KR20240139006A - Chemically amplified positive-type photosensitive composition, method for manufacturing substrate with template, and method for manufacturing plated article - Google Patents

Abstract

[Task] To provide a chemically amplified positive photosensitive composition that forms a pattern that serves as a mold for a process of forming a plated structure on a substrate having a metal layer on its surface, the chemically amplified positive photosensitive composition having a cross-sectional shape in which a large undercut is formed even at low temperatures and which is easy to form a resist pattern having excellent adhesion to the substrate.
[Solution] A chemically amplified positive type photosensitive composition comprising an acid generator (A) which generates an acid when irradiated with active light or radiation, a resin (B) whose solubility in alkali increases by the action of the acid, a sulfur-containing compound (E) containing a sulfur atom capable of coordinating to a metal layer of a substrate, an acid diffusion inhibitor (F), and an organic solvent (S), wherein the sulfur-containing compound (E) contains a nitrogen-containing heterocyclic compound having a mercapto group, or a tautomer thereof, wherein a decomposition rate (%) of the acid generator (A) obtained by specific steps 1) to 4) exceeds 10, is used.

Description

{CHEMICALLY AMPLIFIED POSITIVE-TYPE PHOTOSENSITIVE COMPOSITION, METHOD FOR MANUFACTURING SUBSTRATE WITH TEMPLATE, AND METHOD FOR MANUFACTURING PLATED ARTICLE}

The present invention relates to a chemically amplified positive photosensitive composition, a method for producing a mold-attached substrate using the chemically amplified positive photosensitive composition, and a method for producing a plated article using the mold-attached substrate.

Currently, photofabrication is becoming the mainstream of precision microfabrication technology. Photofabrication is a general term for a technology for manufacturing various precision parts such as semiconductor packages by applying a photoresist composition to the surface of a workpiece to form a photoresist layer, patterning the photoresist layer using photolithography technology, and performing electroforming, mainly chemical etching, electrolytic etching, or electroplating, using the patterned photoresist layer (photoresist pattern) as a mask.

In addition, in recent years, with the downsizing of electronic devices, high-density mounting technology for semiconductor packages has been progressing, and efforts are being made to improve mounting density based on multi-pin thin-film mounting of packages, miniaturization of package size, two-dimensional mounting technology using the flip chip method, and three-dimensional mounting technology. In such high-density mounting technology, as connection terminals, for example, protruding electrodes (mounting terminals) such as bumps protruding on the package, or metal posts that connect rewiring extended from peripheral terminals on the wafer to mounting terminals, are arranged with high precision on the substrate.

In the photofabrication as described above, a photoresist composition is used. As a photoresist composition, a chemically amplified photoresist composition containing an acid generator is known (see Patent Documents 1, 2, etc.). In a chemically amplified photoresist composition, acid is generated from an acid generator by radiation irradiation (exposure). Diffusion of the generated acid is promoted by heat treatment after exposure. As a result, an acid catalytic reaction occurs for a base resin, etc. in the composition, and the alkali solubility of the composition changes.

This chemically amplified photoresist composition is used, in addition to forming a patterned insulating film or an etching mask, for example, in forming plating structures such as bumps, metal posts, and Cu rewiring by a plating process. Specifically, first, using the chemically amplified photoresist composition, a photoresist layer having a predetermined film thickness is formed on a support such as a metal substrate (a substrate having a metal layer on its surface). Next, the photoresist layer is exposed through a predetermined mask pattern. The exposed photoresist layer is developed, and a portion filled with copper, etc. by plating is selectively removed (peeled). In this way, a photoresist pattern used as a mold for forming a plating structure is formed. After filling an equivalent conductor in the portion of the mold removed by development (non-resist portion) by plating, the photoresist pattern around it is removed, thereby forming a bump, a metal post, and Cu rewiring.

Patent Document 1: Japanese Patent Application Laid-Open No. 9-176112 Patent Document 2: Japanese Patent Application Laid-Open No. 11-52562

After forming a plated structure such as a bump, a metal post, or a wiring, the substrate surface is rinsed with a rinse solution, gas is sprayed onto the substrate surface for the purpose of drying, chemical treatment such as etching is performed, or a material for forming another member is applied or filled onto the substrate for the purpose of providing another member on the substrate. In this case, various loads such as forces are applied to the plated structure on the substrate. In particular, if a load is applied to a fine plated structure, there is a risk that the plated structure may collapse. Therefore, it is desirable that the plated structure is unlikely to collapse even if the load applied to the plated structure fluctuates. In other words, a plated structure having an excellent destruction margin is desirable.

In order to form a plated sculpture with an excellent collapse margin, it can be considered to make it difficult for the plated sculpture to fall over by making the plated sculpture have a footed shape. "The plated sculpture has a footed shape" means that, on the contact surface side of the plated sculpture and the substrate, the plated sculpture protrudes toward the area where the plated sculpture is not formed. When the cross-sectional shape of the plated sculpture has a footed shape, for example, the width of the plated sculpture on the contact surface side (bottom) of the substrate is wider than the width of the side opposite to the contact surface side with the substrate (top). And, if the protrusion of the plated sculpture toward the area where the plated sculpture is not formed is large, that is, if the footing of the plated sculpture is large, it can be considered that the plated sculpture is less likely to fall over.

In order for the plated structure to have a footed shape, the resist pattern (resist portion (2) and non-resist portion (3)) which serves as the mold of the plated structure preferably has an undercut shape, as shown in Fig. 1. "The resist pattern has an undercut shape" means that the non-resist portion (3) of the resist pattern is eroded toward the inside of the resist portion (2) on the surface side of the substrate (1). When the cross-sectional shape of the resist pattern is an undercut shape, for example, the width of the resist portion (2) of the resist pattern on the side (bottom) of the contact surface with the substrate (1) is narrower than the width on the side (top) opposite to the side of the contact surface with the substrate (1). And, by making the erosion of the resist portion of the non-resist portion toward the inside near the surface of the substrate larger in this way, it is thought that the footing of the plated structure can be increased, making the plated structure more difficult to fall over. In addition, Fig. 1 is a drawing schematically showing a cross-section parallel to the thickness direction of the substrate of the resist pattern.

Therefore, in order to form a plated shape with an excellent destruction margin that is difficult to collapse even when various forces are applied, it is desirable for a large undercut to be formed in the cross-sectional shape of the resist pattern that serves as the mold for the plated shape.

In addition, it is desirable that the adhesiveness to the substrate on which the resist pattern is formed be excellent. By having excellent adhesiveness to the substrate, peeling of the resist pattern during development or plating is suppressed, and a plated shape having a desired shape can be manufactured.

Additionally, in order to avoid adverse effects on the substrate on which the resist pattern is formed, it is desirable to be able to form the resist pattern at a low temperature.

However, when using a conventionally known chemically amplified positive photoresist composition, such as disclosed in Patent Documents 1 and 2, it is often difficult to form a resist pattern having a cross-sectional shape with a large undercut at low temperatures and excellent adhesion to a substrate.

The present invention has been made in view of the above problems, and it is an object of the present invention to provide a chemically amplified positive photosensitive composition which forms a pattern to serve as a mold for a process of forming a plated structure on a substrate having a metal layer on its surface, wherein even at low temperatures, the chemically amplified positive photosensitive composition has a cross-sectional shape with a large undercut and is easy to form a resist pattern having excellent adhesion to a substrate, a method for producing a mold-attached substrate using the chemically amplified positive photosensitive composition, and a method for producing a plated structure using the mold-attached substrate.

The present inventors, as a result of intensive research to achieve the above object, have found that the above problem can be solved by a chemically amplified positive type photosensitive composition comprising an acid generator (A) which generates an acid by irradiation with active light or radiation, a resin (B) whose solubility in alkali increases by the action of the acid, a sulfur-containing compound (E) containing a sulfur atom capable of coordinating to a metal layer of a substrate, an acid diffusion inhibitor (F), and an organic solvent (S), wherein the sulfur-containing compound (E) contains a nitrogen-containing heterocyclic compound having a mercapto group or a tautomer of the nitrogen-containing heterocyclic compound having a mercapto group, and which satisfies the following [requirement 1], thereby completing the present invention. Specifically, the present invention provides the following.

[1] A chemically amplified positive photosensitive composition that forms a pattern that serves as a mold for a process of forming a plating structure on a substrate having a metal layer on the surface.

An acid generator (A) that generates an acid by irradiation with active light or radiation, a resin (B) whose solubility in alkali increases by the action of the acid, a sulfur-containing compound (E) containing a sulfur atom capable of coordinating to the metal layer, an acid diffusion inhibitor (F), and an organic solvent (S).

The above sulfur-containing compound (E) comprises a nitrogen-containing heterocyclic compound having a mercapto group, or a tautomer of the nitrogen-containing heterocyclic compound having the mercapto group,

A chemically amplified positive photosensitive composition satisfying the following [requirement 1].

[Requirement 1]

The decomposition rate (%) of the acid generator (A) obtained by the following processes 1) to 4) is greater than 10.

1) By applying the chemically amplified positive photosensitive composition to a substrate having a copper layer formed on the surface by a sputtering method, a resin film having a thickness of 8.5 μm is formed.

2) The substrate on which the resin film is formed is heated at 140°C for 300 seconds.

3) After the heating, a portion of the resin film is shaved off, the shaved resin film is dissolved in propylene glycol monomethyl ether acetate so that the solid concentration becomes 20 mass%, and then acetonitrile in a mass 15 times the mass of the shaved resin film is added, and the liquid obtained by excluding the precipitate is used as a test solution.

4) After diluting the chemically amplified positive type photosensitive composition with propylene glycol monomethyl ether acetate so that the solid content concentration becomes 20 mass%, adding acetonitrile in a mass 15 times the mass of the solid content of the chemically amplified positive type photosensitive composition, analyzing the liquid from which the precipitate is removed and the test solution, respectively, by liquid chromatography, the decomposition rate (%) of the acid generator (A) represented by the following formula (a) is obtained.

Decomposition rate (%) of acid generator (A) = (1-(x/y))Х100　　　···(a)

(In formula (a), x is the content (mass%) of the acid generator (A) in the resin film,

y is the content (mass%) of the acid generator (A) in the solid content of the chemically amplified positive photosensitive composition.)

[2] A chemically amplified positive-type photosensitive composition as described in [1], wherein the acid generator (A) comprises a coumarin compound in which -CO-NR ^a1 -OSO ₂ -R ^a2 (R ^a1 represents a hydrogen atom or a hydrocarbon group, and R ^a2 represents an organic group) is bonded to a coumarin skeleton which may have a substituent.

[3] A chemically amplified positive photosensitive composition according to [1] or [2], wherein the decomposition rate (%) of the acid generator (A) obtained by the above processes 1) to 4) is 25 or more.

[4] The resin (B) is a chemically amplified positive photosensitive composition according to any one of [1] to [3], comprising a polyhydroxystyrene resin (B2).

[5] A process for laminating a photosensitive layer made of a chemically amplified positive photosensitive composition described in any one of [1] to [4] on a substrate having a metal layer on the surface,

A process of heating the above photosensitive layer to a temperature of 60℃ or higher and 130℃ or lower,

A process of selectively irradiating the photosensitive layer with active light or radiation after the heating,

A method for manufacturing a mold-attached substrate, comprising a step of developing the photosensitive layer after the above investigation to create a mold for forming a plated structure having a pattern shape.

[6] A method for manufacturing a plated article, comprising a step of forming a plated article within the mold by applying plating to the mold attachment substrate manufactured by the method described in [5] above.

According to the present invention, there can be provided a chemically amplified positive photosensitive composition which forms a pattern to serve as a mold for a process of forming a plated structure on a substrate having a metal layer on its surface, wherein the chemically amplified positive photosensitive composition has a cross-sectional shape with a large undercut even at a low temperature and is easy to form a resist pattern having excellent adhesion to the substrate, a method for producing a mold-attached substrate using the chemically amplified positive photosensitive composition, and a method for producing a plated structure using the mold-attached substrate.

[Figure 1] This is a drawing schematically showing a cross-section parallel to the thickness direction of the substrate of the resist pattern.
[Figure 2] This is a drawing schematically showing a cross-section of a resist pattern parallel to the thickness direction of a substrate, in which an undercut is observed using a scanning electron microscope in examples and comparative examples.

≪Chemically amplified positive photosensitive composition≫

A chemically amplified positive type photosensitive composition (hereinafter also referred to as the photosensitive composition) is a chemically amplified positive type photosensitive composition that forms a pattern that serves as a mold for a process of forming a plating structure on a substrate having a metal layer on the surface. The photosensitive composition contains an acid generator (A) (hereinafter also referred to as the acid generator (A)) that generates an acid when irradiated with actinic light or radiation, a resin (B) (hereinafter also referred to as the resin (B)) whose solubility in an alkali increases by the action of an acid, a sulfur-containing compound (E) (hereinafter also referred to as the sulfur-containing compound (E)) containing a sulfur atom capable of coordinating to a metal layer of the substrate, an acid diffusion inhibitor (F), and an organic solvent (S).

The sulfur-containing compound (E) includes a nitrogen-containing heterocyclic compound having a mercapto group, or a tautomer of a nitrogen-containing heterocyclic compound having a mercapto group.

In addition, the photosensitive composition satisfies the following [requirement 1].

[Requirement 1]

The decomposition rate (%) of the acid generator (A) obtained by the following processes 1) to 4) is greater than 10.

1) By applying a chemically amplified positive photosensitive composition to a substrate having a copper layer formed on the surface by a sputtering method, a resin film having a thickness of 8.5 μm is formed.

2) Heat the substrate on which the resin film has been formed at 140°C for 300 seconds.

3) After heating, a portion of the resin film is shaved off, the shaved resin film is dissolved in propylene glycol monomethyl ether acetate so that the solid concentration becomes 20 mass%, then acetonitrile is added in a mass 15 times that of the mass of the shaved resin film, and the liquid from which the precipitate is removed is used as the test solution.

4) After diluting the chemically amplified positive type photosensitive composition with propylene glycol monomethyl ether acetate so that the solid content concentration becomes 20 mass%, adding acetonitrile in a mass 15 times the mass of the solid content of the chemically amplified positive type photosensitive composition, analyzing the liquid from which the precipitate is removed and the test liquid, respectively, by liquid chromatography, the decomposition rate (%) of the acid generator (A) represented by the following formula (a) is obtained.

Decomposition rate (%) of acid generator (A) = (1-(x/y))Х100　　　···(a)

(In formula (a), x is the content (mass%) of the acid generator (A) in the resin film,

y is the content (mass%) of the acid generator (A) in the solid content of the chemically amplified positive photosensitive composition.)

By using such a photosensitive composition, as shown in the examples described below, a resist pattern having a cross-sectional shape with a large undercut and excellent adhesion to the substrate can be formed even at low temperatures on a substrate having a metal layer on the surface.

The reason why a resist pattern having a cross-sectional shape with a large undercut and excellent adhesion to the substrate can be formed even at a low temperature on a substrate having a metal layer on the surface is unclear, but it is assumed as follows.

When a photosensitive layer formed using the photosensitive composition having the above-described components and satisfying [requirement 1] on a substrate having a metal layer on its surface is heated, even at a low heating temperature (for example, 60°C or more and 130°C or less), the acid generator (A) partially decomposes on the substrate surface to generate acid. Due to this reaction, the solubility of the resin (B) in an alkali increases in an area near the substrate surface. Thereafter, the acid generator (A) decomposes by exposure to generate acid, so that the solubility of the resin (B) in an alkali increases in the exposed portion. For this reason, in a resist pattern formed by subsequent development, the amount of undercut in which the non-resist portion is greatly eroded from the substrate surface side to the inside of the resist portion increases, and the undercut becomes large.

In addition, the photosensitive composition satisfying the above [requirement 1] contains, together with the resin (B), a sulfur-containing compound (E) containing a sulfur atom capable of coordinating to the metal layer of the substrate, a nitrogen-containing heterocyclic compound having a mercapto group, or a tautomer of a nitrogen-containing heterocyclic compound having a mercapto group, thereby forming a resist pattern having a large undercut and excellent adhesion to the substrate.

On the other hand, when a photosensitive composition that does not satisfy [Requirement 1] is used, it is difficult to form a resist pattern having a cross-sectional shape with a large undercut at a low temperature and excellent adhesion to a substrate. Specifically, this applies when a photosensitive composition having a decomposition rate (%) of the acid generator (A) of [Requirement 1] is used, or a photosensitive composition that does not include a nitrogen-containing heterocyclic compound having a mercapto group or a tautomer of a nitrogen-containing heterocyclic compound having a mercapto group as the sulfur-containing compound (E).

For example, if a photosensitive composition is used that does not contain a nitrogen-containing heterocyclic compound having a mercapto group or a tautomer of a nitrogen-containing heterocyclic compound having a mercapto group, the resist pattern formed has poor adhesion to a substrate and is likely to peel off from the substrate. If a photosensitive composition in which the decomposition rate (%) of the acid generator (A) of [Requirement 1] is 10 or less is used, it is difficult to form an undercut shape.

