry film is produced by applying the above-mentioned photosensitive resin composition on a base film to form a photosensitive resin layer.
When forming the photosensitive resin layer on the base film, an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, or the like is used, and the film thickness after drying on the base film is preferably 0. The photosensitive resin composition is applied and dried so as to be 5 μm or more and 300 μm or less, more preferably 1 μm or more and 300 μm or less, and particularly preferably 3 μm or more and 100 μm or less.

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

<< Manufacturing method of patterned resist film and substrate with mold >>
The method for forming a patterned resist film on the metal surface of a substrate having a metal surface by 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.
The preferred method is
A laminating step of laminating a photosensitive resin layer made of a photosensitive resin composition on a metal surface of a substrate having a metal surface, and
An exposure process in which the photosensitive resin layer is exposed by irradiating the photosensitive resin layer with active light or radiation in a regioselective manner.
A developing process that develops the photosensitive resin layer after exposure,
Examples thereof include a patterned resist film containing.
The method for manufacturing a substrate with a mold provided with a mold for forming a plated molded product is to manufacture a patterned resist film in the developing process, except for creating a mold for forming the plated molded product by development. Similar to the method.

The substrate on which the photosensitive resin layer is laminated is not particularly limited, and a conventionally known substrate can be used. Examples thereof include a substrate for electronic components and a substrate on which a predetermined wiring pattern is formed. be able to. As the substrate, a substrate having a metal surface is used, and as the metal species constituting the metal surface, copper, gold, and aluminum are preferable, and copper is more preferable.

The photosensitive resin layer is laminated on the substrate as follows, for example. That is, a liquid photosensitive resin composition is applied onto the substrate, and the solvent is removed by heating to form a photosensitive resin layer having a desired film thickness. The thickness of the photosensitive resin layer is not particularly limited as long as the resist pattern used as a mold can be formed with a desired film thickness. The film 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.

As a method for applying the photosensitive resin composition on the substrate, a spin coating method, a slit coating method, a roll coating method, a screen printing method, an applicator method, or the like can be adopted. It is preferable to prebake the photosensitive resin layer. The prebaking conditions vary depending on the type, blending ratio, coating film thickness, etc. of each component in the photosensitive resin composition, 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 longer. It takes about 120 minutes or less.

The photosensitive resin layer formed as described above is selectively irradiated (exposed) with active light or radiation, for example, ultraviolet rays having a wavelength of 300 nm or more and 500 nm or less or visible light through a mask having a predetermined pattern. Will be done.

As the radiation source, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, or the like can be used. Further, the radiation includes microwaves, infrared rays, visible rays, ultraviolet rays, X-rays, γ-rays, electron beams, proton beams, neutron beams, ion rays and the like. Dose of radiation varies depending on the film thickness and the like of the composition of the photosensitive resin composition and a photosensitive resin layer, for example, in the case of ultra-high pressure mercury lamp used is 100 mJ / cm ² or more 10000 mJ / cm ² or less. Further, the radiation includes a light beam that activates the acid generator (A) in order to generate an acid.

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

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

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

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

After development, it is washed with running water for 30 seconds or more and 90 seconds or less, and dried using an air gun, an oven, or the like. In this way, a resist pattern patterned in a desired shape is formed on the metal surface of the substrate having the metal surface. Further, in this way, a substrate with a mold having a resist pattern serving as a mold can be manufactured on the metal surface of the substrate having a metal surface.

≪Manufacturing method of plated objects≫
A plated model is manufactured by plating a substrate with a mold manufactured by the above method. Specifically, by embedding a conductor such as metal by plating in the non-resist portion (the portion removed by the developing solution) in the mold of the substrate with a mold formed by the above method, for example, a bump or a metal post. It is possible to form a plated object such as a connection terminal such as. The plating treatment method is not particularly limited, and various conventionally known methods can be adopted. As the plating solution, solder plating, copper plating, gold plating, and nickel plating solution are particularly preferably used. Finally, the remaining mold is removed using a stripping solution or the like according to a conventional method.

Hereinafter, the present invention will be described in more detail 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 cooling tube and a nitrogen introduction tube, and the mixture was heated to 80 ° C.
Separately, 70.0 g of ethylcyclohexyl 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), and the like. A dropping solution was prepared by dissolving 60.0 g of tetrahydrofurfuryl acrylate (THFA) and 24.9 g of the initiator V-601HP (manufactured by Fuji Film Wako Pure Chemical Industries, Ltd.) in 252 g of methoxybutyl acetate.
The prepared dropping solution was dropped into a three-necked flask over 3 hours. After the dropping was completed, the mixture was stirred for 3 hours while maintaining 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 Mw10600.

[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 the composition 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]
Biphenyl-4,4'-dicarboxylic acid 10g, 1-ethyl-3- (3-dimethylaminopropyl) carbodiimide hydrochloride 24.35g, N, N-dimethyl-4-aminopyridine 0.1g, and ethylene glycol monovinyl ether. 10 g was stirred in 40 g of methylene chloride under a nitrogen atmosphere at room temperature for 24 hours. Then, the reaction solution was washed 5 times with 50 g of pure water, and then the solvent was distilled off from the washed reaction solution to obtain a crude product. The obtained crude product was recrystallized from methylene chloride to obtain 4.38 g of the following VE2, which is a polyfunctional vinyl ether monomer (B).
The measurement result of ¹ H-NMR of VE2 was as follows. ^{1 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 is changed to stilbene-4,4'-dicarboxylic acid having an equimolar amount of 10 g of biphenyl-4,4'-dicarboxylic acid. The following VE3, which is a polyfunctional vinyl ether monomer (B), was obtained.
The measurement result of ¹ H-NMR of VE3 was as follows. ^{1 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, the following VE1 to VE4 were used as the polyfunctional vinyl ether monomers (B) (component (B)). As VE1, the following compounds synthesized by the method described in Journal of Materials Chemistry, Volume 19, Issue 24, Pages 4085-4087 were used.

In Examples and Comparative Examples, the following PAG1 to PAG4 were used as acid generators (C) (components (C)) that generate acid by irradiation with active light 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 Examples and Comparative Examples, the following E1 to E4 were used as the acid diffusion control agents (F) (component (F)).
E1: Tri-n-pentylamine E2: Tetrakis (1,2,2,6,6-pentamethyl-4-piperidyl) 1,2,3,4-butanetetracarboxylate 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 the cross-linking agent (D) in the amount shown in Table 2, the sulfur-containing compound (E) in the amount shown in Table 2, and the acid diffusion control agent of the type and amount shown in Table 2. (F) and 0.05 parts by mass of a surfactant (BYK310, manufactured by Big Chemie) were uniformly mixed and dissolved in 3-methoxybutyl acetate so that the solid content concentration was 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. The results of these evaluations are shown in Table 2.

<Crack resistance evaluation>
The photosensitive resin compositions of the respective examples and comparative examples were applied onto a copper substrate having a diameter of 8 inches to form a photosensitive resin layer having a film thickness of 55 μm. The photosensitive resin layer was then prebaked at 140 ° C. for 5 minutes. After prebaking, using a mask with a square pattern having a diameter of 30 μm and an exposure device Prisma GHI (manufactured by Ultratech), at an exposure amount at which a pattern of a predetermined size (CD at the top of the resist pattern is 35 μm) is formed. The pattern was exposed with a ghi line. The substrate was then placed on a hot plate and exposed and then heated (PEB) at 100 ° C. for 3 minutes. Then, a 2.38 wt% aqueous solution of tetramethylammonium hydroxide (developing solution, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) is added dropwise to the exposed photosensitive resin layer, and then the mixture is allowed to stand at 23 ° C. for 60 seconds. Was repeated 4 times in total. Then, after washing the surface of the resist pattern with running water, nitrogen blow was performed to obtain a resist pattern. This resist pattern was observed with a scanning electron microscope to observe the presence or absence of cracks.
When cracks were observed, it was judged as x, and when no cracks were observed, it was judged as ◯.