Here, the photosensitive composition satisfying the above [requirement 1] can be manufactured by adjusting the types or blending amounts of the components (particularly, the acid generator (A) and the acid diffusion inhibitor (F)). In addition, the decomposition rate (%) of the acid generator (A) of the above [requirement 1] does not depend only on the acid generator (A) included in the photosensitive composition, but may also depend on components included in the photosensitive composition, such as the acid diffusion inhibitor (F).

The decomposition rate (%) of the acid generator (A) of [Requirement 1] may be greater than 10, but with respect to the lower limit, it is preferably 15 or more, more preferably 20 or more, still more preferably 25 or more, and may also be 30 or more. With respect to the upper limit of the decomposition rate (%) of the acid generator (A) of [Requirement 1], it is preferably 40 or less, and more preferably 35 or less.

The film thickness of the resist pattern formed using the photosensitive composition is not particularly limited. Specifically, the film thickness of the resist pattern formed using the photosensitive composition is preferably 0.5 μm or more, more preferably 0.5 μm or more and 300 μm or less, still more preferably 0.5 μm or more and 200 μm or less, and particularly preferably 0.5 μm or more and 150 μm or less.

The upper limit of the film thickness may be, for example, 100 μm or less. The lower limit of the film thickness may be, for example, 1 μm or more or 3 μm or more.

For example, when a line-and-space pattern is formed using a photosensitive composition, the width of the resist portion (line portion) of the line-and-space pattern is not particularly limited. The width of the resist portion is the width of the surface opposite to the surface of the resist portion in contact with the substrate. Specifically, the width of the resist portion of the line-and-space pattern formed using the photosensitive composition is preferably 0.05 μm or more and 20 μm or less, more preferably 0.5 μm or more and 10 μm or less, and still more preferably 1.0 μm or more and 4.0 μm or less.

Hereinafter, essential or optional components included in the photosensitive composition and a method for producing the photosensitive composition are described.

<Acid generator (A)>

The acid generator (A) is not particularly limited as long as the photosensitive composition satisfies [requirement 1] described above. The acid generator (A) is a compound that generates an acid upon irradiation with active light or radiation, and is a compound that directly or indirectly generates an acid by light.

As the acid generator (A), an aromatic compound having a group represented by -CO-NR ^a1 -OSO ₂ -R ^a2 (R ^a1 represents a hydrogen atom or a hydrocarbon group, and R ^a2 represents an organic group), or a compound having an oxime sulfonate group is preferable, an aromatic compound in which a group represented by -CO-NR ^a1 -OSO ₂ -R ^a2 is bonded to a condensed ring which contains an aromatic ring and which may have a substituent, is more preferable, a naphthalene-based compound in which a group represented by -CO-NR ^a1 -OSO ₂ -R ^a2 is bonded to a naphthalene skeleton which may have a substituent, and a coumarin-based compound in which a group represented by -CO-NR ^a1 -OSO ₂ -R ^a2 is bonded to a coumarin skeleton which may have a substituent are still more preferable, and a coumarin-based compound in which a group represented by -CO-NR ^a1 -OSO ₂ -R ^a2 is bonded to a coumarin skeleton which may have a substituent is particularly preferable.

As a coumarin compound in which a group represented by -CO-NR ^a1 -OSO ₂ -R ^a2 (R ^a1 represents a hydrogen atom or a hydrocarbon group, and R ^a2 represents an organic group) is bonded to a coumarin skeleton which may have a substituent, a compound represented by the following formula (i) can be exemplified.

In the above formula (i), R ^a1 represents a hydrogen atom or a hydrocarbon group, R ^a2 represents an organic group, R ^a3 represents an alkyl group, a cycloalkyl group, a fluoroalkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, or a halogen atom, and n1 represents an integer of 0 to 4.)

As hydrocarbon groups as R ^a1 , alkyl groups, cycloalkyl groups, alkenyl groups, alkynyl groups, aryl groups, and combinations thereof can be mentioned.

The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 18. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-tetradecyl group, an n-hexadecyl group, an n-octadecyl group, and an isooctadecyl group.

The number of carbon atoms in the cycloalkyl group is preferably 3 or more and 18 or less. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

The alkenyl group may be linear or branched. The number of carbon atoms in the alkenyl group is preferably 2 or more and 18 or less. Specific examples of the alkenyl group include a vinyl group, an allyl group, a 1-propenyl group, an isopropenyl group, a 1-butenyl group, a 2-butenyl group, a 3-butenyl group, a 1-methyl-1-propenyl group, a 1-methyl-2-propenyl group, a 2-methyl-1-propenyl group, a 2-methyl-2-propenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-methyl-1-butenyl group, a 2-methyl-2-butenyl group, a 3-methyl-2-butenyl group, a 1,2-dimethyl-1-propenyl group, a 1-decenyl group, a 2-decenyl group, an 8-decenyl group, a 1-dodecenyl group, a 2-dodecenyl group, and a 10-dodecenyl group.

The alkynyl group may be linear or branched. The number of carbon atoms in the alkynyl group is preferably 2 to 18. Specific examples of the alkynyl group include an ethynyl group, a 1-propynyl group, a 2-propynyl group, a 1-butynyl group, a 2-butynyl group, a 3-butynyl group, a 1-methyl-2-propynyl group, a 1-pentynyl group, a 2-pentynyl group, a 3-pentynyl group, a 4-pentynyl group, a 1-methyl-2-butynyl group, a 1,2-dimethyl-2-propynyl group, a 1-decynyl group, a 2-decynyl group, an 8-decynyl group, a 1-dodecynyl group, a 2-dodecynyl group, and a 10-dodecynyl group.

The number of carbon atoms in the aryl group is preferably 6 or more and 18 or less. Specific examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group, an anthracenyl group, and a biphenyl group.

As R ^a1 , a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable.

The organic group as R ^a2 may have a heteroatom such as O, N, S, P, or a halogen atom, and may have a substituent. The organic group may be linear, branched, cyclic, or a combination thereof.

As the organic group as R ^a2 , an alkyl group, a cycloalkyl group, an aryl group, a heterocyclic group, and a combination thereof can be mentioned.

The alkyl group may be linear or branched. The number of carbon atoms in the alkyl group is preferably 1 to 18. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-tetradecyl group, an n-hexadecyl group, an n-octadecyl group, and an isooctadecyl group.

The number of carbon atoms in the cycloalkyl group is preferably 3 or more and 18 or less. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, and a 10-camphoryl group.

The number of carbon atoms in the aryl group is preferably 6 or more and 18 or less. Specific examples of the aryl group include a phenyl group, a tolyl group, a naphthyl group, an anthracenyl group, and a biphenyl group.

The number of carbon atoms of the heterocyclic group is preferably 4 or more and 20 or less. Specific examples of the heterocyclic group include a thienyl group, a furanyl group, a pyranyl group, a pyrrolyl group, an oxazolyl group, a thiazolyl group, a pyridyl group, a pyrimidyl group, a pyrazinyl group, an indolyl group, a benzofuranyl group, a benzothienyl group, a quinolyl group, an isoquinolyl group, a quinoxalinyl group, a quinazolyl group, a carbazolyl group, an acridinyl group, a phenothiadinyl group, a phenodinyl group, a phenodinyl group, a xanthenyl group, a thianthrenyl group, a phenoxadinyl group, a phenoxathiinyl group, a chromanyl group, an isochromanyl group, a dibenzothienyl group, a xanthonyl group, a thioxanthonyl group, and a dibenzofuranyl group.

As a substituent that the organic group as R ^a2 may have, there may be mentioned an alkyl group, a cycloalkyl group, a fluoroalkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group, and a halogen atom.

The alkyl group as a substituent may be linear or branched. The number of carbon atoms of the alkyl group is preferably 1 to 18. Specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, a tert-pentyl group, an isohexyl group, an n-octyl group, an n-decyl group, an n-dodecyl group, an n-tetradecyl group, an n-hexadecyl group, an n-octadecyl group, and an isooctadecyl group.

The number of carbon atoms of the cycloalkyl group as a substituent is preferably 3 or more and 18 or less. Specific examples of the cycloalkyl group include a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, and a cyclohexyl group.

As fluoroalkyl groups as substituents, examples include a trifluoromethyl group, a pentafluoroethyl group, a heptafluoropropyl group, and a heptafluorobutyl group.

The alkoxy group as a substituent may be linear or branched. The number of carbon atoms of the alkoxy group is preferably 1 to 18. Specific examples of the alkoxy group include a methoxy group, an ethoxy group, a propoxy group, an isopropoxy group, a butoxy group, an isobutoxy group, a sec-butoxy group, a tert-butoxy group, a hexyloxy group, a decyloxy group, a dodecyloxy group, and an octadecyloxy group.

The alkylcarbonyl group as a substituent may be linear or branched. The number of carbon atoms of the alkylcarbonyl group is preferably 2 to 18. Specific examples of the alkylcarbonyl group include an acetyl group, a propionyl group, a butanoyl group, a 2-methylpropionyl group, a heptanoyl group, a 2-methylbutanoyl group, a 3-methylbutanoyl group, an octanoyl group, a decanoyl group, a dodecanoyl group, and an octadecanoyl group.

The number of carbon atoms of the arylcarbonyl group as a substituent is preferably 7 or more and 11 or less. Specific examples of the arylcarbonyl group include a benzoyl group and a naphthoyl group.

The alkoxycarbonyl group as a substituent may be linear or branched. The number of carbon atoms in the alkoxycarbonyl group is preferably 2 to 19. Specific examples of the alkoxycarbonyl group include a methoxycarbonyl group, an ethoxycarbonyl group, a propoxycarbonyl group, an isopropoxycarbonyl group, a butoxycarbonyl group, an isobutoxycarbonyl group, a sec-butoxycarbonyl group, a tert-butoxycarbonyl group, an octyloxycarbonyl group, a tetradecyloxycarbonyl group, and an octadecyloxycarbonyl group.

The number of carbon atoms of the aryloxycarbonyl group as a substituent is preferably 7 or more and 11 or less. Specific examples of the aryloxycarbonyl group include a phenoxycarbonyl group and a naphthoxycarbonyl group.

The number of carbon atoms of the arylthiocarbonyl group as a substituent is preferably 7 or more and 11 or less. Specific examples of the arylthiocarbonyl group include a phenylthiocarbonyl group and a naphthoxythiocarbonyl group.

The acyloxy group as a substituent may be linear or branched. The number of carbon atoms of the acyloxy group is preferably 2 to 19. Specific examples of the acyloxy group include an acetoxy group, an ethylcarbonyloxy group, a propylcarbonyloxy group, an isopropylcarbonyloxy group, a butylcarbonyloxy group, an isobutylcarbonyloxy group, a sec-butylcarbonyloxy group, a tert-butylcarbonyloxy group, an octylcarbonyloxy group, a tetradecylcarbonyloxy group, and an octadecylcarbonyloxy group.

The number of carbon atoms of the arylthio group as a substituent is preferably 6 or more and 20 or less. Specific examples of the arylthio group include a phenylthio group, a 2-methyl phenylthio group, a 3-methyl phenylthio group, a 4-methyl phenylthio group, a 2-chlorophenylthio group, a 3-chlorophenylthio group, a 4-chlorophenylthio group, a 2-bromophenylthio group, a 3-bromophenylthio group, a 4-bromophenylthio group, a 2-fluorophenylthio group, a 3-fluorophenylthio group, a 4-fluorophenylthio group, a 2-hydroxyphenylthio group, a 4-hydroxyphenylthio group, a 2-methoxy phenylthio group, a 4-methoxy phenylthio group, a 1-naphthylthio group, a 2-naphthylthio group, a 4-[4-(phenylthio)benzoyl]phenylthio group, a 4-[4-(phenylthio) Examples thereof include 4-[4-(phenylthio)phenyl]phenylthio, 4-(phenylthio)phenylthio, 4-benzoyl phenylthio, 4-benzoyl-2-chlorophenylthio, 4-benzoyl-3-chlorophenylthio, 4-benzoyl-3-methylthio phenylthio, 4-benzoyl-2-methylthio phenylthio, 4-(4-methylthio benzoyl) phenylthio, 4-(2-methylthio benzoyl) phenylthio, 4-(p-methyl benzoyl) phenylthio, 4-(p-ethyl benzoyl) phenylthio, 4-(p-isopropyl benzoyl) phenylthio, and 4-(p-tert-butyl benzoyl) phenylthio.

The alkylthio group as a substituent may be linear or branched. The number of carbon atoms of the alkylthio group is preferably 1 to 18. Specific examples of the alkylthio group include methylthio, ethylthio, propylthio, isopropylthio, butylthio, isobutylthio, sec-butylthio, tert-butylthio, pentylthio, isopentylthio, neopentylthio, tert-pentylthio, octylthio, decylthio, dodecylthio, and isooctadecylthio.

The number of carbon atoms of the aryl group as a substituent is preferably 6 or more and 10 or less. Specific examples of the aryl group include a phenyl group, a tolyl group, a dimethylphenyl group, and a naphthyl group.

The number of carbon atoms of the heterocyclic group as a substituent is preferably 4 or more and 20 or less. Specific examples of the heterocyclic group include a thienyl group, a furanyl group, a pyranyl group, a pyrrolyl group, an oxazolyl group, a thiazolyl group, a pyridyl group, a pyrimidyl group, a pyridinyl group, an indolyl group, a benzofuranyl group, a benzothienyl group, a quinolyl group, an isoquinolyl group, a quinoxalinyl group, a quinazolyl group, a carbazolyl group, an acridinyl group, a phenothiadinyl group, a phenodinyl group, a phenadienyl group, a xanthenyl group, a thianthrenyl group, a phenoxadinyl group, a phenoxathiinyl group, a chromanyl group, an isochromanyl group, a dibenzothienyl group, a xanthonyl group, a thioxanthonyl group, and a dibenzofuranyl group.

The number of carbon atoms of the aryloxy group as a substituent is preferably 6 or more and 10 or less. Specific examples of the aryloxy group include a phenoxy group, a naphthyloxy group, and the like.

The alkylsulfinyl group as a substituent may be linear or branched. The number of carbon atoms of the alkylsulfinyl group is preferably 1 to 18. Specific examples of the alkylsulfinyl group include a methylsulfinyl group, an ethylsulfinyl group, a propylsulfinyl group, an isopropylsulfinyl group, a butylsulfinyl group, an isobutylsulfinyl group, a sec-butylsulfinyl group, a tert-butylsulfinyl group, a pentylsulfinyl group, an isopentylsulfinyl group, a neopentylsulfinyl group, a tert-pentylsulfinyl group, an octylsulfinyl group, and an isooctadecylsulfinyl group.

The number of carbon atoms of the arylsulfinyl group as a substituent is preferably 6 or more and 10 or less. Specific examples of the arylsulfinyl group include a phenylsulfinyl group, a tolylsulfinyl group, and a naphthylsulfinyl group.

The alkylsulfonyl group as a substituent may be linear or branched. The number of carbon atoms of the alkylsulfonyl group is preferably 1 to 18. Specific examples of the alkylsulfonyl group include a methylsulfonyl group, an ethylsulfonyl group, a propylsulfonyl group, an isopropylsulfonyl group, a butylsulfonyl group, an isobutylsulfonyl group, a sec-butylsulfonyl group, a tert-butylsulfonyl group, a pentylsulfonyl group, an isopentylsulfonyl group, a neopentylsulfonyl group, a tert-pentylsulfonyl group, an octylsulfonyl group, and an octadecylsulfonyl group.

The number of carbon atoms of the arylsulfonyl group as a substituent is preferably 6 or more and 10 or less. Specific examples of the arylsulfonyl group include a phenylsulfonyl group, a tolylsulfonyl group (tosyl group), and a naphthylsulfonyl group.

Halogen atoms that act as substituents include fluorine atoms, chlorine atoms, bromine atoms, and iodine atoms.

As R ^a2 , an alkyl group having 6 to 10 carbon atoms, a 10-camphoryl group, or a phenyl group which may have a substituent is preferable.

With respect to the alkyl group, cycloalkyl ^group , fluoroalkyl group, hydroxy group, alkoxy group, alkylcarbonyl group, arylcarbonyl group, alkoxycarbonyl group, aryloxycarbonyl group, arylthiocarbonyl group, acyloxy group, arylthio group, alkylthio group, aryl group, heterocyclic group, aryloxy group, alkylsulfinyl group, arylsulfinyl group, alkylsulfonyl group, arylsulfonyl group, and halogen atom as R a3, they are each the same as the groups explained as the substituents which the organic group as R ^a2 may have.

As R ^a3 , an alkyl group having 1 to 4 carbon atoms or an alkoxy group having 1 to 4 carbon atoms is preferable.

It is desirable that n1 be 1.

In formula (i), the position of the group represented by -CO-NR ^a1 -OSO ₂ -R ^a2 in the coumarin skeleton is not particularly limited. In formula (i), the group represented by -CO-NR ^a1 -OSO ₂ -R ^a2 is preferably bonded to a carbon atom adjacent to the carbonyl group of the coumarin skeleton.

Specific examples of the compound represented by formula (i) include the following compounds. In the formula below, Bu represents a butyl group and iPR represents an isopropyl group. Specific examples of the compound represented by formula (i) include compounds in which Bu in the following compound is substituted with a methyl group, an ethyl group, or a propyl group, compounds in which iPr in the following compound is substituted with a methyl group, an ethyl group, or a butyl group, and compounds in which -C ₈ H ₁₇ in the following compound is substituted with -C ₆ H ₁₃ , -C ₇ H ₁₅ , -C ₉ H ₁₉ , or -C ₁₀ H ₂₁ .

As a naphthalene compound in which -CO-NR ^a1 -OSO ₂ -R ^a2 (R ^a1 represents a hydrogen atom or a hydrocarbon group, and R ^a2 represents an organic group) is bonded to a naphthalene skeleton which may have a substituent, a compound represented by the following formula (ii) can be exemplified.

In the above formula (ii), R ^a1 represents a hydrogen atom or a hydrocarbon group, R ^a2 represents an organic group, R ^a3 and R ^a4 each independently represent an alkyl group, a cycloalkyl group, a fluoroalkyl group, a hydroxy group, an alkoxy group, an alkylcarbonyl group, an arylcarbonyl group, an alkoxycarbonyl group, an aryloxycarbonyl group, an arylthiocarbonyl group, an acyloxy group, an arylthio group, an alkylthio group, an aryl group, a heterocyclic group, an aryloxy group, an alkylsulfinyl group, an arylsulfinyl group, an alkylsulfonyl group, an arylsulfonyl group or a halogen atom, n2 represents an integer of 0 to 4, and n3 represents an integer of 0 to 3.)

R ^a1 in formula (ii) is the same as R ^a1 in formula (i).

R ^a2 in formula (ii) is the same as R ^a2 in formula (i).

R ^a3 and R ^a4 in formula (ii) are the same as R ^a3 in formula (i).

As R ^a1 , a hydrogen atom and an alkyl group having 1 to 4 carbon atoms are preferable.

As R ^a2 , an alkyl group having 6 to 10 carbon atoms or a 10-camphoryl group is preferable.

As R ^a3 and R ^a4 , an alkoxy group having 1 to 4 carbon atoms is preferable.

It is desirable that n2 be 1.

It is desirable that n3 be 1.

Specific examples of compounds represented by formula (ii) include the following compounds. In the formula below, Ph represents a phenyl group. Specific examples of compounds represented by formula (ii) include compounds in which -C ₈ H ₁₇ in the following compounds is substituted with -C ₆ H ₁₃ , -C ₇ H ₁₅ , -C ₉ H ₁₉ , or -C ₁₀ H _{21 .}

As the oxime sulfonate group possessed by a compound having an oxime sulfonate group, a group represented by the following formula (iii) can be exemplified.

In the above formula (iii), R ^a8 is an organic group which may have a substituent.

The organic group as R ^a8 is the same as the organic group as R ^a2 .

The substituents that the organic group as R ^a8 may have are the same as the substituents that the organic group as R ^a2 may have.

As compounds having an oxime sulfonate group, compounds represented by the following formulae (iv) to (vi) can be mentioned.

In the above formula (iv), R ^a8 is the same as R ^a8 in formula (iii), R ^a9 represents a monovalent, divalent, or trivalent organic group, and n4 represents the number of repeating units of the structure in parentheses and is an integer greater than or equal to 1 and less than or equal to 3.

As the acid generator represented by the above formula (iv), a compound in which, when n4 = 1, R ^a9 is any one of a phenyl group, a methylphenyl group, and a methoxyphenyl group, and R ^a9 is a methyl group is preferable. Specific examples of such compounds include α-(methylsulfonyloxyimino)-1-phenylacetonitrile, α-(methylsulfonyloxyimino)-1-(p-methylphenyl) acetonitrile, α-(methylsulfonyloxyimino)-1-(p-methoxyphenyl) acetonitrile, [2-(propylsulfonyloxyimino)-2,3-dihydroxythiophene-3-ylidene](o-tolyl) acetonitrile, and the like. When n4 = 2, specific examples of the acid generator represented by the above formula (iv) include an acid generator represented by the following formula.

In the above formulas (v) and (vi), m is 0 or 1,

n5 is 1 or 2,

R ^a10 , when m is 1, is a phenyl group or a heteroaryl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, or, when m is 0, is a phenyl group or a heteroaryl group which may have an alkyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a phenoxycarbonyl group, or CN,

R ^a11 , when m is 1, is a phenyl group or a heteroaryl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, and when m is 0, is a phenyl group or a heteroaryl group which may be substituted by an alkyl group having 1 to 12 carbon atoms, an alkoxycarbonyl group having 2 to 6 carbon atoms, a phenoxycarbonyl group, or CN.

R ^a12 , when n5 is 1, is an alkyl group having 1 to 18 carbon atoms, and when n5 is 2, is an alkylene group or phenylene group having 2 to 12 carbon atoms,

R ^a13 and R ^a14 are, each independently, a hydrogen atom, a halogen, an alkyl having 1 to 6 carbon atoms,

R ^a15 is an alkyl group having 1 to 18 carbon atoms,

A is S, O, or -NR ¹⁷ ,

R ¹⁷ is a hydrogen atom or a phenyl group,

R ^a16 is an alkylene group having 2 to 12 carbon atoms.

It is desirable that m be 0.

It is desirable that n5 be 1.

It is preferable that R ^a10 is a phenyl group which may have an alkyl group having 1 to 4 carbon atoms.

It is preferable that R ^a11 is CN.

It is preferable that R ^a12 is an alkyl group having 1 to 4 carbon atoms.

It is preferred that R ^a13 and R ^a14 are hydrogen atoms.

It is preferable that R ^a15 is an alkyl group having 1 to 4 carbon atoms.

It is desirable that A be S.

From the point of view that it is easy to obtain a photosensitive composition satisfying [requirement 1] of the above, it is preferable that the acid generator (A) contains the above coumarin-based compound, and it is preferable that it contains the compound represented by the above formula (i).

This acid generator (A) may be used alone, or two or more types may be used in combination. In addition, the content of the acid generator (A) is preferably 0.1 mass% or more and 10 mass% or less, more preferably 0.2 mass% or more and 6 mass% or less, and particularly preferably 0.5 mass% or more and 3 mass% or less, based on the total solid content of the photosensitive composition. By setting the amount of the acid generator (A) to be used within the above range, it is easy to prepare a photosensitive composition having good sensitivity, as a uniform solution, and excellent storage stability.

In addition, in this specification, the solid content refers to a component other than a solvent.

<Suji (B)>

As the resin (B) whose solubility in an alkali increases by the action of an acid, there is no particular limitation, and any resin whose solubility in an alkali increases by the action of an acid can be used. As the resin (B), a novolac resin (B1), a polyhydroxystyrene resin (B2), or an acrylic resin (B3) can be mentioned. The resin (B) preferably contains a polyhydroxystyrene resin (B2) or an acrylic resin (B3), and more preferably contains a polyhydroxystyrene resin (B2).

[Novolac Resin (B1)]

As the novolac resin (B1), a resin containing a constituent unit represented by the following formula (b1) can be used.

In the above formula (b1), R ^1b represents an acid-dissociable, dissolution-inhibiting group, and R ^2b and R ^3b each independently represent a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.

As the acid dissociation dissolution inhibiting group represented by the above R ^1b , it is preferable that it is a group represented by the following formulas (b2) and (b3), a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, a vinyloxyethyl group, a tetrahydropyranyl group, a tetrahydrofuranyl group, or a trialkylsilyl group.

In the above formulas (b2) and (b3), R ^4b and R ^5b each independently represent a hydrogen atom or a linear or branched alkyl group having 1 to 6 carbon atoms, R ^6b represents a linear, branched, or cyclic alkyl group having 1 to 10 carbon atoms, R ^7b represents a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms, and o 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. In addition, examples of the cyclic alkyl group include a cyclopentyl group, a cyclohexyl group, and the like.

Here, specific examples of the acid dissociable, dissolution inhibiting group represented by the above formula (b2) include a methoxyethyl group, an ethoxyethyl group, an n-propoxyethyl group, an isopropoxyethyl group, an n-butoxyethyl group, an isobutoxyethyl group, a tert-butoxyethyl group, a cyclohexyloxyethyl group, a methoxypropyl group, an ethoxypropyl group, a 1-methoxy-1-methyl-ethyl group, a 1-ethoxy-1-methyl ethyl group, and the like. In addition, specific examples of the acid dissociable, dissolution inhibiting group represented by the above formula (b3) include a tert-butoxycarbonyl group, a tert-butoxycarbonyl methyl group, and the like. In addition, examples of the above trialkylsilyl group include groups in which each alkyl group has 1 to 6 carbon atoms, such as a trimethylsilyl group and a tri-tert-butyldimethylsilyl group.

[Polyhydroxystyrene resin (B2)]

As the polyhydroxystyrene resin (B2), a resin containing a structural unit represented by the following formula (b4) can be used.

The content ratio of the constituent unit represented by the following formula (b4) in the polyhydroxystyrene resin (B2) (the total content ratio in the case of containing multiple types) is preferably 20 mass% or more and 80 mass% or less, more preferably 30 mass% or more and 70 mass% or less, and particularly preferably 40 mass% or more and 60 mass% or less.

In the above formula (b4), R ^8b represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms, and R ^9b represents an acid-dissociable, dissolution-inhibiting group.

The alkyl group having 1 to 6 carbon atoms is, for example, a linear, branched, or cyclic alkyl group having 1 to 6 carbon atoms. Examples of linear or branched alkyl groups 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, and examples of cyclic alkyl groups include a cyclopentyl group, a cyclohexyl group, and the like.

As the acid dissociable dissolution inhibiting group represented by the above R ^9b , acid dissociable dissolution inhibiting groups similar to those exemplified in the above formulas (b2) and (b3), a tert-butyl group, a cyclohexyl ethyl group, a cyclopentyl ethyl group, a cyclohexyl propyl group, a cyclopentyl propyl group, etc. can be used.

In addition, the polyhydroxystyrene resin (B2) can contain other polymerizable compounds as constituent units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anion polymerizable compounds. In addition, examples of such polymerizable compounds include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, formic acid, and itaconic acid; methacrylic acid derivatives having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, and n-butyl (meth)acrylate; (Meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, etc.; (Meth)acrylic acid aryl esters such as phenyl (meth)acrylate, benzyl (meth)acrylate, etc.; dicarboxylic acid diesters such as diethyl maleate, dibutyl formate, etc.; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, α-ethylhydroxystyrene, etc.; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene, isoprene, etc.; nitrile group-containing polymerizable compounds such as acrylonitrile, methacrylonitrile, etc.; chlorine-containing polymerizable compounds such as vinyl chloride, vinylidene chloride, etc. Examples thereof include polymerizable compounds containing amide bonds, such as acrylamide and methacrylamide;

[Acrylic Resin (B3)]

As for the acrylic resin (B3), it is an acrylic resin whose solubility in alkali increases by the action of an acid, and is not particularly limited as long as it is an acrylic resin that has been conventionally mixed in various photosensitive compositions.

The acrylic resin (B3) may contain a structural unit (b-3) derived from an acrylic acid ester containing, for example, a -SO ₂ - containing cyclic group or a lactone containing cyclic group.

(-SO ₂ - containing cyclic group)

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

-SO ₂ - containing cyclic group is preferably a cyclic group containing -SO ₂ - in its ring skeleton, i.e., a cyclic group containing a sultone ring in which -OS- of -SO ₂ - forms part of the ring skeleton.

-The number of carbon atoms in the SO ₂ - containing cyclic group is preferably 3 to 30, more preferably 4 to 20, still more preferably 4 to 15, and 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, it is a -SO ₂ - containing aliphatic cyclic group.

- As the aliphatic cyclic group containing -SO ₂ -, a group can be exemplified which has at least one hydrogen atom removed from an aliphatic hydrocarbon ring in which some of the carbon atoms constituting the ring skeleton are substituted with -SO ₂ - or -SO ₂ -. More specifically, a group can be exemplified which has at least one hydrogen atom removed from an aliphatic hydrocarbon ring in which -CH ₂ - constituting the ring skeleton is substituted with -SO ₂ -, a group in which at least one hydrogen atom is removed from an aliphatic hydrocarbon ring in which -CH ₂ -CH ₂ - constituting the ring is substituted with -SO ₂ -, and the like.

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

-SO ₂ - containing cyclic groups may have substituents. Examples of such substituents include alkyl groups, alkoxy groups, halogen atoms, halogenated alkyl groups, hydroxyl groups, oxygen atoms (=O), -COOR", -OC(=O)R", hydroxyalkyl groups, cyano groups, etc.

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. Specifically, a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, a neopentyl group, an n-hexyl group, and the like can be mentioned. 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. Specifically, a group in which an alkyl group listed as the above-mentioned substituent is bonded to an oxygen atom (-O-) can be mentioned.

As the halogen atom as the substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferable.

As the halogenated alkyl group of the substituent in question, a group in which some or all of the hydrogen atoms of the above-mentioned alkyl group are replaced with the above-mentioned halogen atoms can be exemplified.

As the halogenated alkyl group as the substituent, a group in which some or all of the hydrogen atoms of the alkyl group listed as the above-mentioned substituent are replaced with the above-mentioned halogen atoms can be exemplified. As the halogenated alkyl group, a fluorinated alkyl group is preferable, and a perfluoroalkyl group is particularly preferable.

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

When "R" is a straight-chain or branched-chain alkyl group, the number of carbon atoms of the chain alkyl group is preferably 1 to 10, more preferably 1 to 5, 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 to 15, more preferably 4 to 12, and particularly preferably 5 to 10. Specifically, examples thereof include groups in which one or more hydrogen atoms are removed from a monocycloalkane, a bicycloalkane, a tricycloalkane, a tetracycloalkane, or the like, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. More specifically, examples thereof include groups in which one or more hydrogen atoms are removed from a monocycloalkane, such as cyclopentane or cyclohexane, or a polycycloalkane, such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.

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 listed as the above-mentioned substituent is replaced with a hydroxyl group can be mentioned.

As a _-SO2- containing cyclic group, more specifically, groups represented by the following formulas (3-1) to (3-4) can be mentioned.

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

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

When the alkylene group in question contains an oxygen atom or a sulfur atom, specific examples thereof include groups in which -O- or -S- is present at the terminal or between carbon atoms of the above-mentioned alkylene group, and examples thereof include -O-CH ₂ -, -CH ₂ -O-CH ₂ -, -S-CH ₂ -, -CH ₂ -S-CH ₂ -, etc. 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 one of 0, 1, and 2, with 0 being most preferred. When z is 2, the plurality of R ^10b may be the same or different.

As the alkyl group, alkoxy group, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group in R ^10b , the alkyl group, alkoxy group, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group listed as substituents that the -SO ₂ -containing cyclic group may have are the same as those described above.

Below, specific cyclic groups represented by the aforementioned formulas (3-1) to (3-4) are exemplified. In addition, “Ac” in the formulas represents an acetyl group.

- As the -SO ₂ - containing cyclic group, among the above, a group represented by the above-mentioned formula (3-1) is preferable, and at least one selected from the group consisting of a group represented by any one of the above-mentioned chemical formulas (3-1-1), (3-1-18), (3-3-1), and (3-4-1) is more preferable, and a group represented by the above-mentioned chemical formula (3-1-1) is most preferable.

(Lactone-containing cyclic group)

"Lactone-containing cyclic group" refers to a cyclic group containing a ring (lactone ring) containing -O-C(=O)- in its ring skeleton. The lactone ring is counted as the first ring, and if it is only a lactone ring, it is called a monocyclic group, and if it additionally has another ring structure, it is called a polycyclic group regardless of the structure. The lactone-containing cyclic group may be a monocyclic group or a polycyclic group.

As the lactone-containing cyclic group in the constituent unit (b-3), any one can be used without particular limitation. Specifically, examples of the lactone-containing monocyclic group include a group in which one hydrogen atom is removed from a 4-6 membered ring lactone, for example, a group in which one hydrogen atom is removed from β-propionolactone, a group in which one hydrogen atom is removed from γ-butyrolactone, a group in which one hydrogen atom is removed from δ-valerolactone, and the like. Furthermore, examples of the lactone-containing polycyclic group include a group in which one hydrogen atom is removed from a bicycloalkane, a tricycloalkane, or a tetracycloalkane having a lactone ring.

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

[Composition unit (b-3-S)]

As an example of a constituent unit (b-3-S), more specifically, a constituent unit represented by the following formula (b-S1) can be mentioned.

(In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms, R ^11b is a -SO ₂ - containing cyclic group, and R ^12b is a single bond or a divalent linking group.)

In formula (b-S1), R is as above.

R ^11b is the same as the -SO ₂ - containing cyclic groups listed above.

R ^12b 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.

As the divalent linking group for R ^12b , there is no particular limitation, but a divalent hydrocarbon group which may have a substituent, a divalent linking group containing a hetero atom, etc. are suitable examples.

·A divalent hydrocarbon group that may have a substituent

The hydrocarbon group as the two-valent linking group may be an aliphatic hydrocarbon group or an aromatic hydrocarbon group. The aliphatic hydrocarbon group means a hydrocarbon group that does not have aromaticity. The aliphatic hydrocarbon group may be saturated or unsaturated. Usually, a saturated hydrocarbon group is preferable. More specifically, as the aliphatic hydrocarbon group, a linear or branched aliphatic hydrocarbon group, an aliphatic hydrocarbon group including a ring in the structure, etc. can be mentioned.