<Plating resistance evaluation>
The resist pattern formed in the crack resistance evaluation was immersed in a copper sulfate plating solution at 28 ° C. for 1 hour, and then the top CD of the resist pattern was measured to measure the top CD of the resist pattern after immersion and the resist before immersion. When the fluctuation of the top of the pattern with respect to the CD was ± 5% or more, it was judged as x, and when the fluctuation was less than ± 5%, it was judged as ◯.

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

Claims (12)

It contains a base polymer (A) and a polyfunctional vinyl ether monomer (B).
The base polymer (A) has a carboxy group and / or a hydroxyl group, and has
The 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 the formula (B1), R ^B is a monocyclic skeleton, and / or two or more single rings are n1 divalent linking group containing a condensed cyclic skeleton fused, the number of monocyclic skeleton in R ^B And the total number of monocycles constituting the fused cyclic skeleton are 2 or more, R ^b1 is a single bond or a divalent linking group, and 2 or more R ^b1s are different even if they are the same. A photosensitive resin composition used for forming a mold for forming a plated model, wherein n1 is an integer of 2 or more. Contains an acid generator (C) that generates an acid upon irradiation with active light or radiation.
The photosensitive resin composition according to claim 1, wherein the base polymer (A) is a resin (C1) whose solubility in alkali is increased by 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, which comprises an acid diffusion control agent (F). The photosensitive resin composition according to claim 1, which comprises a photosensitive agent (G) having a quinonediazide group. The compound represented by the formula (B1) is the following formula (B2):
^{R B - (- R b2 -R} b3 -O-CH = CH 2) n1 ··· (B2)
It is a compound represented by
In the formula (B2), ^{R B} and n1 is the same as the formula ^{(B1), R b2} is an ether bond or an ester ^{bond, R b3} is a divalent hydrocarbon group, claims 1 to 5 The photosensitive resin composition according to any one of the above. The compound represented by the formula (B2) is the following formula (B3):
R ^B1- (-CO-O-R ^b3 -O-CH = CH ₂ ) _n2 ... (B3)
It is a compound represented by
In the formula (B3), R ^b3 is the same as the 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- P ^B2 -... (B3-1)
-R ^B2 -R ^b4 -R ^B3 <... (B3-2)
> R ^B3- R ^b4- R ^B3 <... (B3-3)
It is a linking group of divalent or more and tetravalent or less represented by any of the above, ^RB2 is a phenylene group which may have a substituent, and ^RB3 is a benzenetriyl group which may have a substituent. The photosensitive resin composition according to claim 6, wherein R ^b4 is a single-bonded or divalent linking group. It has a base film and a photosensitive resin layer formed on the surface of the base film, and the photosensitive resin layer comprises the photosensitive resin composition according to any one of claims 1 to 7. Photosensitive dry film. A method for producing a photosensitive dry film, which comprises applying the photosensitive resin composition according to any one of claims 1 to 7 on a base film to form a photosensitive resin layer. A laminating step of laminating a photosensitive resin layer made of the photosensitive resin composition according to any one of claims 1 to 7 on a substrate having a metal surface.
An exposure step of irradiating the photosensitive resin layer with active rays or radiation in a regioselective manner.
A method for producing a patterned resist film, which comprises a developing step of developing the photosensitive resin layer after exposure. A laminating step of laminating a photosensitive resin layer having a photosensitive resin composition according to any one of claims 1 to 7 on a substrate having a metal surface.
An exposure step of irradiating the photosensitive resin layer with active light or radiation,
A developing step of developing the photosensitive resin layer after exposure to prepare a substrate with a mold for forming a plated model, and a developing process.
The process of plating the substrate with a mold to form a plated object in the mold, and
A method for manufacturing a plated model, including. The following formula (B3):
R ^B1- (-CO-O-R ^b3 -O-CH = CH ₂ ) _n2 ... (B3)
Represented by
In the 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)
It is a linking group of divalent or more and tetravalent or less represented by any of the above, ^RB2 is a phenylene group which may have a substituent, and ^RB3 is a benzenetriyl group which may have a substituent. A polyfunctional vinyl ether compound in which R ^b4 is a single bond or a divalent linking group.