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

As the straight-chain aliphatic hydrocarbon group, a straight-chain 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 -], a pentamethylene group [-(CH ₂ ) ₅ -], etc. can be mentioned.

As the branched-chain aliphatic hydrocarbon group, a branched-chain alkylene group is preferable. Specifically, alkyl methylene groups such as -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-; alkyl ethylene groups such as -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 -; -CH(CH ₃ )CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ -, etc.; Alkyl alkylene groups such as alkyl tetramethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, etc. are exemplified. As the alkyl group in the alkyl alkylene group, a straight-chain alkyl group having 1 to 5 carbon atoms is preferable.

The above linear or branched aliphatic hydrocarbon group may or may not have a substituent (a group or atom other than a hydrogen atom) that substitutes 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, an oxo group (=O), etc.

Among the above structures, examples of the aliphatic hydrocarbon group including a ring include a cyclic aliphatic hydrocarbon group (a group in which two hydrogen atoms are removed from the aliphatic hydrocarbon ring) that may include a substituent including a hetero atom in the ring structure, a group in which the cyclic aliphatic hydrocarbon group is bonded to the terminal of a straight-chain or branched-chain aliphatic hydrocarbon group, a group in which the cyclic aliphatic hydrocarbon group is interposed in the middle of a straight-chain or branched-chain aliphatic hydrocarbon group, and the like. Examples of the above-mentioned straight-chain or branched-chain aliphatic hydrocarbon group include those similar to those described above.

The number of carbon atoms in the aliphatic hydrocarbon group of the fantasy is preferably 3 to 20, more preferably 3 to 12.

The aliphatic hydrocarbon group of the ring may be polycyclic or monocyclic. As the monocyclic aliphatic hydrocarbon group, a group having two hydrogen atoms removed 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 having two hydrogen atoms removed 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, and tetracyclododecane.

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

As the alkyl group as the above substituent, an alkyl group having 1 to 5 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.

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

As the halogen atom as the above substituent, a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom can be mentioned, and a fluorine atom is preferable.

As the halogenated alkyl group as the above substituent, a group in which some or all of the hydrogen atoms of the above-mentioned alkyl group are replaced with the above-mentioned halogen atoms can be exemplified.

The aliphatic hydrocarbon group of the ring structure may have some of the carbon atoms constituting it substituted with -O- or -S-. As the substituent containing the hetero atom, -O-, -C(=O)-O-, -S-, -S(=O) ₂ -, -S(=O) ₂ -O- are preferable.

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

Specific examples of aromatic rings include aromatic hydrocarbon rings such as benzene, naphthalene, anthracene, and phenanthrene; aromatic heterocycles in which some of the carbon atoms constituting the aromatic hydrocarbon ring are replaced with heteroatoms; and the like. Examples of heteroatoms in the aromatic heterocycle include oxygen atoms, sulfur atoms, nitrogen atoms, and the like. Specific examples of the aromatic heterocycle include a pyridine ring, a thiophene ring, and the like.

As an aromatic hydrocarbon group as a divalent hydrocarbon group, specific examples thereof include a group having two hydrogen atoms removed from the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle (arylene group or heteroarylene group); a group having two hydrogen atoms removed from an aromatic compound containing two or more aromatic rings (for example, biphenyl, fluorene, etc.); a group having one hydrogen atom removed from the above-mentioned aromatic hydrocarbon ring or aromatic heterocycle (aryl group or heteroaryl group) replaced with an alkylene group (for example, a group having one additional hydrogen atom removed from the aryl group in an arylalkyl group such as a benzyl group, a phenethyl group, a 1-naphthylmethyl group, a 2-naphthylmethyl group, a 1-naphthylethyl group, a 2-naphthylethyl group, etc.); etc.

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

The above-mentioned aromatic hydrocarbon group may have a hydrogen atom of the aromatic hydrocarbon group replaced by a substituent. For example, a hydrogen atom bonded to an aromatic ring in the aromatic hydrocarbon group may be replaced by a substituent. Examples of the substituent include an alkyl group, an alkoxy group, a halogen atom, a halogenated alkyl group, a hydroxyl group, an oxo group (=O), and the like.

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

As the halogen atom as the above substituent, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. can be mentioned, and a fluorine atom is preferable.

As the halogenated alkyl group as the above substituent, a group in which some or all of the hydrogen atoms of the above-mentioned alkyl group are replaced with the above-mentioned halogen atoms can be exemplified.

·Divalent linking group containing heteroatom

In a divalent linking group containing a hetero atom, a hetero atom is an atom other than a carbon atom and a hydrogen atom, and examples thereof include an oxygen atom, a nitrogen atom, a sulfur atom, and a halogen atom.

As a divalent linking group containing a hetero atom, specific examples thereof include non-hydrocarbon linking groups such as -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-, combinations of at least one of these non-hydrocarbon linking groups and a divalent hydrocarbon group, and the like. As the divalent hydrocarbon group, examples thereof include the same divalent hydrocarbon groups which may have a substituent described above, and a straight-chain or branched-chain aliphatic hydrocarbon group is preferable.

Among the above, -NH-, -NH-, -NH-C(=NH)- in -C(=O)-NH- may be substituted with a substituent such as an alkyl group or an acyl group. The number of carbon atoms of the substituent is preferably 1 to 10, more preferably 1 to 8, and particularly preferably 1 to 5.

As the divalent linking group for R ^12b , a linear or branched alkylene group, a cyclic aliphatic hydrocarbon group, or a divalent linking group containing a hetero atom is particularly preferable.

When the divalent linking group in R ^12b is a straight-chain or branched-chain alkylene group, the number of carbon atoms of the alkylene group is preferably 1 to 10, more preferably 1 to 6, particularly preferably 1 to 4, and most preferably 1 to 3. Specifically, among the description of the "divalent hydrocarbon group which may have a substituent" as the divalent linking group mentioned above, examples thereof include the same linear alkylene groups and branched alkylene groups as those listed as linear or branched aliphatic hydrocarbon groups.

In the case where the divalent linking group in R ^12b is a cyclic aliphatic hydrocarbon group, examples of the cyclic aliphatic hydrocarbon group include those similar to the cyclic aliphatic hydrocarbon groups listed as “aliphatic hydrocarbon groups containing a ring in the structure” in the description of “divalent hydrocarbon groups which may have a substituent” as the above-mentioned divalent linking group.

As the aliphatic hydrocarbon group of the present invention, a group having two or more hydrogen atoms removed from cyclopentane, cyclohexane, norbornane, isobornane, adamantane, tricyclodecane, or tetracyclododecane is particularly preferable.

In the case where the divalent linking group in R ^12b is a divalent linking group containing a hetero atom, preferable examples of the linking group include -O-, -C(=O)-O-, -C(=O)-, -OC(=O)-O-, -C(=O)-NH-, -NH- (H may be substituted with a substituent such as an alkyl group or an acyl group), -S-, -S(=O) ₂ -, -S(=O) ₂ -O-, a group represented by the general formula -Y ¹ -OY ² -, -[Y ¹ -C(=O)-O] _m' -Y ² -, or -Y ¹ -OC(=O)-Y ² - [wherein Y ¹ and Y ² are each independently a divalent hydrocarbon group which may have a substituent, O is an oxygen atom, and m' is an integer of 0 to 3.], etc. You can hear it.

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

In the formulas -Y ¹ -OY ² -, -[Y ¹ -C(=O)-O] _m' -Y ² -, or -Y ¹ -OC(=O)-Y ² -, Y ¹ and Y ² are each independently a divalent hydrocarbon group which may have a substituent. Examples of the divalent hydrocarbon group include those similar to the "divalent hydrocarbon group which may have a substituent" listed in the description of the divalent connecting group.

As Y ¹ , a straight-chain aliphatic hydrocarbon group is preferable, a straight-chain alkylene group is more preferable, a straight-chain alkylene group having 1 to 5 carbon atoms is more preferable, and a methylene group and an ethylene group are particularly preferable.

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 alkyl methylene 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 a methyl group is particularly preferable.

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

For the divalent linking group in R ^12b , an organic group composed of a combination of at least one non-hydrocarbon group and a divalent hydrocarbon group is preferable as the divalent linking group containing a hetero atom. Among these, a straight-chain group having an oxygen atom as the hetero atom, for example, a group containing an ether bond or an ester bond, is preferable, and a group represented by the above-mentioned formula -Y ¹ -OY ² -, -[Y ¹ -C(=O)-O] _m' -Y ² -, or -Y ¹ -OC(=O)-Y ² - is more preferable, and a group represented by the above-mentioned formula -[Y ¹ -C(=O)-O] _m' -Y ² -, or -Y ¹ -OC(=O)-Y ² - is particularly preferable.

As the divalent linking group in R ^12b , it is preferable to include an alkylene group or an ester bond (-C(=O)-O-).

The alkylene group is preferably a linear or branched alkylene group. Suitable examples of the linear aliphatic hydrocarbon group include a methylene group [-CH ₂ -], an ethylene group [-(CH ₂ ) ₂ -], a trimethylene group [-(CH ₂ ) ₃ -], a tetramethylene group [-(CH ₂ ) ₄ -], and a pentamethylene group [-(CH ₂ ) ₅ -]. Suitable examples of the branched alkylene group include alkyl methylene groups such as -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 )-, and -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 trimethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ -, - CH ₂ CH(CH ₃ )CH ₂ -; alkyl alkylene groups such as alkyl tetramethylene groups such as -CH(CH ₃ )CH ₂ CH ₂ CH ₂ -, -CH ₂ CH(CH ₃ )CH ₂ CH ₂ -, etc.

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

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

As for R ^13b , there is no particular limitation, and for example, the same two-valent linker as in the aforementioned R ^12b can be mentioned.

As the divalent linking group of R ^13b , a straight-chain or branched-chain alkylene group, an aliphatic hydrocarbon group containing a ring in the structure, or a divalent linking group containing a hetero atom is preferable, and a straight-chain or branched-chain alkylene group, or a divalent linking group containing an oxygen atom as a hetero atom is preferable.

As the straight-chain alkylene group, a methylene group or an ethylene group is preferable, and a methylene group is particularly preferable. As the branched-chain alkylene group, an alkyl methylene group or an alkyl ethylene group is preferable, and -CH(CH ₃ )-, -C(CH ₃ ) ₂ -, or -C(CH ₃ ) ₂ CH ₂ - is particularly preferable.

As a divalent linking group containing an oxygen atom, a divalent linking group containing an ether bond or an ester bond is preferable, and the above-mentioned -Y ¹ -OY ² -, -[Y ¹ -C(=O)-O] _m' -Y ² -, or -Y ¹ -OC(=O)-Y ² - are more preferable. Y ¹ and Y ² are each independently a divalent hydrocarbon group which may have a substituent, and m' is an integer of 0 to 3. Among them, -Y ¹ -OC(=O)-Y ² - is preferable, and a group represented by -(CH ₂ ) _c -OC(=O)-(CH ₂ ) _d - is particularly preferable. c is an integer of 1 to 5, preferably 1 or 2. d is an integer of 1 to 5, preferably 1 or 2.

As the constituent unit (b-3-S), in particular, a constituent unit represented by the following formula (b-S1-11) or (b-S1-12) is preferable, and a constituent unit represented by the formula (b-S1-12) is more preferable.

(In the formula, R, A', R ^10b , z, and R ^13b are each as above.)

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

As R ^13b , a linear or branched alkylene group, or a divalent linking group containing an oxygen atom is preferable. As the linear or branched alkylene group and the divalent linking group containing an oxygen atom for R ^13b , examples thereof include the same groups as the linear or branched alkylene group and the divalent linking group containing an oxygen atom described above, respectively.

As a constituent unit represented by the formula (b-S1-12), in particular, a constituent unit represented by the following formula (b-S1-12a) or (b-S1-12b) is preferable.

(In the formula, R and A' are each the same as above, and c to e are each independently an integer greater than or equal to 1 and less than or equal to 3.)

[Composition unit (b-3-L)]

Examples of the structural unit (b-3-L) include, for example, those in which R ^11b in the above-mentioned formula (b-S1) is substituted with a lactone-containing cyclic group, and more specifically, structural units represented by the following formulas (b-L1) to (b-L5) can be exemplified.

(In the formula, R is a hydrogen atom, an alkyl group having 1 to 5 carbon atoms, or a halogenated alkyl group having 1 to 5 carbon atoms; R' is each independently a hydrogen atom, an alkyl group, an alkoxy group, a halogenated alkyl group, a hydroxyl group, -COOR", -OC(=O)R", a hydroxyalkyl group, or a cyano group; R" is a hydrogen atom or an alkyl group; R ^12b is a single bond or a divalent linking group; s" is an integer of 0 to 2; A" is an alkylene group having 1 to 5 carbon atoms which may include an oxygen atom or a sulfur atom, an oxygen atom, or a sulfur atom; and r is 0 or 1.)

R in equations (b-L1) to (b-L5) is as described above.

As the alkyl group, alkoxy group, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group for R', the same ones as those described above for the alkyl group, alkoxy group, halogenated alkyl group, -COOR", -OC(=O)R", and hydroxyalkyl group listed as substituents that the -SO ₂ - containing cyclic group may have can be exemplified.

Considering that R' is easily obtainable industrially, a hydrogen atom is preferable.

The alkyl group in "R" may be linear, branched, or cyclic.

When "R" is a straight-chain or branched-chain alkyl group, it is preferable that it has 1 to 10 carbon atoms, and more preferably that it has 1 to 5 carbon atoms.

When "R" is a cyclic alkyl group, it is preferably one having 3 to 15 carbon atoms, more preferably one having 4 to 12 carbon atoms, and most preferably one having 5 to 10 carbon atoms. Specifically, examples thereof include groups in which one or more hydrogen atoms are removed from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane, which may or may not be substituted with a fluorine atom or a fluorinated alkyl group. Specifically, examples thereof include groups in which one or more hydrogen atoms are removed from a monocycloalkane such as cyclopentane or cyclohexane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane.

As A", the same ones as A' in the aforementioned formula (3-1) can be mentioned. A" is preferably an alkylene group having 1 to 5 carbon atoms, an oxygen atom (-O-), or a sulfur atom (-S-), and more preferably an alkylene group having 1 to 5 carbon atoms, or -O-. As the alkylene group having 1 to 5 carbon atoms, a methylene group or a dimethyl methylene group is more preferable, and a methylene group is most preferable.

R ^12b is the same as R ^12b in the tactic formula (b-S1).

In formula (b-L1), it is preferable that s" is 1 or 2.

Below, specific examples of the constituent units represented by the aforementioned formulas (b-L1) to (b-L3) are given. In each of the formulas below, R ^α represents a hydrogen atom, a methyl group, or a trifluoromethyl group.

As the constituent unit (b-3-L), at least one selected from the group consisting of constituent units represented by the aforementioned formulae (b-L1) to (b-L5) is preferable, at least one selected from the group consisting of constituent units represented by the aforementioned formulae (b-L1) to (b-L3) is more preferable, and at least one selected from the group consisting of constituent units represented by the aforementioned formulae (b-L1) or (b-L3) is particularly preferable.

Among them, at least one selected from the group consisting of the constituent units represented by the tactic formulas (b-L1-1), (b-L1-2), (b-L2-1), (b-L2-7), (b-L2-12), (b-L2-14), (b-L3-1), and (b-L3-5) is preferable.

In addition, as a constituent unit (b-3-L), a constituent unit represented by the following formulas (b-L6) to (b-L7) is also preferable.

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

In addition, the acrylic resin (B3) includes a structural unit represented by the following formulae (b5) to (b7) having an acid-dissociable group as a structural unit that increases the solubility of the acrylic resin (B3) in alkali by the action of an acid.

In the above formulas (b5) to (b7), R ^14b and R ^18b to R ^23b each independently represent a hydrogen atom, a linear or branched alkyl group having 1 to 6 carbon atoms, a fluorine atom, or a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, R ^15b to R ^17b each independently represent a linear or branched alkyl group having 1 to 6 carbon atoms, a linear or branched fluorinated alkyl group having 1 to 6 carbon atoms, or an aliphatic cyclic group having 5 to 20 carbon atoms, R ^16b and R ^17b may be bonded to each other and form a hydrocarbon ring having 5 to 20 carbon atoms together with the carbon atom to which they are bonded, Y ^b represents an aliphatic cyclic group or alkyl group which may have a substituent, p represents an integer of 0 to 4, q represents 0 or 1.

In addition, 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. In addition, a fluorinated alkyl group is one in which some or all of the hydrogen atoms of the alkyl group are replaced with fluorine atoms.

Specific examples of the aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Specifically, groups in which one hydrogen atom has been removed from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, or cyclooctane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane are mentioned. In particular, groups in which one hydrogen atom has been removed from cyclohexane or adamantane (which may additionally have a substituent) are preferable.

When the above R ^16b and R ^17b do not combine with each other to form a hydrocarbon ring, the above R ^15b , R ^16b and R ^17b are preferably linear or branched alkyl groups having 2 to 4 carbon atoms, from the viewpoint of high contrast and good resolution, depth of focus, etc. The above R ^19b , R ^20b , R ^22b and R ^23b are preferably hydrogen atoms or methyl groups.

The above R ^16b and R ^17b may form an aliphatic cyclic group having 5 to 20 carbon atoms together with the carbon atoms to which they are bonded. Specific examples of such an aliphatic cyclic group include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, and a tetracycloalkane. Specifically, groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, and cyclooctane, or a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, and tetracyclododecane are mentioned. In particular, groups in which one or more hydrogen atoms have been removed from cyclohexane and adamantane (which may additionally have a substituent) are preferable.

In addition, when the aliphatic cyclic group formed by R ^16b and R ^17b has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (=O), and the like, and a straight-chain or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferable.

The above Y ^b is an aliphatic cyclic group or an alkyl group, and examples thereof include groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as a monocycloalkane, a bicycloalkane, a tricycloalkane, or a tetracycloalkane. Specifically, examples thereof include groups in which one or more hydrogen atoms have been removed from a monocycloalkane such as cyclopentane, cyclohexane, cycloheptane, or cyclooctane, or groups in which one or more hydrogen atoms have been removed from a polycycloalkane such as adamantane, norbornane, isobornane, tricyclodecane, or tetracyclododecane. In particular, a group in which one or more hydrogen atoms have been removed from adamantane (which may additionally have a substituent) is preferable.

In addition, when the aliphatic cyclic group of the above Y ^b has a substituent on its ring skeleton, examples of the substituent include polar groups such as a hydroxyl group, a carboxyl group, a cyano group, an oxygen atom (=O), and the like, and a straight-chain or branched alkyl group having 1 to 4 carbon atoms. As the polar group, an oxygen atom (=O) is particularly preferable.

In addition, when Y ^b is an alkyl group, it is preferable that it is a linear or branched alkyl group having 1 to 20 carbon atoms, preferably 6 to 15 carbon atoms. This alkyl group is particularly preferably an alkoxy alkyl group, and examples of this alkoxy alkyl group include a 1-methoxyethyl group, a 1-ethoxyethyl group, a 1-n-propoxyethyl group, a 1-isopropoxyethyl group, a 1-n-butoxyethyl group, a 1-isobutoxyethyl group, a 1-tert-butoxyethyl group, a 1-methoxypropyl group, a 1-ethoxypropyl group, a 1-methoxy-1-methyl-ethyl group, a 1-ethoxy-1-methylethyl group, and the like.

Preferred specific examples of the constituent unit represented by the above formula (b5) include those represented by the following formulas (b5-1) to (b5-33).

In the above formulas (b5-1) to (b5-33), R ^24b represents a hydrogen atom or a methyl group.

Preferred specific examples of the constituent unit represented by the above formula (b6) include those represented by the following formulas (b6-1) to (b6-26).

In the above formulas (b6-1) to (b6-26), R ^24b represents a hydrogen atom or a methyl group.

Preferred specific examples of the constituent unit represented by the above formula (b7) include those represented by the following formulas (b7-1) to (b7-15).

In the above formulas (b7-1) to (b7-15), R ^24b represents a hydrogen atom or a methyl group.

Among the structural units represented by the formulas (b5) to (b7) described above, the structural unit represented by the formula (b6) is preferable because it is easy to synthesize and is also relatively easy to increase sensitivity. Furthermore, among the structural units represented by the formula (b6), the structural unit in which Y ^b is an alkyl group is preferable, and the structural unit in which one or both of R ^19b and R ^20b are alkyl groups is preferable.

The content ratio of the above-mentioned structural unit having an acid-dissociable group in the acrylic resin (B3) (the total content ratio in the case of containing multiple types) is preferably 5 mass% or more and 60 mass% or less, more preferably 10 mass% or more and 55 mass% or less, and particularly preferably 15 mass% or more and 50 mass% or less.

Acrylic resin (B3) is preferably a resin composed of a copolymer including a structural unit derived from a polymerizable compound having an ether bond, together with the structural units represented by the above formulas (b5) to (b7).

As the polymerizable compound having the above ether bond, examples thereof include radical polymerizable compounds such as (meth)acrylic acid derivatives having an ether bond and an ester bond, and specific examples thereof include 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, methoxy triethylene glycol (meth)acrylate, 3-methoxybutyl (meth)acrylate, ethyl galbitol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, and the like. In addition, the polymerizable compound having the ether bond is preferably 2-methoxyethyl (meth)acrylate, 2-ethoxyethyl (meth)acrylate, or methoxy triethylene glycol (meth)acrylate. These polymerizable compounds may be used alone or in combination of two or more.

Additionally, the acrylic resin (B3) may contain other polymerizable compounds as constituent units for the purpose of appropriately controlling physical and chemical properties. Examples of such polymerizable compounds include known radical polymerizable compounds and anion 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, formic acid, and itaconic acid; methacrylic acid derivatives having a carboxy group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; (meth)acrylic acid alkyl esters such as methyl (meth)acrylate, ethyl (meth)acrylate, butyl (meth)acrylate, and cyclohexyl (meth)acrylate; (meth)acrylic acid hydroxyalkyl esters such as 2-hydroxyethyl (meth)acrylate, and 2-hydroxypropyl (meth)acrylate. Examples thereof include (meth)acrylic acid aryl esters such as phenyl (meth)acrylate and benzyl (meth)acrylate; dicarboxylic acid diesters such as diethyl maleate and dibutyl formate; vinyl group-containing aromatic compounds such as styrene, α-methylstyrene, chlorostyrene, chloromethylstyrene, vinyltoluene, hydroxystyrene, α-methylhydroxystyrene, and α-ethylhydroxystyrene; vinyl group-containing aliphatic compounds such as vinyl acetate; conjugated diolefins such as butadiene and isoprene; nitrile group-containing polymerizable compounds such as acrylonitrile and methacrylonitrile; chlorine-containing polymerizable compounds such as vinyl chloride and vinylidene chloride; amide bond-containing polymerizable compounds such as acrylamide and methacrylamide; etc.

As described above, the acrylic resin (B3) may contain a structural unit derived from a polymerizable compound having a carboxyl group, such as the monocarboxylic acid or dicarboxylic acid described above, and in particular, it is preferable that it contains a structural unit derived from (meth)acrylic acid. The proportion of the structural unit derived from (meth)acrylic acid in the acrylic resin (B3) is preferably 5 mass% or more and 20 mass% or less. When it is 5 mass% or more, an undercut shape tends to occur easily, and when it is 20 mass% or less, a resist pattern having a good rectangular cross-sectional shape tends to be formed easily.

In addition, as polymerizable compounds, (meth)acrylic acid esters having an acid-nondissociable aliphatic polycyclic group, vinyl group-containing aromatic compounds, etc. can be mentioned. As the acid-nondissociable aliphatic polycyclic group, a tricyclodecanyl group, an adamantyl group, a tetracyclododecanyl group, an isobornyl group, a norbornyl group, etc. are particularly preferable from the viewpoint of ease of industrial acquisition. These aliphatic polycyclic groups may have a linear or branched alkyl group having 1 to 5 carbon atoms as a substituent.

As a structural unit derived from (meth)acrylic acid esters having a non-dissociable aliphatic polycyclic group, specific examples thereof include those having structures represented by the following formulae (b8-1) to (b8-5).

In the above formulas (b8-1) to (b8-5), R ^25b represents a hydrogen atom or a methyl group.

When the acrylic resin (B3) contains a structural unit (b-3) containing a -SO ₂ - containing cyclic group or a lactone containing cyclic group, the content of the structural unit (b-3) in the acrylic resin (B3) is preferably 5 mass% or more, more preferably 10 mass% or more, particularly preferably 10 mass% or more and 50 mass% or less, and most preferably 10 mass% or more and 30 mass% or less. When the photosensitive resin composition contains the structural unit (b-3) in an amount within the above range, it is easy to achieve both good developability and good pattern shape.

In addition, it is preferable that the acrylic resin (B3) contains 5 mass% or more of the constituent units represented by the aforementioned formulae (b5) to (b7), more preferably 10 mass% or more, and particularly preferably 10 mass% or more and 50 mass% or less.

It is preferable that the acrylic resin (B3) contains a structural unit derived from the polymerizable compound having the above-mentioned ether bond. The content of the structural unit derived from the polymerizable compound having the ether bond in the acrylic resin (B3) is preferably 0 mass% or more and 50 mass% or less, and more preferably 5 mass% or more and 35 mass% or less.

It is preferable that the acrylic resin (B3) contains a structural unit derived from a (meth)acrylic acid ester having the above-mentioned acid non-dissociable aliphatic polycyclic group. The content of the structural unit derived from a (meth)acrylic acid ester having the acid non-dissociable aliphatic polycyclic group in the acrylic resin (B3) is preferably 0 mass% or more and 50 mass% or less, and more preferably 5 mass% or more and 30 mass% or less.

The polystyrene-converted mass average molecular weight of the resin (B) 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 even more preferably 30,000 or more and 300,000 or less. By setting it to such a mass average molecular weight, sufficient strength of the photosensitive layer can be maintained without lowering the peelability from the substrate, and furthermore, swelling of the profile or occurrence of cracks during plating can be prevented.

In addition, the dispersion of the resin (B) is preferably 1.05 or higher. Here, the dispersion is a value obtained by dividing the mass average molecular weight by the number average molecular weight. By setting the dispersion to this degree, it is possible to avoid problems such as stress resistance for desired plating or the metal layer obtained by plating being prone to swelling.

The content of the resin (B) is preferably 5 mass% or more and 98 mass% or less, more preferably 10 mass% or more and 97 mass% or less, more preferably 20 mass% or more and 96 mass% or less, and particularly preferably 25 mass% or more and 60 mass% or less, based on the total solid content of the photosensitive composition.

<Lewis Acid Compound (C)>

The photosensitive composition may or may not contain a Lewis acid compound (C).

By containing a Lewis acid compound (C), it is easy to obtain a highly sensitive photosensitive composition.

In addition, when forming a pattern using a photosensitive composition, if the time required for each process for pattern formation or the time required between each process is long, there are cases where adverse effects such as difficulty in forming a pattern of a desired shape or size or deterioration of developability occur. However, by mixing a Lewis acid compound (C) into the photosensitive composition, such adverse effects on the pattern shape or developability can be alleviated, and the process margin can be widened.

Here, the Lewis acidic compound (C) means "a compound that exhibits the function of an electron pair acceptor and has an empty orbital that can accept at least one electron pair."

As the Lewis acidic compound (C), there is no particular limitation as long as it is a compound that falls under the above definition and is recognized as a Lewis acidic compound by those skilled in the art. As the Lewis acidic compound (C), a compound that does not correspond to a Bronsted acid (protonic acid) is preferably used.

Specific examples of Lewis acid compounds (C) include boron fluoride, ether complexes of boron fluoride (e.g., BF ₃ ·Et ₂ O, BF ₃ ·Me ₂ O, BF ₃ ·THF, etc., where Et is an ethyl group, Me is a methyl group, and THF is tetrahydrofuran), organoboron compounds (e.g., trin-octyl borate, trin-butyl borate, triphenyl borate, and triphenyl boron, etc.), titanium chloride, aluminum chloride, aluminum bromide, gallium chloride, gallium bromide, indium chloride, thallium trifluoroacetate, tin chloride, zinc chloride, zinc bromide, zinc iodide, zinc trifluoromethane sulfonate, zinc acetate, zinc nitrate, zinc tetrafluoroborate, manganese chloride, manganese bromide, nickel chloride, nickel bromide, cyanide. Examples include nickel, nickel acetylacetonate, cadmium chloride, cadmium bromide, stannous chloride, stannous bromide, stannous sulfate, and stannous tartrate.

In addition, other specific examples of Lewis acid compounds (C) include chloride, bromide, sulfate, nitrate, carboxylate, or trifluoromethanesulfonate of rare earth metal elements, cobalt chloride, ferrous chloride, and yttrium chloride.

Here, rare earth metal elements include, for example, lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolinium, ternium, dysprosium, holmium, erbium, thulium, ytterbium, and lutetium.

Because it is easy to obtain and has a good effect upon addition, it is preferable that the Lewis acidic compound (C) contains a Lewis acidic compound containing an element of Group 13 of the periodic table.

Here, elements in Group 13 of the periodic table include boron, aluminum, gallium, indium, and thallium.

Among the elements of Group 13 of the periodic table mentioned above, boron is preferable because of the ease of obtaining the Lewis acid compound (C) and the particularly excellent addition effect. That is, it is preferable that the Lewis acid compound (C) contains a Lewis acid compound containing boron.

As the Lewis acidic compound containing boron, examples thereof include boron halides such as boron fluoride, ether complexes of boron fluoride, boron chloride, and boron bromide, and various organoboron compounds. As the Lewis acidic compound containing boron, an organoboron compound is preferable because the content ratio of halogen atoms in the Lewis acidic compound is low, and the photosensitive composition is easy to apply to applications requiring a low halogen content.

A preferred example of an organoboron compound is the following formula (c1):

B(R ^c1 ) _n1 (OR ^c2 ) _(3-n1) ···(c1)

(In formula (c1), R ^c1 and R ^c2 are each independently a hydrocarbon group having 1 to 20 carbon atoms, the hydrocarbon group may have 1 or more substituents, n1 is an integer of 0 to 3, and when there are plural R ^c1s , two of the plural R ^c1s may be combined with each other to form a ring, and when there are plural OR ^c2s , two of the plural OR ^c2s may be combined with each other to form a ring.)

A boron compound represented by the formula (c1) may be mentioned. It is preferable that the photosensitive composition contains at least one boron compound represented by the formula (c1) as a Lewis acid compound (C).

In formula (c1), when R ^c1 and R ^c2 are hydrocarbon groups, the number of carbon atoms in the hydrocarbon group is 1 to 20. The hydrocarbon group having 1 to 20 carbon atoms may be an aliphatic hydrocarbon group, an aromatic hydrocarbon group, or a hydrocarbon group formed by a combination of an aliphatic group and an aromatic group.

As the hydrocarbon group having 1 to 20 carbon atoms, a saturated aliphatic hydrocarbon group or an aromatic hydrocarbon group is preferable. The number of carbon atoms of the hydrocarbon group as R ^c1 and R ^c2 is preferably 1 to 10. When the hydrocarbon group is an aliphatic hydrocarbon group, the number of carbon atoms is more preferably 1 to 6, and particularly preferably 1 to 4.

The hydrocarbon group as R ^c1 and R ^c2 may be a saturated hydrocarbon group or an unsaturated hydrocarbon group, and is preferably a saturated hydrocarbon group.

When the hydrocarbon groups as R ^c1 and R ^c2 are aliphatic hydrocarbon groups, the aliphatic hydrocarbon groups may be linear, branched, cyclic, or a combination of these structures.

Suitable specific examples of the aromatic hydrocarbon group include a phenyl group, a naphthalen-1-yl group, a naphthalen-2-yl group, a 4-phenyl phenyl group, a 3-phenyl phenyl group, and a 2-phenyl phenyl group. Among these, a phenyl group is preferable.

As the saturated aliphatic hydrocarbon group, an alkyl group is preferable. Suitable specific examples of the alkyl group include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an n-hexyl group, an n-heptyl group, an n-octyl group, a 2-ethylhexyl group, an n-nonyl group, and an n-decyl group.

The hydrocarbon groups as R ^c1 and R ^c2 may have one or more substituents. Examples of the substituents include a halogen atom, a hydroxyl group, an alkyl group, an aralkyl group, an alkoxy group, a cycloalkyloxy group, an aryloxy group, an aralkyloxy group, an alkylthio group, a cycloalkylthio group, an arylthio group, an aralkylthio group, an acyl group, an acyloxy group, an acylthio group, an alkoxycarbonyl group, a cycloalkyloxycarbonyl group, an aryloxycarbonyl group, an amino group, an N-monosubstituted amino group, an N,N-disubstituted amino group, a carbamoyl group (-CO-NH ₂ ), an N-monosubstituted carbamoyl group, an N,N-disubstituted carbamoyl group, a nitro group, and a cyano group.

The number of carbon atoms in the substituent is not particularly limited as long as it does not hinder the purpose of the present invention, but is preferably 1 to 10, more preferably 1 to 6.

Suitable specific examples of the organoboron compound represented by the above formula (c1) include the following compounds. In addition, in the formula below, Pen represents a pentyl group, Hex represents a hexyl group, Hep represents a heptyl group, Oct represents an octyl group, Non represents a nonyl group, and Dec represents a decyl group.

The Lewis acidic compound (C) is preferably used in an amount of 0.01 to 5 parts by mass, more preferably 0.01 to 3 parts by mass, and even more preferably 0.05 to 2 parts by mass, based on 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D) described below.

<Alkali soluble resin (D)>

The photosensitive composition preferably further contains an alkali-soluble resin (D) in order to improve crack resistance. Here, the alkali-soluble resin means a resin film having a thickness of 1 μm formed on a substrate by a resin solution having a resin concentration of 20 mass% (solvent: propylene glycol monomethyl ether acetate), and which dissolves by 0.01 μm or more when immersed in a 2.38 mass% TMAH aqueous solution for 1 minute. The alkali-soluble resin (D) is preferably at least one resin selected from the group consisting of a novolac resin (D1), a polyhydroxystyrene resin (D2), and an acrylic resin (D3).

[Novolac Resin (D1)]

Novolac resins can be obtained, for example, by addition condensation of an aromatic compound having a phenolic hydroxyl group (hereinafter simply referred to as “phenols”) and an aldehyde in the presence of an acid catalyst.

Examples of the above phenols include phenol, o-cresol, m-cresol, p-cresol, o-ethyl phenol, m-ethyl phenol, p-ethyl phenol, o-butyl phenol, m-butyl phenol, p-butyl phenol, 2,3-xylenol, 2,4-xylenol, 2,5-xylenol, 2,6-xylenol, 3,4-xylenol, 3,5-xylenol, 2,3,5-trimethyl phenol, 3,4,5-trimethyl phenol, p-phenyl phenol, resorcinol, hydroquinone, hydroquinone monomethyl ether, pyrogallol, phloroglycinol, hydroxydiphenyl, bisphenol A, gallic acid, gallic acid ester, α-naphthol, β-naphthol, and the like.

Examples of the above aldehydes include formaldehyde, furfural, benzaldehyde, nitrobenzaldehyde, acetaldehyde, etc.

The catalyst used in the addition condensation reaction is not particularly limited, but for example, in acid catalysts, hydrochloric acid, nitric acid, sulfuric acid, formic acid, oxalic acid, acetic acid, etc. are used.

In addition, it is possible to further improve the flexibility of the novolac resin by using o-cresol, replacing the hydrogen atoms of the hydroxyl groups in the resin with other substituents, or using bulky aldehydes.

The weight average molecular weight of the novolac resin (D1) is not particularly limited as long as it does not hinder the purpose of the present invention, but is preferably 1,000 or more and 50,000 or less.

[Polyhydroxystyrene resin (D2)]

As hydroxystyrene compounds constituting the polyhydroxystyrene resin (D2), p-hydroxystyrene, α-methyl hydroxystyrene, α-ethyl hydroxystyrene, etc. can be mentioned. The polyhydroxystyrene resin (D2) may be a homopolymer of a hydroxystyrene compound, or a copolymer of two or more types of hydroxystyrene compounds.

Additionally, the polyhydroxystyrene resin (D2) may be a copolymer of a hydroxystyrene compound and a styrene compound. Examples of the styrene compound include styrene, chlorostyrene, chloromethylstyrene, vinyltoluene, and α-methylstyrene.

The weight average molecular weight of the polyhydroxystyrene resin (D2) is not particularly limited as long as it does not hinder the purpose of the present invention, but is preferably 1,000 or more and 50,000 or less.

[Acrylic Resin (D3)]

As the acrylic resin (D3), it is preferable to include a structural unit derived from a polymerizable compound having an ether bond and a structural unit derived from a polymerizable compound having a carboxyl group.

As the polymerizable compound having the above ether bond, examples thereof include (meth)acrylic acid derivatives having ether bonds and ester bonds, such as 2-methoxy ethyl (meth)acrylate, methoxy triethylene glycol (meth)acrylate, 3-methoxy butyl (meth)acrylate, ethyl galbitol (meth)acrylate, phenoxy polyethylene glycol (meth)acrylate, methoxy polypropylene glycol (meth)acrylate, and tetrahydrofurfuryl (meth)acrylate. The polymerizable compound having the above ether bond is preferably 2-methoxy ethyl acrylate and methoxy triethylene glycol acrylate. These polymerizable compounds may be used alone or in combination of two or more.

As the polymerizable compound having the above carboxyl group, examples thereof include monocarboxylic acids such as acrylic acid, methacrylic acid, and crotonic acid; dicarboxylic acids such as maleic acid, formalic acid, and itaconic acid; compounds having a carboxyl group and an ester bond such as 2-methacryloyloxyethyl succinic acid, 2-methacryloyloxyethyl maleic acid, 2-methacryloyloxyethyl phthalic acid, and 2-methacryloyloxyethyl hexahydrophthalic acid; and the like. The polymerizable compound having the above carboxyl group is preferably acrylic acid or methacrylic acid. These polymerizable compounds may be used alone or in combination of two or more.

The weight average molecular weight of the acrylic resin (D3) is not particularly limited as long as it does not hinder the purpose of the present invention, but is preferably 50,000 or more and 800,000 or less.

The content of the alkali-soluble resin (D) is preferably 0 parts by mass or more and 80 parts by mass or less, and more preferably 0 parts by mass or more and 60 parts by mass or less, when the total of the resin (B) and the alkali-soluble resin (D) is 100 parts by mass. By setting the content of the alkali-soluble resin (D) within the above range, crack resistance tends to be improved and film reduction during development can be prevented.

<Sulfur compound (E)>

The photosensitive composition contains a sulfur-containing compound (E).

The sulfur compound (E) is a compound containing a sulfur atom that can be coordinated to a metal layer on the surface of a substrate forming a pattern.

The sulfur-containing compound (E) includes a nitrogen-containing heterocyclic compound having a mercapto group, or a tautomer of a nitrogen-containing heterocyclic compound having a mercapto group.

As a preferable example of a nitrogen-containing heterocyclic compound having a mercapto group as a sulfur-containing compound (E) or a tautomer of a nitrogen-containing heterocyclic compound having a mercapto group, a compound represented by the following formula (e1-1) or (e1-2) and a tautomer thereof can be mentioned.

(Among equations (e1-1) and (e1-2),

Ring A _e is a monocyclic ring having 4 to 8 ring atoms, or a polycyclic ring having 5 to 20 ring atoms,

X ^1e is -CR ^11e R ^12e -, -NR ^13e -, -O-, -S-, -Se-, -Te-, =CR ^14e -, or =N-,

X ^2e is -CR ^11e =, or -N=,

R ^11e , R ^12e , R ^13e , and R ^14e are each independently a hydrogen atom, an alkyl group having 1 to 8 carbon atoms which may have a substituent, an alkenyl group having 1 to 8 carbon atoms which may have a substituent, an alkynyl group having 1 to 8 carbon atoms which may have a substituent, an aromatic group having 4 to 20 carbon atoms which may have a substituent, or a carboxyl group.

A tautomer of a compound represented by the above formula (e1-1) is, for example, a compound represented by the following formula (e1-1'). A tautomer of a compound represented by the above formula (e1-2) is, for example, a compound represented by the following formula (e1-2').

(In formulas (e1-1') and (e1-2'), ring A _e , X ^1e , R ^11e , R ^12e , R ^13e , and R ^14e are as in formulas (e1-1) and (e1-2), respectively, and X ^3e H is -CR ^11e H-, or -NH-.)

Ring A _e may be either an aromatic heterocycle or an aliphatic heterocycle.

When ring A _e is monocyclic, the number of ring constituent atoms is preferably 5 or more and 7 or less, and more preferably 5 or 6.

Specific examples of the monocyclic ring A _e include a pyrrole ring, an imidazoline ring, an imidazole ring, a triazole ring, a pyridine ring, a pyrimidine ring, a pyridazine ring, a pyrazine ring, a triazine ring, and a thiadiazole ring.

When ring A _e is polycyclic, the number of monocyclic rings constituting the polycyclic ring is preferably 1 or more and 3 or less, and more preferably 1 or 2.

Specific examples of polycyclic rings A _e include an indole ring, a benzimidazole ring, a purine ring, a quinoline ring, an isoquinoline ring, a quinazoline ring, a naphthyridine ring, and a pteridine ring.

Ring A _e may have a substituent. Examples of the substituent that ring A _e may have include a hydroxy group, a mercapto group, an amino group, an amide group, an imide group, a carboxyl group, an alkoxy group, a carboxylic acid ester group, a halogen atom, a saturated or unsaturated hydrocarbon group, an aromatic group that may have a substituent such as a hydroxy group, etc.

As the alkyl group having 1 to 8 carbon atoms which may have a substituent as R ^11e , R ^12e , R ^13e , and R ^14e , examples thereof include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, an isobutyl group, a sec-butyl group, a tert-butyl group, an n-pentyl group, an isopentyl group, and a neopentyl group.

As the alkenyl group having 1 to 8 carbon atoms which may have a substituent as R ^11e , R ^12e , R ^13e , and R ^14e , examples thereof include a 3-butenyl group, a pentenyl group, a hexenyl group, a heptenyl group, and an octenyl group.

As the alkynyl group having 1 to 8 carbon atoms which may have a substituent as R ^11e , R ^12e , R ^13e , and R ^14e , examples thereof include a pentynyl group, a hexynyl group, a heptynyl group, and an octynyl group.

As aromatic groups having 4 to 20 carbon atoms which may have a substituent as R ^11e , R ^12e , R ^13e , and R ^14e , examples thereof include aryl groups such as a phenyl group and a naphthyl group, and heteroaryl groups such as a prolyl group and a thienyl group.

As the substituents that may be present in R ^11e , R ^12e , R ^13e , and R ^14e , an alkyl group having 1 to 8 carbon atoms, an alkenyl group having 1 to 8 carbon atoms, an alkynyl group having 1 to 8 carbon atoms, or an aromatic group having 4 to 20 carbon atoms, include a halogen atom, a cyano group, an oxoalkoxy group, a hydroxy group, an amino group, a nitro group, an aryl group, and an alkyl group substituted with a halogen atom.

In formula (e1-1), it is preferable that X ^1e is -NR ^13e - or =N-.

Compounds represented by formula (e1-1) or (e1-2) include mercapto pyridine, mercapto pyrimidine, mercapto pyridazine, mercapto pyrazine, mercapto triazine, mercapto imidazole, mercapto indazole, mercapto triazole, mercapto thiadiazole, mercapto benzimidazole, etc., each of which may be substituted.

Specific examples of compounds represented by formula (e1-1) or (e1-2) include 2-mercapto pyridine, 2-mercapto nicotinic acid, 2-mercapto pyrimidine, 4-mercapto pyrimidine, 3-mercapto pyridazine, 2-mercapto pyrazine, 2-mercapto-1,3,5-triazine, 3-mercapto-1,2,4-triazine, 2-mercapto imidazole, 2-mercapto-1,3,4-thiadiazole, 2-mercapto benzimidazole, and the like, as well as compounds represented by the following formulas.

Compounds represented by the formula (e1-1＇) or (e1-2＇) include 2-thiouracil, 5-methyl-2-thiouracil, 5,6-dimethyl-2-thiouracil, 6-ethyl-5-methyl-2-thiouracil, 6-methyl-5-n-propyl-2-thiouracil, 5-ethyl-2-thiouracil, 5-n-propyl-2-thiouracil, 5-n-butyl-2-thiouracil, 5-n-hexyl-2-thiouracil, 5-n-butyl-6-ethyl-2-thiouracil, 5-hydroxy-2-thiouracil, 5,6-dihydroxy-2-thiouracil, 5-hydroxy-6-n-propyl-2-thiouracil, 5-Methoxy-2-thiouracil, 5-n-butoxy-2-thiouracil, 5-methoxy-6-n-propyl-2-thiouracil, 5-bromo-2-thiouracil, 5-chloro-2-thiouracil, 5-fluoro-2-thiouracil, 5-amino-2-thiouracil, 5-amino-6-methyl-2-thiouracil, 5-amino-6-phenyl-2-thiouracil, 5,6-diamino-2-thiouracil, 5-aryl-2-thiouracil, 5-aryl-3-ethyl-2-thiouracil, 5-aryl-6-phenyl-2-thiouracil, 5-benzyl-2-thiouracil, 5-benzyl-6-methyl-2-thiouracil, 5-Acetamido-2-thiouracil, 6-methyl-5-nitro-2-thiouracil, 6-amino-2-thiouracil, 6-amino-5-methyl-2-thiouracil, 6-amino-5-n-propyl-2-thiouracil, 6-bromo-2-thiouracil, 6-chloro-2-thiouracil, 6-fluoro-2-thiouracil, 6-bromo-5-methyl-2-thiouracil, 6-hydroxy-2-thiouracil, 6-acetamido-2-thiouracil, 6-n-octyl-2-thiouracil, 6-dodecyl-2-thiouracil, 6-tetradodecyl-2-thiouracil, 6-hexadecyl-2-thiouracil, 6-(2-Hydroxyethyl)-2-thiouracil, 6-(3-isopropyloctyl)-5-methyl-2-thiouracil, 6-(m-nitrophenyl)-2-thiouracil, 6-(m-nitrophenyl)-5-n-propyl-2-thiouracil, 6-α-naphthyl-2-thiouracil, 6-α-naphthyl-5-t-butyl-2-thiouracil, 6-(p-chlorophenyl)-2-thiouracil, 6-(p-chlorophenyl)-2-ethyl-2-thiouracil, 5-ethyl-6-eicosyl-2-thiouracil, 6-acetamido-5-ethyl-2-thiouracil, 6-eicosyl-5-aryl-2-thiouracil, Examples of thiouracil derivatives include 5-amino-6-phenyl-2-thiouracil, 5-amino-6-(p-chlorophenyl)-2-thiouracil, 5-methoxy-6-phenyl-2-thiouracil, 5-ethyl-6-(3,3-dimethyloctyl)-2-thiouracil, and 6-(2-bromoethyl)-2-thiouracil.

The amount of the sulfur compound (E) to be used is preferably 0.01 parts by mass or more and 5 parts by mass or less, 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, based on 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D).

<Mountain diffusion control agent (F)>

The photosensitive composition contains an acid diffusion inhibitor (F). The acid diffusion inhibitor (F) is not particularly limited as long as the photosensitive composition satisfies the above-mentioned [requirement 1]. The acid diffusion inhibitor (F) can improve the shape of a resist pattern used as a template, the storage stability of a photosensitive composition film, etc. As the acid diffusion control agent (F), a nitrogen-containing compound (F1) is preferable, and additionally, an organic carboxylic acid, a phosphorus oxo acid, or a derivative thereof (F2) can be contained, if necessary.

[Nitrogen compound (F1)]

Nitrogen-containing compounds (F1) include trimethylamine, diethylamine, triethylamine, di-n-propylamine, tri-n-propylamine, tri-n-pentylamine (triamylamine), tribenzylamine, diethanolamine, triethanolamine, 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, propionamide, benzamide, Examples thereof include pyrrolidone, N-methylpyrrolidone, methylurea, 1,1-dimethylurea, 1,3-dimethylurea, 1,1,3,3-tetramethylurea, 1,3-diphenylurea, imidazole, benzimidazole, 4-methylimidazole, 8-oxyquinoline, acridine, purine, pyrrolidine, piperidine, 4-hydroxypentamethylpiperidine, 2,4,6-tri(2-pyridyl)-S-triazine, morpholine, 4-methylmorpholine, piperazine, 1,4-dimethyl piperazine, 1,4-diazabicyclo[2.2.2]octane, pyridine, etc. These may be used alone or in combination of two or more.

In addition, commercially available hindered amine compounds such as Adekastab LA-52, Adekastab LA-57, Adekastab LA-63 P, Adekastab LA-68, Adekastab LA-72, Adekastab LA-77 Y, Adekastab LA-77 G, Adekastab LA-81, Adekastab LA-82, and Adekastab LA-87 (all manufactured by ADEKA) can also be used as the nitrogen-containing compound (F1).

From the point that it is easy to obtain a photosensitive composition satisfying [requirement 1] of the foregoing, the photosensitive composition preferably contains, as the nitrogen-containing compound (F1), an aliphatic tertiary amine such as a trialkylamine, and preferably contains trimethylamine, triethylamine, tripropylamine or tributylamine.

The nitrogen compound (F1) is preferably used in an amount of 0.01 to 3 parts by mass, and particularly preferably used in an amount of 0.05 to 1 part by mass, relative to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D).

[Organic carboxylic acid, or phosphorus oxo acid or its derivative (F2)]

Among organic carboxylic acids, or phosphorus oxo acids or derivatives thereof (F2), specifically, malonic acid, citric acid, malic acid, succinic acid, benzoic acid, salicylic acid, etc. are suitable as organic carboxylic acids, and salicylic acid is particularly preferable.

Examples of the oxo acids of phosphorus or derivatives thereof include derivatives such as phosphoric acid, phosphoric acid di-n-butyl ester, and phosphoric acid diphenyl ester and their esters; derivatives such as phosphonic acid, phosphonic acid dimethyl ester, phosphonic acid di-n-butyl ester, phenyl phosphonic acid, phosphonic acid diphenyl ester, and phosphonic acid dibenzyl ester and their esters; derivatives such as phosphinic acid, phenyl phosphinic acid and their esters; and the like. 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 thereof (F2) is usually used in a range of 0 to 5 parts by mass, and particularly preferably used in a range of 0 to 3 parts by mass, with respect to 100 parts by mass of the total mass of the resin (B) and the alkali-soluble resin (D).

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

<Organic solvent (S)>

The photosensitive composition contains an organic solvent (S). The type of the organic solvent (S) is not particularly limited as long as it does not hinder the purpose of the present invention, and can be appropriately selected and used from organic solvents that have been conventionally used in positive-type photosensitive compositions.

Specific examples of the organic solvent (S) include ketones such as acetone, methyl ethyl ketone, cyclohexanone, methyl isoamyl ketone, and 2-heptanone; polyhydric alcohols and derivatives thereof such as ethylene glycol, ethylene glycol monoacetate, diethylene glycol, diethylene glycol monoacetate, propylene glycol, propylene glycol monoacetate, dipropylene glycol, monomethyl ether of dipropylene glycol monoacetate, monoethyl ether, monopropyl ether, monobutyl ether, and monophenyl ether; cyclic ethers such as dioxane; Esters such as ethyl formate, methyl lactate, 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-methyl propionate, methyl 2-hydroxy-3-methyl butanoate, 3-methoxy butyl acetate, and 3-methyl-3-methoxy butyl acetate; aromatic hydrocarbons such as toluene and xylene; etc. These may be used alone or as a mixture of two or more.

The content of the organic solvent (S) is not particularly limited as long as it does not hinder the purpose of the present invention. When the photosensitive composition is used for a thick film application where the film thickness of the photosensitive layer obtained by a spin coating method or the like is 5 μm or more, it is preferable to use the organic solvent (S) in a range where the solid content concentration of the photosensitive composition is 20 mass% or more and 55 mass% or less.

<Other ingredients>

The photosensitive composition may additionally contain a polyvinyl resin in order to improve reversibility. Specific examples of the polyvinyl resin include polyvinyl chloride, polystyrene, polyhydroxystyrene, polyvinyl acetate, polyvinyl benzoic acid, polyvinyl methyl ether, polyvinyl ethyl ether, polyvinyl alcohol, polyvinyl pyrrolidone, polyvinyl phenol, and copolymers thereof. The polyvinyl resin is preferably polyvinyl methyl ether because of its low glass transition point.

In addition, the photosensitive composition may additionally contain an adhesive agent to improve the adhesion between a mold formed using the photosensitive composition and a metal substrate.

In addition, the photosensitive composition may additionally contain a surfactant in order to improve the coating properties, foaming properties, leveling properties, etc. As the surfactant, for example, a fluorine-based surfactant or a silicone-based surfactant is preferably used.

Specific examples of fluorine-based surfactants include commercially available fluorine-based surfactants such as BM-1000, BM-1100 (all manufactured by BM Chemistry), Megapak R-40, Megapak F142D, Megapak F172, Megapak F173, Megapak F183 (all manufactured by DIC), Fluorad FC-135, Fluorad FC-170C, Fluorad FC-430, Fluorad FC-431 (all manufactured by Sumitomo 3M), Surfron S-112, Surfron S-113, Surfron S-131, Surfron S-141, Surfron S-145 (all manufactured by Asahi Glass), SH-28PA, SH-190, SH-193, SZ-6032, and SF-8428 (all manufactured by Toray Silicone). Surfactants include, but are not limited to, these.

As silicone surfactants, unmodified silicone surfactants, polyether-modified silicone surfactants, polyester-modified silicone surfactants, alkyl-modified silicone surfactants, aralkyl-modified silicone surfactants, and reactive silicone surfactants can be preferably used.

As the silicone surfactant, a commercially available silicone surfactant can be used. Specific examples of commercially available silicone surfactants include Painted M (manufactured by Toray/Dow Corning), Topeka K1000, Topeka K2000, and Topeka K5000 (all manufactured by Takachiho Sangyo), XL-121 (polyether-modified silicone surfactant, manufactured by Clariant), and BYK-310 (polyester-modified silicone surfactant, manufactured by Big Chemie).

In addition, the photosensitive composition may additionally contain an acid, an acid anhydride, or a high-boiling-point solvent to perform fine adjustment of solubility in a developer.

Specific examples of acids and acid anhydrides include monocarboxylic acids such as acetic acid, propionic acid, n-butyric acid, isobutyric acid, n-valeric acid, isovaleric acid, benzoic acid, and cinnamic acid; hydroxymonocarboxylic acids such as lactic acid, 2-hydroxybutyric acid, 3-hydroxybutyric acid, salicylic acid, m-hydroxybenzoic acid, p-hydroxybenzoic acid, 2-hydroxycinnamic acid, 3-hydroxycinnamic acid, 4-hydroxycinnamic acid, 5-hydroxyisophthalic acid, and syringic acid; Polyhydric carboxylic acids such as 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, and 1,2,5,8-naphthalenetetracarboxylic acid; Acid anhydrides such as itaconic anhydride, succinic anhydride, citraconic anhydride, dodecenyl succinic anhydride, tricarbanilic anhydride, maleic anhydride, hexahydrophthalic anhydride, methyl tetrahydrophthalic anhydride, himic anhydride, 1,2,3,4-butane tetracarboxylic acid anhydride, cyclopentane tetracarboxylic acid-2 anhydride, phthalic anhydride, pyromellitic anhydride, trimellitic anhydride, benzophenone tetracarboxylic acid anhydride, ethylene glycol bis trimellitate anhydride, and glycerin tris trimellitate anhydride; etc.

In addition, specific examples of high boiling point solvents include N-methyl formamide, N,N-dimethyl formamide, N-methyl formanilide, N-methylacetamide, N,N-dimethylacetamide, N-methyl pyrrolidone, dimethyl sulfoxide, benzyl ethyl ether, dihexyl ether, acetonyl acetone, isophorone, capronic acid, caprylic acid, 1-octanol, 1-nonanol, benzyl alcohol, benzyl acetate, ethyl benzoate, diethyl oxalate, diethyl maleate, γ-butyrolactone, ethylene carbonate, propylene carbonate, phenyl cellosolve acetate, and the like.

Additionally, the photosensitive composition may additionally contain a sensitizer to improve sensitivity.

<Method for preparing chemically amplified positive photosensitive composition>

The chemically amplified positive photosensitive composition is prepared by mixing and stirring the above components in a conventional manner. Devices that can be used when mixing and stirring the above components include a dissolver, a homogenizer, a three-roll mill, etc. After the above components are uniformly mixed, the obtained mixture may be further filtered using a mesh, membrane filter, etc.

≪Photosensitive dry film≫

A photosensitive dry film has a base film and a photosensitive layer formed on the surface of the base film, and the photosensitive layer is made of the above-mentioned photosensitive composition.

As the base film, one having light transmittance is preferable. Specifically, polyethylene terephthalate (PET) film, polypropylene (PP) film, polyethylene (PE) film, etc. can be mentioned, but polyethylene terephthalate (PET) film is preferable because it has an excellent balance of light transmittance and breaking strength.

A photosensitive dry film is manufactured by forming a photosensitive layer by applying the aforementioned photosensitive composition onto a substrate film.

In forming a photosensitive layer on a substrate film, an applicator, a bar coater, a wire bar coater, a roll coater, a curtain flow coater, or the like is used, and a photosensitive composition is applied onto the substrate film and dried so that the film thickness after drying is preferably 0.5 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 additionally have a protective film on the photosensitive layer. Examples of the protective film include polyethylene terephthalate (PET) film, polypropylene (PP) film, and polyethylene (PE) film.

≪Method for manufacturing a mold-attached substrate≫

The method for forming a patterned resist film on a substrate using the photosensitive composition described above is not particularly limited. This patterned resist film is suitably used as a mold for forming an insulating film, an etching mask, and a plating structure.

A suitable method for manufacturing such a mold-attached substrate is as follows:

A process for laminating a photosensitive layer made of the above-described photosensitive composition on a substrate having a metal layer on the surface,

A process of heating the photosensitive layer to a temperature of 60℃ or higher and 130℃ or lower,

A process of selectively irradiating active light or radiation to a photosensitive layer after heating,

A process of developing a photosensitive layer after irradiation to create a mold for forming a plated object having a pattern shape.

A method including:

Each process is described below. The process of laminating a photosensitive layer made of the above-described photosensitive composition on a substrate having a metal layer on the surface is also referred to as a “lamination process.” The process of heating the photosensitive layer is also referred to as a “heating process.” The process of selectively irradiating the heated photosensitive layer with active light or radiation is also referred to as an “exposure process.” The process of developing the irradiated photosensitive layer to create a mold for forming a plated shape having a pattern shape is also referred to as a “development process.”

<Lamination process>

In the lamination process, a photosensitive layer made of the above-described photosensitive composition is laminated on a substrate having a metal layer on its surface.

When manufacturing a mold-attached substrate having a mold for forming a plated shape, a substrate having a metal layer on its surface (a substrate having a metal surface) is used as the substrate. As the metal species constituting the metal layer, copper, gold, and aluminum are preferable, and copper is more preferable.

The photosensitive layer is laminated on a substrate having a metal layer on its surface, for example, by applying a liquid photosensitive composition onto the metal layer on the surface of the substrate. Additionally, the photosensitive layer may be laminated on the substrate using the above-described photosensitive dry film.

The thickness of the photosensitive layer is not particularly limited as long as the resist pattern to be used as the mold can be formed to a desired film thickness, 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 composition onto a 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.

<Heating process (pre-bake)>

In the heating process, the photosensitive layer is heated to a temperature of 60°C or higher and 130°C or lower. In this way, since the heating temperature is low, adverse effects on the substrate due to heating are suppressed.

By heating, the solvent (organic solvent (S)) is removed.

The heating temperature is 60℃ or higher and 130℃ or lower, preferably 80℃ or higher and 130℃ or lower, and more preferably 105℃ or higher and 125℃ or lower.

The heating time is preferably 60 seconds or more and 550 seconds or less, and more preferably 90 seconds or more and 240 seconds or less.

In the heating process, as the solvent is removed, the acid generator (A) partially decomposes and generates acid by reacting with the metal layer on the substrate surface, and furthermore, this reaction is promoted by the acid diffusion inhibitor (F). As a result, in the region near the substrate surface of the photosensitive layer, the solubility of the resin (B) in alkali increases.

<Exposure process>

In the exposure process, the photosensitive layer after heating is selectively irradiated with active light or radiation. The selective exposure is performed so that the location where the plated structure is formed is removed by development.

Specifically, for the photosensitive layer after heating, active light or radiation, for example, ultraviolet light or visible light having a wavelength of 300 nm or more and 500 nm or less, is selectively irradiated (exposed) through a mask of a predetermined pattern. By selectively irradiating (exposing) with active light or radiation, the acid generator (A) decomposes to generate acid in the exposed portion, and the solubility of the resin (B) in alkali increases.

As a source of radiation, a low-pressure mercury lamp, a high-pressure mercury lamp, an ultra-high-pressure mercury lamp, a metal halide lamp, an argon gas laser, etc. can be used. In addition, radiation includes microwaves, infrared rays, visible light, ultraviolet rays, X-rays, γ-rays, electron rays, proton rays, neutron rays, ion rays, etc. The dose of radiation varies depending on the composition of the photosensitive composition or the film thickness of the photosensitive layer, but, for example, in the case of using an ultra-high-pressure mercury lamp, it is 100 mJ/cm ² or more and 10,000 mJ/cm ² or less. In addition, radiation includes light rays that activate an acid generator (A) in order to generate acid.

After exposure, the photosensitive layer is heated (PEB) using a known method to promote acid diffusion, thereby changing the alkaline solubility of the photosensitive layer in the exposed portion of the photosensitive layer.

The post-exposure heating (PEB) conditions are not particularly limited. The heating temperature is preferably 60°C or more and 130°C or less, and more preferably 80°C or more and 120°C or less. The heating time is preferably 30 seconds or more and 240 seconds or less, and more preferably 60 seconds or more and 180 seconds or less.

<Phenomena Process>

In the development process, the photosensitive layer after irradiation is developed to create a mold for forming a plated shape having a pattern shape.

By dissolving and removing unnecessary parts through the development, a resist pattern that serves as a mold for forming a plated structure having a pattern shape is formed. At this time, an alkaline aqueous solution is used as the developing solution.

As the developer, for example, an aqueous solution of an alkali such as sodium hydroxide, potassium hydroxide, sodium carbonate, sodium silicate, sodium metasilicate, ammonia water, ethylamine, n-propylamine, diethylamine, di-n-propylamine, triethylamine, methyl diethylamine, dimethyl ethanolamine, triethanolamine, tetramethyl ammonium hydroxide, tetraethyl ammonium hydroxide, pyrrole, piperidine, 1,8-diazabicyclo[5,4,0]-7-undecene, 1,5-diazabicyclo[4,3,0]-5-nonane can be used. In addition, 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 aqueous solution of the above alkali can also be used as the developer.

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

After development, perform water washing for 30 to 90 seconds, and dry using an air arm or oven.

The resist pattern formed in this way has a cross-sectional shape with a large undercut because it uses the photosensitive composition described above, and also has excellent adhesion to the substrate.

≪Method for manufacturing plated sculptures≫

A method for manufacturing a plated shape includes a process of forming a plated shape within a mold by applying plating to a mold-attached substrate formed by the above-described method.

Specifically, by plating a conductor such as a metal into a non-resist portion (a portion removed by a developer) of a mold of a mold-attached substrate formed by the above-mentioned method, for example, a connection terminal such as a bump or a metal post, or a plated structure such as a Cu rewiring can be formed. In addition, the plating treatment method is not particularly limited, and various methods known in the art can be adopted. As the plating solution, a hand plating solution, a copper plating solution, a gold plating solution, or a nickel plating solution is particularly suitably used. Finally, the remaining mold is removed using a stripping solution or the like according to a commercial method.

When manufacturing a plated shape, it is preferable to perform an ashing treatment on the non-resist portion of the resist pattern that serves as a mold for forming the plated shape. If the above ashing treatment is performed, it is easy to form a plated shape that adheres better to the metal surface.

The ashing treatment is not particularly limited as long as it does not cause damage to the resist pattern that serves as a mold for forming a plated shape to the extent that a plated shape of the desired shape cannot be formed.

A preferred ashing treatment method is a method using oxygen plasma. In order to ashing a metal surface on a substrate using oxygen plasma, a known oxygen plasma generator is used to generate oxygen plasma, and the oxygen plasma is irradiated onto the metal surface on the substrate.

As the gas used for generating oxygen plasma, various gases that have been conventionally used for plasma treatment together with oxygen can be mixed within a range that does not hinder the purpose of the present invention. Examples of such gases include nitrogen gas, hydrogen gas, and CF ₄ gas.

The processing conditions using oxygen plasma are not particularly limited as long as they do not impede the purpose of the present invention, but the processing time is, for example, in a range of 10 seconds to 20 minutes, preferably in a range of 20 seconds to 18 minutes, and more preferably in a range of 30 seconds to 15 minutes.

By setting the treatment time by oxygen plasma within the above range, it becomes easy to achieve the effect of improving the adhesion of the plated structure without causing a change in the shape of the resist pattern.

According to the above method, a resist pattern having a cross-sectional shape with a large undercut and excellent adhesion to a substrate can be used as a mold for forming a plated shape.

Since the resist pattern has a cross-sectional shape in which a large undercut is formed, a plated structure with a large footing can be formed. For this reason, the plated structure is unlikely to collapse, and a plated structure with an excellent destruction margin can be formed. Therefore, for example, after forming a plated structure such as a bump, a metal post, or a wiring, even if the substrate surface is rinsed with a rinse solution, gas is sprayed on the substrate surface for the purpose of drying, or a chemical treatment such as etching is performed, or a material for forming another member is applied or filled on the substrate for the purpose of providing another member on the substrate, the plated structure is unlikely to collapse.

In addition, since the adhesion to the substrate is excellent, peeling of the resist pattern during development or plating is suppressed, and a plated shape of a desired shape can be manufactured.

[Example]

Hereinafter, the present invention will be described in further detail by examples, but the present invention is not limited to these examples.

[Examples 1 to 65 and Comparative Examples 1 to 6]

In Examples 1 to 65 and Comparative Examples 1 to 6, compounds A1 to A13 of the following formula were used as acid generators (A). In the formula below, Bu represents a butyl group and iPR represents an isopropyl group.

In Examples 1 to 65 and Comparative Examples 1 to 6, the following Resins B1 to B10 were used as the resin (Resin (B)) whose solubility in alkali increases by the action of an acid. The number on the lower right of the parentheses in each structural unit in the structural formula below represents the content (mass%) of the structural unit in each resin. The mass average molecular weight (Mw) of Resin B1 is 20000. The mass average molecular weights (Mw) of Resin B2 and Resin B3 are 10000. The mass average molecular weight (Mw) of Resin B4 is 40000, and the dispersity (Mw/Mn) of Resin B4 is 12. The mass average molecular weight (Mw) of Resin B5 is 40000, and the dispersity (Mw/Mn) of Resin B5 is 12. The mass average molecular weight (Mw) of Resin B6 is 40000, and the polydispersity (Mw/Mn) of Resin B6 is 12. The mass average molecular weight (Mw) of Resin B7 is 40000, and the polydispersity (Mw/Mn) of Resin B7 is 12. The mass average molecular weight (Mw) of Resin B8 is 10000, and the polydispersity (Mw/Mn) of Resin B8 is 2. The mass average molecular weight (Mw) of Resin B9 is 10000, and the polydispersity (Mw/Mn) of Resin B9 is 2. The mass average molecular weight (Mw) of Resin B10 is 10000, and the polydispersity (Mw/Mn) of Resin B10 is 2.

As the alkali-soluble resin (D), the following resins D1 to D3 were used. The mass average molecular weight (Mw) of D1 (novolac resin) is 16000, and the dispersity (Mw/Mn) of resin D1 is 18. The mass average molecular weight (Mw) of D2 (novolac resin) is 5000, and the dispersity (Mw/Mn) of resin D2 is 6. The mass average molecular weight (Mw) of D3 (polyhydroxystyrene resin) is 2500, and the dispersity (Mw/Mn) of resin D3 is 2.

As sulfur compounds (E), the following compounds E1 to E8 were used.

As a acid diffusion inhibitor (F), the following F1 was used.

F1: Tributylamine

The types and amounts (mass parts) of the acid generator (A), the resin (B), the alkali-soluble resin (D), the sulfur-containing compound (E), 0.20 mass parts of F1 (acid diffusion inhibitor (F)), and 0.04 mass parts of the surfactant (Megapack R-40, manufactured by DIC Corporation) described in Tables 1 to 4 were dissolved in propylene glycol monomethyl ether acetate so that the solid concentration became 30 mass%, thereby obtaining the photosensitive compositions of each example and comparative example.

For each example and each comparative example, it was confirmed whether the photosensitive composition satisfied the above-mentioned [Requirement 1] or not. The specific prescription is written below.

First, a photosensitive composition (chemically amplified positive photosensitive composition) was applied to a substrate (copper substrate) having a copper layer formed on the surface by a sputtering method, thereby forming a resin film having a thickness of 8.5 μm (process 1).

The substrate on which the resin film was formed was heated at 140°C for 300 seconds (process 2).

After heating, a portion of the resin film was shaved off, the shaved resin film was dissolved in propylene glycol monomethyl ether acetate so that the solid concentration became 20 mass%, and then acetonitrile in a mass 15 times the mass of the shaved resin film was added, and the liquid from which the sediment was removed was used as test solution 1 (process 3).

In addition, the photosensitive composition (chemically amplified positive type photosensitive composition) was diluted with propylene glycol monomethyl ether acetate so that the solid content concentration became 20 mass%, and then acetonitrile was added in an amount 15 times the mass of the solid content of the photosensitive composition (chemically amplified positive type photosensitive composition), and the liquid after excluding the precipitate was used as test solution 2. This test solution 2 and the test solution 1 obtained in step 3 were each analyzed by liquid chromatography, thereby obtaining the decomposition rate (%) of the acid generator (A) represented by the following formula (a) (step 4). In addition, the quantification of the acid generator (A) by liquid chromatography used an external standard method using the acid generator (A) in each photosensitive composition as a standard substance.

Decomposition rate (%) of acid generator (A) = (1-(x/y))Х100　　　···(a)

(In formula (a), x is the content (mass%) of the acid generator (A) in the resin film, and can be obtained from the analysis results of test solution 1. In addition, y is the content (mass%) of the acid generator (A) in the solid content of the photosensitive composition (chemically amplified positive type photosensitive composition), and can be obtained from the analysis results of test solution 2.)

The decomposition rate (%) of the acid generator (A) represented by the obtained formula (a) is written in the “Acid generator decomposition rate (%)” column of Tables 1 to 4.

[Formation of the registration pattern]

<Formation of a line and space pattern with a line width of 1.0 μm and a space width of 1.0 μm>

The photosensitive compositions of the examples and comparative examples were applied onto a copper substrate having a diameter of 8 inches (a substrate having a copper layer formed on the surface by a sputtering method) to form a photosensitive layer having a film thickness of 5.0 μm. Next, the photosensitive layer was prebaked at 120°C for 180 seconds. After the prebaking, a mask having a line-and-space pattern with a line width of 1.0 μm and a space width of 1.0 μm and an exposure device FPA-5510 iV (manufactured by Canon Inc.) were used to perform pattern exposure with the i-line (wavelength: 365 nm). The exposure dose was set to an exposure dose such that the pattern width (width of the resist portion) (Wm) of the middle part of the thickness direction of the substrate of the resist pattern cross-section became 1.0 μm. Next, the substrate was placed on a hot plate and post-exposure baking (PEB) was performed at 90°C for 90 seconds. Thereafter, a 2.38 wt% aqueous solution of tetramethyl ammonium hydroxide (developer, NMD-3, manufactured by Tokyo Ohka Kogyo Co., Ltd.) was dropped onto the exposed photosensitive layer, followed by incubation at 23°C for 30 seconds. This operation was repeated a total of three times. Thereafter, the resist pattern surface was washed with running water, and then nitrogen was blown to obtain a resist pattern.

<Formation of a line and space pattern with a line width of 2.0 μm and a space width of 2.0 μm>

As a mask, a mask having a line-and-space pattern with a line width of 2.0 μm and a space width of 2.0 μm was used, and the exposure dose was set to such that the pattern width (width of the resist portion) (Wm) of the middle part of the thickness direction of the substrate of the resist pattern cross-section was 2.0 μm, and a resist pattern was obtained in the same manner as in the above <Formation of a line-and-space pattern with a line width of 1.0 μm and a space width of 1.0 μm>.

<Formation of a line and space pattern with a line width of 4.0 μm and a space width of 4.0 μm>

As a mask, a mask having a line-and-space pattern with a line width of 4.0 μm and a space width of 4.0 μm was used, and the exposure dose was set to an exposure dose such that the pattern width (width of the resist portion) (Wm) of the middle part of the thickness direction of the substrate of the resist pattern cross-section was 4.0 μm, and a resist pattern was obtained in the same manner as in the above <Formation of a line-and-space pattern with a line width of 1.0 μm and a space width of 1.0 μm>.

[Evaluation of the adhesion of the resist pattern to the substrate (peeling from the substrate)]

The obtained resist pattern was observed with a scanning electron microscope, and a case in which no peeling was observed at all between 1.0 μm and 4.0 μm was judged as ◎, a case in which peeling was observed at 1.0 μm but not at 2.0 μm and 4.0 μm was judged as ○, and a case in which peeling was observed at all between 1.0 μm and 4.0 μm was judged as Х. The results are shown in Tables 1 to 4.

[Evaluation of shape] Evaluation of undercut in the cross section of the resist pattern

For the obtained resist pattern, the cross-sectional shape was observed by a scanning electron microscope, and the amount of undercut was measured as follows. Fig. 2 is a diagram schematically showing a cross-section parallel to the thickness direction of the substrate of the resist pattern in which the undercut was observed by a scanning electron microscope in the examples and comparative examples.

In Fig. 2, a resist pattern having a resist portion (12) and a non-resist portion (13) is formed on a substrate (11). First, on a side wall (14), which is an interface between the resist portion (12) and the non-resist portion (13), an inflection point (15), which is a location where undercutting on the side wall (14) begins, is determined. A perpendicular line (16) is drawn from the inflection point (15) toward the surface of the substrate (11), and the intersection of the perpendicular line (16) and the surface of the substrate (11) is set as the undercut starting point (17). In addition, the intersection of the curve of the side wall (14) and the surface of the substrate (11) is set as the undercut ending point (18). The width (Wu) between the undercut starting point (17) and the undercut ending point (18) determined in this manner is set as the undercut amount. From the obtained undercut amount value, the degree of undercut was evaluated according to the following criteria.

In addition, in any one of the embodiments and comparative examples, <Formation of a line-and-space pattern with a line width of 1.0 μm and a space width of 1.0 μm>, <Formation of a line-and-space pattern with a line width of 2.0 μm and a space width of 2.0 μm>, and <Formation of a line-and-space pattern with a line width of 4.0 μm and a space width of 4.0 μm>, the amount of undercut was the same.

<Evaluation criteria>

When the undercut amount (Wu) (the amount of erosion of the resist pattern on the substrate surface side) exceeded 0.25 μm, it was judged as ◎, when it was 0.20 μm or more and 0.25 μm or less, it was judged as ○, and when it was less than 0.20 μm, it was judged as Х. The results are shown in Tables 1 to 4.

Resin (B) Alkali soluble resin (D) Acid generator (A) Sulfur compounds (E) Acid generator decomposition rate (%) Pattern peeling Undercut Type/mass Type/mass Type/mass Type/mass Example 1 B1/60 D1/40 A1/1.5 E1/0.05 28 ◎ ◎ Example 2 A2/1.5 25 ◎ ◎ Example 3 A3/1.5 20 ◎ ○ Example 4 A4/1.5 34 ◎ ◎ Example 5 A5/1.5 28 ◎ ◎ Example 6 A6/1.5 35 ◎ ◎ Example 7 A7/1.5 27 ◎ ◎ Example 8 A8/1.5 34 ◎ ◎ Example 9 A9/1.5 31 ◎ ◎ Example 10 A10/1.5 25 ◎ ◎ Example 11 A11/1.5 19 ◎ ○ Example 12 A1/0.75
A2/0.75 27 ◎ ◎ Example 13 A2/0.75
A3/0.75 23 ◎ ○ Example 14 A3/0.75
A4/0.75 27 ◎ ◎

Resin (B) Alkali soluble resin (D) Acid generator (A) Sulfur compounds (E) Acid generator decomposition rate (%) Pattern peeling Undercut Type/mass Type/mass Type/mass Type/mass Example 15 B1/60 D1/40 A1/1.5 E1/0.10 28 ◎ ◎ Example 16 E1/0.08 28 ◎ ◎ Example 17 E2/0.05 28 ◎ ◎ Example 18 E3/0.05 28 ◎ ◎ Example 19 E4/0.05 28 ◎ ◎ Example 20 E5/0.05 28 ◎ ◎ Example 21 A2/1.5 E1/0.08 25 ◎ ◎ Example 22 E2/0.05 25 ◎ ◎ Example 23 E3/0.05 25 ◎ ◎ Example 24 E4/0.05 25 ◎ ◎ Example 25 E5/0.05 25 ◎ ◎ Example 26 A4/1.5 E1/0.08 34 ◎ ◎ Example 27 E2/0.05 34 ◎ ◎ Example 28 E3/0.05 34 ◎ ◎ Example 29 E4/0.05 34 ◎ ◎ Example 30 E5/0.05 34 ◎ ◎ Example 31 A1/0.75
A2/0.75 E1/0.05
E2/0.05 27 ◎ ◎ Example 32 A2/0.75
A3/0.75 23 ◎ ○ Example 33 A3/0.75
A4/0.75 27 ◎ ◎ Example 34 B2/60 D1/40 A1/1.5 E1/0.05 28 ◎ ◎ Example 35 B3/60 28 ◎ ◎ Example 36 B8/60 28 ◎ ◎ Example 37 B9/60 28 ◎ ◎ Example 38 B1/60 A4/1.5 34 ◎ ◎ Example 39 B2/60 34 ◎ ◎ Example 40 B3/60 34 ◎ ◎ Example 41 B4/60 34 ◎ ◎ Example 42 B5/60 34 ◎ ◎ Example 43 B6/60 34 ◎ ◎ Example 44 B7/60 34 ◎ ◎ Example 45 B8/60 34 ◎ ◎ Example 46 B9/60 34 ◎ ◎ Example 47 B10/60 34 ◎ ◎

Resin (B) Alkali soluble resin (D) Acid generator (A) Sulfur compounds (E) Acid generator decomposition rate (%) Pattern peeling Undercut Type/mass Type/mass Type/mass Type/mass Example 48 B1/60 D2/40 A1/1.5 E1/0.05 28 ◎ ◎ Example 49 B1/60 D2/40 A4/1.5 34 ◎ ◎ Example 50 B1/40 D1/20
D3/40 A1/1.5 28 ◎ ◎ Example 51 B1/40
B4/20 D1/40 28 ◎ ◎ Example 52 B1/80
B4/20 - 28 ◎ ◎ Example 53 B1/80
B5/20 - 28 ◎ ◎ Example 54 B1/80
B6/20 - 28 ◎ ◎ Example 55 B1/80
B7/20 - 28 ◎ ◎ Example 56 B1/80
B10/20 - 28 ◎ ◎ Example 57 B1/40
B4/20 D1/40 A4/1.5 34 ◎ ◎ Example 58 B1/80
B4/20 - 34 ◎ ◎ Example 59 B1/80
B5/20 - 34 ◎ ◎ Example 60 B1/80
B6/20 - 34 ◎ ◎ Example 61 B1/80
B7/20 - 34 ◎ ◎ Example 62 B1/80
B8/20 - 34 ◎ ◎ Example 63 B1/80
B9/20 - 34 ◎ ◎ Example 64 B1/80
B10/20 - 34 ◎ ◎ Example 65 B1/100 - A1/1.5 28 ◎ ◎

Resin (B) Alkali soluble resin (D) Acid generator (A) Sulfur compounds (E) Acid generator decomposition rate (%) Pattern peeling Undercut Type/mass Type/mass Type/mass Type/mass Comparative Example 1 B1/60 D1/40 A1/1.5 - 28 × ◎ Comparative Example 2 A12/1.5 E1/0.10 2 ○ × Comparative Example 3 A13/1.5 2 ○ × Comparative Example 4 A1/1.5 E6/0.10 28 × ◎ Comparative Example 5 E7/0.10 28 × ◎ Comparative Example 6 E8/0.10 28 × ◎

According to Examples 1 to 65, it was found that a photosensitive composition comprising an acid generator (A) that generates an acid by irradiation with active light or radiation, a resin (B) whose solubility in alkali increases by the action of the acid, a sulfur-containing compound (E) containing a sulfur atom capable of coordinating to a metal layer of a substrate, an acid diffusion inhibitor (F), and an organic solvent (S), wherein the sulfur-containing compound (E) contains a nitrogen-containing heterocyclic compound having a mercapto group, and further satisfying the above [requirement 1] (i.e., the decomposition rate (%) of the acid generator (A) obtained by Steps 1 to 4 is more than 10), can form a resist pattern having a cross-sectional shape in which a large undercut is formed on a substrate having a metal layer on the surface even at a low temperature, and further having excellent adhesion to the substrate so that peeling from the substrate is suppressed. On the other hand, according to Comparative Examples 1 to 6, a photosensitive composition that does not satisfy the above [requirement 1] or a sulfur-containing It was found that a photosensitive composition that does not contain a nitrogen-containing heterocyclic compound having a mercapto group or a tautomer of a nitrogen-containing heterocyclic compound having a mercapto group as a compound (E) has a cross-sectional shape with a large undercut and cannot form a resist pattern having excellent adhesion to a substrate.

Claims (6)

A chemically amplified positive photosensitive composition that forms a pattern that serves as a mold for a process of forming a plated structure on a substrate having a metal layer on the surface,
An acid generator (A) that generates an acid by irradiation with active light or radiation, a resin (B) whose solubility in alkali increases by the action of the acid, a sulfur-containing compound (E) containing a sulfur atom capable of coordinating to the metal layer, an acid diffusion inhibitor (F), and an organic solvent (S).
The above sulfur-containing compound (E) comprises a nitrogen-containing heterocyclic compound having a mercapto group, or a tautomer of the nitrogen-containing heterocyclic compound having the mercapto group,
A chemically amplified positive photosensitive composition satisfying the following [requirement 1].
[Requirement 1]
The decomposition rate (%) of the acid generator (A) obtained by the following processes 1) to 4) is greater than 10.
1) By applying the chemically amplified positive photosensitive composition to a substrate having a copper layer formed on the surface by a sputtering method, a resin film having a thickness of 8.5 μm is formed.
2) The substrate on which the resin film is formed is heated at 140°C for 300 seconds.
3) After the heating, a portion of the resin film is shaved off, the shaved resin film is dissolved in propylene glycol monomethyl ether acetate so that the solid concentration becomes 20 mass%, and then acetonitrile in a mass 15 times the mass of the shaved resin film is added, and the liquid obtained by excluding the precipitate is used as a test solution.
4) After diluting the chemically amplified positive type photosensitive composition with propylene glycol monomethyl ether acetate so that the solid content concentration becomes 20 mass%, adding acetonitrile in a mass 15 times the mass of the solid content of the chemically amplified positive type photosensitive composition, analyzing the liquid from which the precipitate is removed and the test solution, respectively, by liquid chromatography, the decomposition rate (%) of the acid generator (A) represented by the following formula (a) is obtained.
Decomposition rate (%) of acid generator (A) = (1-(x/y))Х100 ···(a)
(In formula (a), x is the content (mass%) of the acid generator (A) in the resin film,
y is the content (mass%) of the acid generator (A) in the solid content of the chemically amplified positive photosensitive composition.) In claim 1,
A chemically amplified positive-type photosensitive composition, wherein the acid generator (A) comprises a coumarin compound in which a coumarin skeleton, which may have a substituent, is bonded with -CO-NR ^a1 -OSO ₂ -R ^a2 (R ^a1 represents a hydrogen atom or a hydrocarbon group, and R ^a2 represents an organic group). In claim 1,
A chemically amplified positive photosensitive composition having a decomposition rate (%) of an acid generator (A) of 25 or more, obtained by the above processes 1) to 4). In claim 1,
The above resin (B) is a chemically amplified positive photosensitive composition containing a polyhydroxystyrene resin (B2). A process for laminating a photosensitive layer comprising a chemically amplified positive photosensitive composition according to any one of claims 1 to 4 on a substrate having a metal layer on the surface,
A process of heating the above photosensitive layer to a temperature of 60℃ or higher and 130℃ or lower,
A process of selectively irradiating the photosensitive layer with active light or radiation after the heating,
A method for manufacturing a mold-attached substrate, comprising a step of developing the photosensitive layer after the above investigation to create a mold for forming a plated structure having a pattern shape. A method for manufacturing a plated article, comprising the step of forming a plated article within the mold by applying plating to the mold attachment substrate manufactured by the method of claim 5.